EP2552713A2 - Use of precipitated silica containing aluminium and 3-acryloxy-propyltriethoxysilane in an isoprenic elastomer composition - Google Patents
Use of precipitated silica containing aluminium and 3-acryloxy-propyltriethoxysilane in an isoprenic elastomer compositionInfo
- Publication number
- EP2552713A2 EP2552713A2 EP11712249A EP11712249A EP2552713A2 EP 2552713 A2 EP2552713 A2 EP 2552713A2 EP 11712249 A EP11712249 A EP 11712249A EP 11712249 A EP11712249 A EP 11712249A EP 2552713 A2 EP2552713 A2 EP 2552713A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- elastomer
- isoprene
- composition
- weight
- precipitated silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 238
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 229920001971 elastomer Polymers 0.000 title claims abstract description 119
- 239000000806 elastomer Substances 0.000 title claims abstract description 119
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 112
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 71
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000004411 aluminium Substances 0.000 title abstract 3
- 239000007822 coupling agent Substances 0.000 claims abstract description 46
- 239000011256 inorganic filler Substances 0.000 claims abstract description 45
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 45
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 27
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 56
- 239000012429 reaction media Substances 0.000 claims description 56
- -1 aluminum compound Chemical class 0.000 claims description 37
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 36
- 239000002535 acidifier Substances 0.000 claims description 32
- 238000004073 vulcanization Methods 0.000 claims description 28
- 244000043261 Hevea brasiliensis Species 0.000 claims description 27
- 229920003049 isoprene rubber Polymers 0.000 claims description 27
- 229920003052 natural elastomer Polymers 0.000 claims description 27
- 229920001194 natural rubber Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229920003051 synthetic elastomer Polymers 0.000 claims description 13
- 229920003244 diene elastomer Polymers 0.000 claims description 12
- 150000001993 dienes Chemical class 0.000 claims description 12
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 239000003223 protective agent Substances 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 239000012936 vulcanization activator Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000001012 protector Effects 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- 239000011148 porous material Substances 0.000 description 24
- 238000005259 measurement Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 239000004115 Sodium Silicate Substances 0.000 description 14
- 229910052911 sodium silicate Inorganic materials 0.000 description 14
- 229940126062 Compound A Drugs 0.000 description 13
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 9
- 229960002447 thiram Drugs 0.000 description 9
- 241001441571 Hiodontidae Species 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 230000002787 reinforcement Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000000518 rheometry Methods 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005485 electric heating Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000012763 reinforcing filler Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 3
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Chemical class [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- IVLBGFRTARNACQ-UHFFFAOYSA-N [3-[3,3-bis(triethoxysilyl)propyltetrasulfanyl]-1-triethoxysilylpropyl]-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)C([Si](OCC)(OCC)OCC)CCSSSSCCC([Si](OCC)(OCC)OCC)[Si](OCC)(OCC)OCC IVLBGFRTARNACQ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 2
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- PVSKJBDIJJFTBV-UHFFFAOYSA-N 1,1-ditert-butyl-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(C(C)(C)C)(C(C)(C)C)C1 PVSKJBDIJJFTBV-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical class COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- MIIBUHIQXLFJFP-UHFFFAOYSA-N 3-methyl-1-[[3-[(3-methyl-2,5-dioxopyrrol-1-yl)methyl]phenyl]methyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1CC1=CC=CC(CN2C(C(C)=CC2=O)=O)=C1 MIIBUHIQXLFJFP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical class NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ZNJLLWWCBTZFSB-UHFFFAOYSA-N OC(CCSSSSCCC(O)[SiH](C)C)[SiH](C)C Chemical compound OC(CCSSSSCCC(O)[SiH](C)C)[SiH](C)C ZNJLLWWCBTZFSB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-XVNBXDOJSA-N [(1e)-buta-1,3-dienyl]benzene Chemical compound C=C\C=C\C1=CC=CC=C1 XZKRXPZXQLARHH-XVNBXDOJSA-N 0.000 description 1
- WYLHTRARPYBQHG-UHFFFAOYSA-N [2-[(2-dimethylsilyl-1-ethoxypropan-2-yl)tetrasulfanyl]-1-ethoxypropan-2-yl]-dimethylsilane Chemical compound CCOCC(C)([SiH](C)C)SSSSC(C)([SiH](C)C)COCC WYLHTRARPYBQHG-UHFFFAOYSA-N 0.000 description 1
- AJUWFXDHBFMLFT-UHFFFAOYSA-N [3-[(3-dimethylsilyl-3-ethoxypropyl)disulfanyl]-1-ethoxypropyl]-dimethylsilane Chemical compound C(C)OC(CCSSCCC([SiH](C)C)OCC)[SiH](C)C AJUWFXDHBFMLFT-UHFFFAOYSA-N 0.000 description 1
- GPZLQABYHZCVJJ-UHFFFAOYSA-N [3-[3,3-bis(triethoxysilyl)propyldisulfanyl]-1-triethoxysilylpropyl]-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)C([Si](OCC)(OCC)OCC)CCSSCCC([Si](OCC)(OCC)OCC)[Si](OCC)(OCC)OCC GPZLQABYHZCVJJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007907 direct compression Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011975 tartaric acid Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000007979 thiazole derivatives Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
Definitions
- the invention relates to the joint use, in elastomer compositions (s) comprising an isoprene elastomer, such as natural rubber, of a particular reinforcing inorganic filler and a particular inorganic filler - elastomer coupling agent.
- elastomer compositions comprising an isoprene elastomer, such as natural rubber, of a particular reinforcing inorganic filler and a particular inorganic filler - elastomer coupling agent.
- the elastomeric articles are generally subjected to various constraints, for example such as a temperature variation, a significant frequency stress variation in dynamic regime, a significant static stress and / or fatigue in significant bending in dynamic mode.
- Such articles are, for example, tires, shoe soles, floor coverings, conveyor belts, power transmission belts, hoses, seals, especially appliance seals, role of engine vibration extractors either with metal reinforcements or with a hydraulic fluid inside the elastomer, cable sheaths, cables, ropeway rollers.
- a coupling agent also called a binding agent
- a binding agent whose function is, in particular, to providing the connection between the surface of the inorganic filler particles (for example a precipitated silica) and the elastomer (s), while facilitating the dispersion of this inorganic filler within the elastomeric matrix.
- inorganic filler-elastomer coupling agent is understood to mean an agent capable of establishing a sufficient chemical and / or physical connection between the inorganic filler and the elastomer.
- Such a coupling agent at least bifunctional, has for example as simplified general formula "N-V-M", in which:
- N represents a functional group ("N" function) capable of binding physically and / or chemically to the inorganic filler, such a bond being able to be established, for example, between a silicon atom of the coupling agent and the groups hydroxyl (OH) on the surface of the inorganic filler (for example surface silanols when it is silica);
- M represents a functional group ("M" function) capable of binding physically and / or chemically to the elastomer, in particular via a suitable atom or group of atoms (for example an atom of sulfur);
- - V represents a group (divalent / hydrocarbon) for connecting "N" and "M”.
- the coupling agents should not be confused with simple inorganic filler agents which, in a known manner, may have the "N" function active with respect to the inorganic filler but lack the "M” function. active with respect to the elastomer.
- Coupling agents in particular (silica-elastomer), have been described in numerous documents of the state of the art, the best known being (poly) sulphide silanes, in particular (poly) sulphidized alkoxysilanes.
- (Poly) sulfurized silanes mention may in particular be made of bis-triethoxysilylpropyl tetrasulfide (abbreviated to TESPT), which is generally still considered today as a product providing, for vulcanizates comprising an inorganic filler as a reinforcing filler, such as silica, a very good, or even the best, compromised in terms of safety roasting, ease of implementation and strengthening power.
- TESPT bis-triethoxysilylpropyl tetrasulfide
- precipitated silica in particular highly dispersible silica and a silane (or organosilic compound functionalized) polysulfide in a modified elastomer composition (s) allowed the development of the "green tire” for passenger vehicles (Light vehicles).
- This combination achieved a wear resistance performance comparable to that of carbon black-reinforced elastomer blends, while significantly improving rolling resistance (resulting in lower fuel consumption). fuel), and grip on wet ground.
- an inorganic filler such as silica in tires for trucks, tires which are obtained from compositions based on isoprene elastomer (s), mainly natural rubber.
- the object of the present invention is to propose in particular the combination for elastomer compositions comprising a diene elastomer, such as natural rubber, with a particular coupling agent with a particular reinforcing inorganic filler, this combination consisting of as an alternative to the use of known coupling agents with known reinforcing inorganic fillers, this combination further providing said elastomer compositions with a very favorable property compromise. satisfactory, especially in terms of their rheological properties, mechanical and / or dynamic, including hysteresis.
- it allows an improvement in the wear resistance and hysteresis / reinforcement compromise.
- the elastomer compositions obtained preferably have very good adhesion to both the reinforcing inorganic filler used and the substrates to which they are subsequently applied.
- the invention relates in its first object to the use in an elastomer composition (s), comprising at least one isoprene elastomer:
- 3-acryloxypropyltriethoxysilane (or ⁇ -acryloxypropyltriethoxysilane), as an inorganic filler-elastomer coupling agent.
- Said precipitated silica used generally has an aluminum content of at most 7.0% by weight, preferably at most 5.0% by weight, in particular at most 3.5% by weight, for example at most 3.0% by weight.
- its aluminum content is between 0.75 and 4.0% by weight, even more preferably between 0.8 and 3.5% by weight, in particular between 0.9 and 3.2% by weight. weight, especially between 0.9 and 2.5% by weight or between 1.0 and 3.1% by weight. It is for example between 1.0 and 3.0% by weight, or even between 1.0 and 2.0% by weight.
- the amount of aluminum can be measured by any suitable method, for example by ICP-AES ("Inductively Coupled Plasma - Atomic Emission Spectroscopy") after dissolution in water in the presence of hydrofluoric acid.
- ICP-AES Inductively Coupled Plasma - Atomic Emission Spectroscopy
- Aluminum is, in general, essentially on the surface of the precipitated silica.
- aluminum may be present in both tetrahedral, octahedral and pentahedral form, particularly in the form of tetrahedral and in octahedral form, in the precipitated silica used in the invention, it is preferably essentially in tetrahedral form (more than 50%, in particular at least 90%, especially at least 95% by number, of the aluminum species are then in tetrahedral form); the links are then rather essentially of the SiOAI type.
- Said precipitated silica containing aluminum used in the invention is advantageously highly dispersible, that is to say that in particular it has an ability to deagglomerate and to disperse in a very important polymeric matrix, in particular observable by electron or optical microscopy, on thin sections.
- the precipitated silica used according to the invention has a CTAB specific surface area of between 70 and 240 m 2 / g.
- This may be between 70 and 100 m 2 / g, for example between 75 and 95 m 2 / g.
- its CTAB surface area is between 100 and 240 m 2 / g, in particular between 140 and 200 m 2 / g.
- the precipitated silica used according to the invention has a BET specific surface area of between 70 and 240 m 2 / g.
- This can be between 70 and 100 m 2 / g, for example between 75 and
- its BET surface area is between 100 and 240 m 2 / g, in particular between 140 and 200 m 2 / g.
- the CTAB specific surface area is the external surface, which can be determined according to the NF T 45007 method (November 1987).
- the BET surface area can be measured according to the method of BRUNAUER - EMMETT - TELLER described in "The Journal of the American Chemical Society", vol. 60, page 309 (1938) and corresponding to standard NF T 45007 (November 1987).
- the dispersibility (and disagglomeration) ability of the precipitated silica implemented according to the invention can be assessed by means of the following test, by a granulometric measurement (by laser diffraction) carried out on a Silica suspension previously deagglomerated by ultra-sonification (breaking objects from 0.1 to a few tens of microns).
- Ultrasonic deagglomeration is carried out using a VIBRACELL BIOBLOCK (750 W) sonicator equipped with a 19 mm diameter probe.
- the particle size measurement is carried out by laser diffraction on a SYMPATEC granulomer, using the Fraunhofer theory.
- a pillbox (height: 6 cm and diameter: 4 cm)
- 2 grams of silica are weighed and the mixture is made up to 50 grams by addition of deionized water: a 4% aqueous suspension of silica is thus obtained which is homogenized during 2 minutes by magnetic stirring.
- the deagglomeration is then carried out under ultrasound as follows: the probe being immersed over a length of 4 cm, it is put into action for 5 minutes and 30 seconds at 80% of its nominal power (amplitude).
- the particle size measurement is then carried out by introducing into the vat of the granulometer a volume V (expressed in ml) of the homogenized suspension necessary to obtain an optical density of about 20.
- the value of the median diameter 050 obtained according to this test is even lower than the silica has a high ability to deagglomerate.
- a disaggregation factor F D is given by the equation:
- This disaggregation factor F D is indicative of the rate of particles smaller than 0.1 ⁇ which are not detected by the granulometer. This factor is all the higher as the silica has a high deagglomeration ability.
- the precipitated silica containing aluminum used according to the invention has a median diameter ⁇ 50 , after deagglomeration with ultrasound, less than 5 ⁇ , in particular less than 4 ⁇ , in particular less than 3.5. ⁇ , for example less than 3 ⁇ .
- the DOP oil uptake of the precipitated aluminum-containing silica used according to the invention may be less than 300 ml / 100 g, for example between 200 and 295 ml / 100 g. DOP oil uptake can be determined according to ISO 787/5 by using dioctylphthalate.
- One of the parameters of the precipitated silica implemented in the invention may reside in the distribution, or distribution, of its pore volume, and in particular in the distribution of the pore volume which is generated by pores with diameters less than or equal to 400 ⁇ . .
- This latter volume corresponds to the useful pore volume of the charges used in the reinforcement of the elastomers.
- this precipitated silica may have, in a first variant, a porous distribution (and this may be illustrated by the analysis of porograms) such as the pore volume generated by the pores whose diameter is between 175 and 275 ⁇ (V2) represents less than 50% of the pore volume generated by pores with diameters less than or equal to 400 ⁇ (V1), it may also be advantageous to use, in a second variant, a precipitated silica having a porous distribution such as the porous volume generated by the pores whose diameter is between 175 and 275 ⁇ (V2) represents at least 50% (for example between 50 and 60%) of the pore volume generated by pores with diameters less than or equal to 400 ⁇ (V1).
- a porous distribution such as the porous volume generated by the pores whose diameter is between 175 and 275 ⁇ (V2) represents at least 50% (for example between 50 and 60%) of the pore volume generated by pores with diameters less than or equal to 400 ⁇ (V1).
- porous volumes and pore diameters are measured by mercury porosimetry (Hg), using a MICROMERITICS Autopore 9520 porosimeter, and are calculated by the WASHBURN relation with a theta contact angle of 130 ° and a voltage.
- superficial gamma equal to 484 Dynes / cm (DIN 66133 standard).
- the pH of the precipitated silica used according to the invention is generally between 6.3 and 8.0, for example between 6.3 and 7.6.
- the pH is measured according to the following method deriving from the ISO 787/9 standard (pH of a suspension at 5% in water):
- Apparatus - calibrated pH meter (reading accuracy at 1 / 100th)
- the physical state in which the precipitated silica to be used according to the invention is present may be arbitrary, that is to say that it may be, for example, in the form of microbeads (substantially spherical beads), powder or granules.
- substantially spherical beads of average size of at least 80 ⁇ m, preferably at least 150 ⁇ m, in particular between 150 and 270 ⁇ m; this average size is determined according to standard NF X 1 1507 (December 1970) by dry sieving and determination of the diameter corresponding to a cumulative refusal of 50%.
- It may be in the form of a powder of average size of at least 3 ⁇ , in particular at least 10 ⁇ , preferably at least 15 ⁇ .
- the precipitated silica having an aluminum content greater than 0.5% by weight, used according to the invention may have:
- CTAB specific surface area of between 140 and 200 m 2 / g
- the precipitated silica may for example have a porous distribution such that the pore volume generated by the pores whose diameter is between 175 and 275 ⁇ (V 2) represents at least 50%, for example between 50 and 60% of the pore volume generated by pores with diameters less than or equal to 400 ⁇ (V1).
- the precipitated silica having an aluminum content greater than 0.5% by weight, used according to the invention may exhibit:
- CTAB specific surface area of between 140 and 200 m 2 / g
- V 2 a porous distribution such that the pore volume constituted by the pores whose diameter is between 175 and 275 ⁇ (V 2) represents less than 50% of the pore volume constituted by pores with diameters less than or equal to 400 ⁇ (V 1), and
- ⁇ 50 a median diameter ⁇ 50 , after deagglomeration with ultrasound, less than 5 ⁇ .
- the precipitated silica having an aluminum content greater than 0.5% by weight, used according to the invention may exhibit:
- CTAB specific surface area of between 140 and 200 m 2 / g
- the pore volume constituted by the pores whose diameter is between 175 and 275 ⁇ (V 2) represents at least 50%, for example between 50 and 60%, of the pore volume constituted by pores with diameters less than or equal to 400 ⁇ (V1), and
- ⁇ 50 a median diameter ⁇ 50 , after deagglomeration with ultrasound, less than 5 ⁇ .
- the precipitated silica implemented in the context of the invention may be prepared for example by a process as described in patent applications EP-A-0762992, EP-A-0762993, EP-A-0983966, EP-A -1355856.
- the precipitated silica employed in the invention can be obtained by a preparation process comprising the precipitation reaction between a silicate and an acidifying agent whereby a suspension of precipitated silica is obtained, followed by separation and drying. of this suspension, in which:
- said method comprising one of the following three operations (a), (b) or (c):
- step (iii) is carried out by simultaneously adding to the reaction medium acidifying agent, a silicate and at least one compound B of aluminum.
- this preparation process is a precipitation silica synthesis process, that is to say that it is made to act, under particular conditions, an acidifying agent with a silicate.
- the acidifying agent used is a strong mineral acid such as sulfuric acid, nitric acid or hydrochloric acid, or an organic acid such as acetic acid, formic acid or carbonic acid.
- the acidifying agent may be diluted or concentrated; its normality can be between 0.4 and 36 N, for example between 0.6 and 1.5 N.
- the acidifying agent is sulfuric acid
- its concentration may be between 40 and 180 g / l, for example between 60 and 130 g / l.
- silicate any current form of silicates such as metasilicates, disilicates and advantageously an alkali metal silicate, in particular sodium or potassium silicate.
- the silicate may have a concentration (expressed as SiO 2 ) of between 40 and 330 g / l, for example between 60 and 300 g / l.
- sulfuric acid is used as acidifying agent and sodium silicate as silicate.
- sodium silicate In the case where sodium silicate is used, it generally has a weight ratio SiO 2 / Na 2 O of between 2.5 and 4, for example between 3.1 and 3.8.
- reaction of the silicate with the acidifying agent is in a specific manner according to the following steps.
- a stock which comprises silicate and an electrolyte (step (i)).
- the amount of silicate present in the initial stock is advantageously only a part of the total amount of silicate involved in the reaction.
- electrolyte is understood here in its normal acceptation, that is to say that it means any ionic or molecular substance which, when in solution, decomposes or dissociates to form ions or particles. loaded.
- electrolyte mention may be made of a salt of the group of alkali and alkaline earth metal salts, in particular the salt of the starting silicate metal and of the acidifying agent, for example sodium chloride in the case of the reaction of a sodium silicate with hydrochloric acid or, preferably, sodium sulfate in the case of the reaction of a sodium silicate with sulfuric acid.
- the concentration of electrolyte in the initial stock is (greater than 0 g / L and) less than 17 g / l, for example less than 14 g / l.
- the silicate concentration (expressed in SiO 2 ) in the initial stock is (greater than 0 g / L and) less than 100 g / L; preferably, this concentration is less than 90 g / l, especially less than 85 g / l.
- the second step consists in adding the acidifying agent to the stock base composition described above (step (ii)).
- This addition which causes a correlative drop in the pH of the reaction medium, is carried out until a pH value of at least 7, generally between 7 and 8, is reached.
- step (Ni)) of acidifying agent and silicate is carried out.
- This preparation method comprises one of the three operations (a), (b) or (c) mentioned above, that is to say:
- a basic agent is added to the reaction medium, preferably until a pH value of the reaction medium of between 6.5 and 10 is obtained, in particular between 7.2 and 8.6, and then
- acidifying agent is added to the reaction medium, preferably until a pH value of the reaction medium of between 3 and 5, in particular between 3.4 and 4.5, is obtained.
- Step (v) may be performed simultaneously or, preferably, after step (iv).
- the reaction medium may be cured, this curing may for example last from 1 to 60 minutes, in particular from 3 to 30 minutes.
- step (iii) and step (iv) it may be desirable, between step (iii) and step (iv), and in particular before said optional maturing, to add to the reaction medium an additional amount of acidifying agent.
- This addition is generally carried out until a pH value of the reaction medium of between 3 and 6.5, in particular between 4 and 6, is obtained.
- the acidifying agent used during this addition is generally identical to that used in steps (ii), (iii) and (vi) of the first variant of the process.
- Ripening of the reaction medium is usually carried out between step (v) and step (vi), for example for 2 to 60 minutes, in particular for 5 to 45 minutes.
- a ripening of the reaction medium is most often carried out after step (vi), for example for 2 to 60 minutes, in particular for 5 to 30 minutes.
- the basic agent used in step (v) may be an ammonia solution or, preferably, a solution of sodium hydroxide (or sodium hydroxide).
- a step (iv) which consists in adding to the reaction medium simultaneously a silicate and at least one compound A of aluminum.
- step (iii) by step (iv), which in fact means that step (iii) and step (iv) then form only one step, the compound A of aluminum then playing the role of acidifying agent.
- step (iv) is generally carried out in such a way that the pH value of the reaction medium is constantly equal (within +/- 0.1) to that reached at the end of the step ( iii) or step (ii).
- step (iv) it is possible, after the simultaneous addition of step (iv), to ripen the reaction medium, which curing may for example last from 2 to 60 minutes, in particular from 5 to 30 minutes.
- step (iv) it may be desirable, after step (iv), and in particular after this optional ripening, to add to the reaction medium an additional quantity of acidifying agent.
- This addition is generally carried out until a pH value of the reaction medium of between 3 and 6.5, in particular between 4 and 6, is obtained.
- the acidifying agent used during this addition is generally identical to that used in step (ii) of the second variant of the process. Ripening of the reaction medium is usually carried out after this addition of acidifying agent, for example for 1 to 60 minutes, in particular for 3 to 30 minutes.
- the aluminum compound A used in the preparation process is generally an organic or inorganic salt of aluminum.
- organic salt mention may be made in particular of carboxylic or polycarboxylic acid salts, such as the salts of acetic, citric, tartaric or oxalic acid.
- inorganic salt mention may in particular be made of halides and oxyhalides (such as chlorides, oxychlorides), nitrates, phosphates, sulphates and oxysulphates.
- compound A of aluminum may be used in the form of a solution, generally aqueous.
- Aluminum compound A is preferably used as aluminum compound A.
- a step (iii) which consists in adding to the reaction medium simultaneously with the acidifying agent, a silicate and at least one compound B of aluminum.
- step (iii) it may be desirable, after step (iii), to add to the reaction medium an additional amount of acidifying agent. This addition is generally done until a pH value of the reaction medium of between 3 and 6.9, in particular between 4 and 6.6, is obtained.
- the acidifying agent used during this addition is generally identical to that used in steps (ii) and (iii). Ripening of the reaction medium is usually carried out after this addition of acidifying agent, for example for 1 to 60 minutes, in particular for 3 to 30 minutes.
- the compound B of the aluminum employed in the third variant is, in general, an alkali metal aluminate, in particular potassium or, preferably, sodium.
- the temperature of the reaction medium is generally between 70 and 98 ° C.
- the reaction is carried out at a constant temperature of between 75 and 96 ° C.
- the end-of-reaction temperature is higher than the reaction start temperature: thus, the temperature at the start of the reaction is preferably maintained between 70 and 96 ° C., and then the temperature is raised. in a few minutes, preferably to a value between 80 and 98 ° C, the value at which it is maintained until the end of the reaction; the operations (a) or (b) are thus usually performed at this constant temperature value.
- this separation comprises a filtration (followed by a washing if necessary) and a disintegration, said disintegration can be then (preferably in the case of the first two variants mentioned, possibly in the case of the third variant) carried out in the presence at least one aluminum compound B and, optionally, in the presence of an acidifying agent as described above (in the latter case, the compound B of the aluminum and the acidifying agent are advantageously added simultaneously ).
- the disintegration operation which can be carried out mechanically, for example by passing the filter cake in a colloidal or ball mill, notably makes it possible to lower the viscosity of the suspension to be dried (in particular to be atomized) subsequently.
- the aluminum compound B is usually different from the aluminum compound A mentioned above and generally consists of an alkali metal aluminate, especially potassium or, preferably, sodium aluminate.
- the amounts of aluminum compounds A and B used in this preparation process are such that the precipitated silica obtained has more than 0.5% by weight of aluminum, and in particular a preferred amount of aluminum as mentioned above. high.
- the separation carried out in this process usually comprises filtration (with washing if necessary) carried out using any suitable method, for example by means of a belt filter, a vacuum filter or, preferably, a filter. a filter press.
- the precipitated silica suspension thus recovered (filter cake) is then dried.
- this suspension must present immediately before drying a dry matter content of at most 24% by weight, preferably at most 22% by weight.
- This drying can be done by any means known per se.
- the drying is done by atomization.
- any suitable type of atomizer may be used, such as a turbine, nozzle, liquid pressure or two-fluid atomizer.
- a turbine nozzle
- liquid pressure two-fluid atomizer.
- the precipitated silica that can then be obtained is usually in the form of substantially spherical beads.
- the precipitated silica that can then be obtained is generally in the form of a powder.
- the precipitated silica that may then be obtained may be in the form of a powder.
- the dried product in particular by a turbine atomizer or milled as indicated above may optionally be subjected to an agglomeration step, which consists, for example, of a direct compression, a wet-path granulation (that is, with the use of a binder such as water, silica suspension, etc.), extrusion or, preferably, dry compaction.
- agglomeration step which consists, for example, of a direct compression, a wet-path granulation (that is, with the use of a binder such as water, silica suspension, etc.), extrusion or, preferably, dry compaction.
- deaerate operation also called pre-densification or degassing
- the precipitated silica that can then be obtained by this agglomeration step is generally in the form of granules.
- the 3-acryloxypropyltriethoxysilane (or ⁇ -acryloxypropyltriethoxysilane) used in the invention as an inorganic filler-elastomer coupling agent can be prepared by a process as described in US-A-3179612, starting from US Pat. allyl acrylate and triethoxysilane.
- the aluminum-containing precipitated silica used according to the present invention as the reinforcing inorganic filler and the 3-acryloxypropyltriethoxysilane used according to the present invention as the reinforcing inorganic filler-elastomer coupling agent may be mixed together prior to their use.
- a first variant is that the 3-acryloxypropyltriethoxysilane is not grafted onto said precipitated silica;
- a second variant is that the 3-acryloxypropyltriethoxysilane is grafted onto said precipitated silica which will thus be "pre-coupled” before mixing with the elastomer composition (s).
- this solid support that can be for example, carbon black or, preferably, precipitated aluminum-containing silica used in accordance with the present invention.
- the elastomer compositions in which 3-acryloxypropyltriethoxysilane is used according to the invention may contain at least one precipitated silica covering agent used as a reinforcing filler.
- This covering agent is capable, in a known manner, of improving the processability of the elastomer compositions in the green state.
- Such a coating agent may consist, for example, of an alkylalkoxysilane (in particular an alkyltriethoxysilane), a polyol, a polyether (in particular a polyethylene glycol), a polyetheramine, a primary, secondary or tertiary amine (in particular a trialkanol amine), a ⁇ , ⁇ -dihydroxylated polydimethylsiloxane or an ⁇ , ⁇ -diamine polydimethylsiloxane.
- an alkylalkoxysilane in particular an alkyltriethoxysilane
- a polyol in particular a polyethylene glycol
- a polyetheramine in particular a polyethylene glycol
- a polyetheramine in particular a primary, secondary or tertiary amine (in particular a trialkanol amine)
- This coating agent may optionally be mixed with said precipitated silica and 3-acryloxypropyltriethoxysilane prior to their use.
- the elastomer compositions in which the 3-acryloxypropyltriethoxysilane and the precipitated silica described above are used according to the invention may optionally comprise at least one other inorganic filler-elastomer coupling agent, in particular a sulphurised silane. or polysulfide.
- TESPD bis-triethoxysilylpropyl disulphide
- TESPT bis-triethoxysilylpropyl tetrasulfide
- MESPD bis-monoethoxydimethylsilylpropyl disulfide
- MESPT bis-monoethoxydinethylsilylpropyl tetrasulfide
- MESiPrT bis-monoethoxydimethylsilylisopropyl tetrasulfide
- said elastomer compositions (s) do not contain any other inorganic filler-elastomer coupling agent other than 3-acryloxypropyltriethoxysilane.
- the use according to the invention may optionally be carried out in the presence of a free radical initiator (for example from 0.02 to 5%, in particular from 0.05 to 0.5%, by weight relative to the amount in question. weight of elastomer (s)), that is to say of a compound (especially organic compound) susceptible, in particular following energetic activation, to generate free radicals in situ, in its surrounding environment, in this case in the elastomer (s).
- a free radical initiator for example from 0.02 to 5%, in particular from 0.05 to 0.5%, by weight relative to the amount in question. weight of elastomer (s)
- the initiator of free radicals is here an initiator of the type with thermal initiation, that is to say that the energy supply, for the creation of free radicals, is in thermal form. Its decomposition temperature should generally be below 180 ° C, in particular below 160 ° C.
- organic peroxides for example chosen from the group consisting of organic peroxides, organic hydroperoxides, azido compounds, bis (azo) compounds, peracids, peresters or a mixture of at least two of these compounds.
- organic peroxide for example benzoyl peroxide, acetyl peroxide, lauryl peroxide, peroxide of 1, 1 bis (t-butyl) -3,3,5-trimethylcyclohexane, peroxide optionally being placed on a solid support, such as calcium carbonate.
- the invention is implemented in the absence of any free radical initiator.
- the elastomer composition (s) employed in the invention may advantageously not comprise other elastomers than the isoprene elastomer (s) it contains.
- it may optionally comprise at least one isoprene elastomer (for example natural rubber) and at least one diene elastomer other than isoprene, the amount of isoprene elastomer (s) relative to the total amount of elastomer (s) then being preferably greater than 50% (generally less than 99.5%, and for example between 70 and 99%) by weight.
- the elastomer composition (s) used according to the invention generally comprises at least one isoprene elastomer (natural or synthetic) chosen from:
- conjugated diene monomers other than isoprene, having from 4 to 22 carbon atoms, such as, for example, butadiene-1,3, 2,3-dimethyl-1,3-butadiene, 2-chloro butadiene-1,3 (or chloroprene), 1-phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene;
- aromatic vinyl monomers having 8 to 20 carbon atoms, such as, for example, styrene, ortho-, meta- or paramethylstyrene, the commercial "vinyl-toluene" mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes vinylmesitylene, divinylbenzene, vinylnaphthalene;
- vinyl nitrile monomers having 3 to 12 carbon atoms, such as, for example, acrylonitrile, methacrylonitrile;
- acrylic ester monomers derived from acrylic acid or methacrylic acid with alkanols having from 1 to 12 carbon atoms such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate;
- copolymeric polyisoprenes containing between 20 and 99% by weight of isoprenic units and between 80 and 1% by weight of diene units, aromatic vinyls, vinyl nitriles and / or acrylic esters, and consisting, for example, in poly (isoprene-butadiene) ), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene);
- (6) a mixture containing more than 50% (preferably less than 99.5%, and for example 70-99%) by weight of the aforementioned elastomer (1) or (3) and less than 50% (preferably more than 0.5%, and for example between 1 and 30% by weight of one or more diene elastomers other than isoprenic.
- diene elastomer other than isoprene is meant in a manner known per se including: homopolymers obtained by polymerization of one of the conjugated diene monomers defined above in (2.1), such as polybutadiene and polychloroprene; copolymers obtained by copolymerization of at least two of the abovementioned conjugated dienes (2.1) with one another or by copolymerization of one or more of the abovementioned conjugated dienes (2.1) with one or more unsaturated monomers mentioned above (2.2), (2.3) and / or or (2.4), such as poly (butadiene-styrene) and poly (butadiene-acrylonitrile); ternary copolymers obtained by copolymerization of ethylene, a ⁇ -olefin having from 3 to 6 carbon atoms with a non-conjugated diene monomer containing from 6 to 12 carbon atoms, for example elastomers obtained from ethylene propylene
- the elastomer composition (s) comprises at least one isoprene elastomer chosen from:
- (6) a mixture containing more than 50% (preferably less than 99.5%, and for example 70-99%) by weight of the aforementioned elastomer (1) or (3) and less than 50% (preferably more than 0.5%, and for example from 1 to 30% by weight of non-isoprene diene elastomer consisting of polybutadiene, polychloroprene, polybutadiene-styrene, polybutadiene-acrylonitrile or a terpolymer (ethylene - propylene - nonconjugated monomeric diene).
- non-isoprene diene elastomer consisting of polybutadiene, polychloroprene, polybutadiene-styrene, polybutadiene-acrylonitrile or a terpolymer (ethylene - propylene - nonconjugated monomeric diene).
- the elastomer composition (s) comprises at least one isoprene elastomer chosen from: (1) homopolymeric synthetic polyisoprenes; (3) natural rubber; (5) a mixture of the aforementioned elastomers (1) and (3); (6) a mixture containing more than 50% (preferably less than 99.5%, and for example 70-99%) by weight of the aforementioned elastomer (1) or (3) and less than 50% (preferably more than 0.5%, for example from 1 to 30% by weight of diene elastomer other than isoprene, consisting of polybutadiene or polybutadiene-styrene.
- isoprene elastomer chosen from: (1) homopolymeric synthetic polyisoprenes; (3) natural rubber; (5) a mixture of the aforementioned elastomers (1) and (3); (6) a mixture containing more than 50% (preferably less than 99.5%, and for example 70-99%) by weight of the aforementioned elastomer (1) or (3) and less than 50% (
- the elastomer composition (s) comprises as isoprene elastomer at least natural rubber, or even only natural rubber.
- the elastomer composition (s) comprises as elastomer (s) only natural rubber.
- the elastomer composition (s) used according to the invention also comprises all or part of the other constituents and auxiliary additives usually employed in the field of elastomeric compositions.
- vulcanizing agents for example sulfur or a sulfur-donor compound (such as a thiuram derivative)
- vulcanization accelerators for example a guanidine derivative or a thiazole derivative
- vulcanization activators for example, stearic acid, zinc stearate and zinc oxide, which may optionally be introduced in a fractional manner during the preparation of the composition
- carbon protective agents (especially antioxidants and / or antiozonants, such as, for example, N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine), antireversions (such as for example hexamethylene-1,6-bis (thiosulfate), 1,3-bis (citraconimidomethyl) benzene), plasticizers.
- vulcanizing agents for example sulfur or a sulfur-donor compound (such as a thiuram derivative)
- vulcanization accelerators for example a guanidine derivative or a thiazo
- the combined use according to the invention of the aluminum-containing precipitated silica described in the preceding discussion and of 3-acryloxypropyltriethoxysilane can be done more particularly in shoe soles, floor coverings, gas barriers. , fire-retardant materials, ropeway rollers, appliance joints, liquid or gas line joints, braking system joints, hoses, ducts (especially cable ducts), cables, engine supports, conveyor belts, transmission belts or, preferably, tires (in particular tire treads), advantageously in tires for heavy goods vehicles, in particular for trucks.
- the elastomer composition (s) obtained according to the use according to the invention contains an effective amount of 3-acryloxypropyltriethoxysilane.
- the elastomer compositions resulting from the invention may comprise (parts by weight), per 100 parts of isoprene elastomer (s): 10 to 200 parts, in particular 20 to 150 parts, especially 30 to 10 parts, for example 30 to 75 parts, of precipitated silica containing aluminum as described above and used as reinforcing inorganic filler;
- 1 to 20 parts in particular 2 to 20 parts, especially 2 to 12 parts, for example 2 to 10 parts, of 3-acryloxypropyltriethoxysilane used as reinforcing inorganic filler-elastomer coupling agent.
- the amount of 3-acryloxypropyltriethoxysilane used is determined so that it generally represents 1 to 20%, in particular 2 to 15%, for example 4 to 12%, by weight relative to the amount used of the precipitated silica containing aluminum as described above.
- the total amounts of coupling agents + optional coating agent are identical to those mentioned above when using, in addition to the coupling agent (3-acryloxypropyltriethoxysilane) used according to the invention.
- another coupling agent especially sulphide or polysulfide
- a covering agent especially sulphide or polysulfide
- the present invention has the second object the elastomer compositions (s) described above, and thus comprising:
- reinforcing inorganic filler and said inorganic filler-elastomer coupling agent are as defined above according to the first subject of the invention, that is to say that said reinforcing inorganic filler is precipitated silica containing aluminum as described in the above discussion and said inorganic filler-elastomer coupling agent is 3-acryloxypropyltriethoxysilane.
- the elastomer compositions according to the invention may be prepared according to any conventional two-phase procedure.
- a first phase (called non-productive) is a thermomechanical work phase at high temperature. It is followed by a second mechanical working phase (so-called productive) at temperatures generally below 110 ° C. in which the vulcanization system is introduced.
- the invention taken in its second subject, relates to elastomer compositions (s) both in the raw state (that is to say before cooking) and in the cooked state (that is to say before cooking). say after crosslinking or vulcanization).
- the elastomer compositions according to the invention can be used to manufacture finished or semi-finished articles comprising said compositions.
- the present invention thus has for third object articles comprising at least one elastomer composition (s) as defined above, these articles consisting of shoe soles, floor coverings, gas barriers, flame retardant materials , ropeway rollers, appliance gaskets, liquid or gas line joints, braking system seals, hoses (hoses), ducts (especially cable ducts), cables, motor mounts, conveyor belts, transmission belts, or, preferably, tires (especially tire treads), advantageously tires for heavy goods vehicles, in particular for trucks.
- elastomer composition s
- these articles consisting of shoe soles, floor coverings, gas barriers, flame retardant materials , ropeway rollers, appliance gaskets, liquid or gas line joints, braking system seals, hoses (hoses), ducts (especially cable ducts), cables, motor mounts, conveyor belts, transmission belts, or, preferably, tires (especially tire treads), advantageously tires for heavy goods vehicles, in particular for trucks.
- compositions comprising at least one reinforcing inorganic filler for elastomer and at least one inorganic filler-elastomer coupling agent, characterized in that said reinforcing inorganic filler and said coupling agent charge inorganic - elastomer are as defined above according to the first subject of the invention, that is to say that said reinforcing inorganic filler is precipitated silica containing aluminum as described in the above disclosure and said inorganic filler-elastomer coupling agent is 3-acryloxypropyltriethoxysilane.
- compositions or kits
- compositions may further comprise at least one covering agent for said precipitated silica used as a reinforcing filler.
- compositions find a particularly advantageous application in elastomer compositions (s) comprising at least one isoprene elastomer, especially in those comprising (for example as sole elastomer) natural rubber.
- a preferred application lies in their use in tires (especially tire treads), advantageously in tires for heavy goods vehicles, in particular for trucks.
- aqueous sodium silicate having a weight ratio SiO 2 / Na 2 O equal to 3.47 and a density at 20 ° C. equal to 1. 230.
- the silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l.
- the mixture is then heated to a temperature of 83 ° C while maintaining stirring. 17470 g of dilute sulfuric acid having a density at 20 ° C. of 1.050 are then introduced in order to obtain a pH value (measured at its temperature) of 8.
- the temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
- the total reaction time is 85 minutes.
- a slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
- the cake obtained is then fluidized by mechanical and chemical action (simultaneous addition of sulfuric acid and a quantity of sodium aluminate corresponding to an Al / SiO 2 weight ratio of 0.3%). After this disintegration operation, the resulting slurry, with a pH equal to 6.5 and a loss on ignition equal to 85.5% (thus a solids content of 14.5% by weight), is spray-dried.
- the characteristics of the silica obtained A1 in the form of powder are then as follows:
- SiO 2 / Na 2 O equal to 3.47 and a density at 20 ° C equal to 1. 230.
- the silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l.
- the mixture is then heated to a temperature of 83 ° C while maintaining stirring.
- 18050 g of dilute sulfuric acid having a density at 20 ° C. of 1.050 are then introduced in order to obtain in the reaction medium a pH value (measured at its temperature) equal to 8.
- the temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
- This step is followed by a simultaneous addition of 4520 g of a solution of aluminum sulphate with a density of 20 ° C. equal to 1.056 and of 2260 g of aqueous sodium silicate of the type described above in such a way that the pH of the reaction medium, during the period of introduction, is constantly equal to 8.0 ⁇ 0.1.
- the total reaction time is 85 minutes.
- a slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
- the cake obtained is then fluidized by mechanical and chemical action (simultaneous addition of sulfuric acid and a quantity of sodium aluminate corresponding to an Al / SiO 2 weight ratio of 0.3%). After this disintegration operation, the resulting slurry, with a pH equal to 6.5 and a loss on ignition equal to 86.0% (thus a solids content of 14.0% by weight), is spray-dried.
- the characteristics of the silica obtained P1 in powder form are then as follows:
- the silica P1 is subjected to the disagglomeration test as defined above in the description.
- the silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l.
- the mixture is then heated to a temperature of 83 ° C while maintaining stirring. 17180 g of dilute sulfuric acid having a density at 20 ° C. of 1.050 are then introduced in order to obtain in the reaction medium a pH value (measured at its temperature) equal to 8.
- the temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
- the total reaction time is 85 minutes.
- a slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
- the cake obtained is then fluidized by mechanical and chemical action (simultaneous addition of sulfuric acid and a quantity of sodium aluminate corresponding to an Al / SiO 2 weight ratio of 0.3%). After this disintegration operation, the resulting slurry, with a pH equal to 6.5 and a loss on ignition equal to 85.0% (thus a solids content of 15.0% by weight), is spray-dried.
- the characteristics of the silica obtained P2 in powder form are then as follows:
- Silica P2 is subjected to the disagglomeration test as defined previously in the description.
- aqueous sodium silicate having a weight ratio SiO 2 / Na 2 O equal to 3.44 and a density at 20 ° C. equal to 1. 230.
- the silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l.
- the mixture is then heated to a temperature of 83 ° C while maintaining stirring. It then introduces 16900 g of dilute sulfuric acid of density at 20 ° C equal to 1.050 in order to obtain in the reaction medium a pH value (measured at its temperature) equal to 8.
- the temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
- the total reaction time is 87 minutes.
- a slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
- the cake obtained is then fluidified by mechanical action. After this disintegration operation, the resulting slurry, with a loss on ignition equal to 84.5% (thus a solids content of 15.5% by weight), is spray-dried.
- the characteristics of the silica obtained P3 in powder form are then as follows:
- the silica P3 is subjected to the disagglomeration test as defined previously in the description.
- a first phase consists in a thermomechanical work phase at high temperature. It is followed by a second phase of mechanical work at temperatures below 110 ° C; this phase allows the introduction of the vulcanization system.
- the first phase is carried out in a Haake type internal mixer (capacity of 300 mL).
- the fill factor is 0.75.
- the initial temperature and the speed of the rotors are fixed each time so as to reach mixing drop temperatures of about 140-160 ° C.
- the first phase is decomposed here in two passes.
- the elastomer natural rubber
- the reinforcing inorganic filler consisting of silica (fractional introduction) with the coupling agent and stearic acid
- the duration of this pass is between 4 and 10 minutes.
- a second pass makes it possible to incorporate the zinc oxide and the protective / antioxidant agents (6-PPD in particular); the duration of this pass is between 2 and 5 minutes.
- the second phase allows the introduction of the vulcanization system (sulfur and accelerators, such as CBS). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 2 and 6 minutes.
- sulfur and accelerators such as CBS
- the Mooney consistency is measured on the compositions in the uncured state at 100 ° C. by means of a MV 2000 rheometer according to the NF ISO 289 standard.
- composition 1 has a satisfactory viscosity at raw water, and especially lower than that of the reference composition (reference 1) containing the same coupling agent but associated with a precipitated silica having an aluminum content that does not conform to that required by the invention. - Rheometry of the compositions
- the composition to be tested is placed in the controlled test chamber at a temperature of 150 ° C. for 30 minutes, and the resistive torque opposed by the composition is measured at a low amplitude oscillation (3 °).
- a biconical rotor included in the test chamber the composition completely filling the chamber in question.
- the roasting time TS2 corresponding to the time required to have a rise of 2 points above the minimum torque at the temperature in question (150 ° C.) and reflecting the time during which it is possible to use the raw mixtures with this temperature without initiation of vulcanization (the mixture cures from TS2).
- compositions Witness 1 Reference 1 Composition 1 Cmin (dNm) 12.8 13.5 13.0
- composition 1 has a very satisfactory set of rheological properties, and especially with respect to the reference composition (reference 1) containing the same coupling agent but associated with a precipitated silica exhibiting aluminum content not in accordance with that required by the invention.
- composition 1 has a good vulcanization kinetics (TS2, T98), especially with respect to the reference composition (reference 1) and even compared to the control composition (control 1) , without penalizing the viscosity of the raw mixture (illustrated in particular by the minimum torque).
- TS2, T98 good vulcanization kinetics
- the measurements are carried out on the optimally vulcanized compositions (T98) for a temperature of 150 ° C.
- the uniaxial tensile tests are carried out in accordance with the NF ISO 37 standard with type H2 specimens at a speed of 500 mm / min on an INSTRON 5564 device.
- the x% modules correspond to the stress measured at x% deformation. in tensile and are expressed, as the breaking strength in MPa. It is possible to determine a reinforcement index (IR) which is equal to the ratio between the 300% deformation modulus and the 100% deformation modulus.
- IR reinforcement index
- composition 1 has a very good compromise of mechanical properties, at least comparable to, or better than, what is obtained with the reference composition (reference 1) or even the control composition (witness 1). Dynamic properties of vulcanisais
- Dynamic properties are measured on a viscoanalyzer (Metravib VA3000) according to ASTM D5992.
- the values of the loss factor (tan ⁇ ) and elastic modulus in dynamic shear (G ') are recorded on vulcanized samples (parallelepipedal specimen of section 8 mm 2 and height 7 mm).
- the sample is subjected to alternating double shear sine wave deformation at a temperature of 40 ° C and a frequency of 10 Hz.
- the scanning processes in amplitude of deformations are carried out according to a round-trip cycle, ranging from 0.1 to 50% and then from 50 to 0.1%.
- composition 1 has very good dynamic properties (hysteretic properties at 60 ° C.), especially with respect to the reference composition (reference 1) and also with respect to the control composition (control 1) .
- composition 1 has a very good compromise of properties.
- Example 2 This example illustrates the use and behavior of the aluminum-containing precipitated silica prepared in Example 2 with 3-acryloxypropyltriethoxysilane in an elastomeric composition.
- elastomeric compositions are prepared whose constitution, expressed in part by weight per 100 parts of elastomers (phr), is given in Table VI below.
- a first phase consists in a thermomechanical work phase at high temperature. It is followed by a second phase of mechanical work at temperatures below 110 ° C; this phase allows the introduction of the vulcanization system.
- the first phase is carried out in a Haake type internal mixer (capacity of 300 mL).
- the fill factor is 0.75.
- the initial temperature and the speed of the rotors are fixed each time so as to reach mixing drop temperatures of about 140-160 ° C.
- the first phase is decomposed here in two passes.
- the elastomer natural rubber
- the reinforcing inorganic filler consisting of silica (fractional introduction) with the coupling agent and stearic acid; the duration of this pass is between 4 and 10 minutes.
- a second pass After cooling the mixture (temperature below 100 ° C.), a second pass makes it possible to incorporate the zinc oxide and the protective / antioxidant agents (6-PPD in particular); the duration of this pass is between 2 and 5 minutes.
- the second phase allows the introduction of the vulcanization system (sulfur and accelerators, such as CBS). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 2 and 6 minutes.
- sulfur and accelerators such as CBS
- the Mooney consistency is measured as in Example 5.
- composition 2 has a very good flood viscosity, lower than that of the reference composition (reference 2) containing the same coupling agent but associated with a precipitated silica having a content aluminum not conforming to that required by the invention, or that of the control composition (control 2) containing the same silica precipitated but associated with another coupling agent.
- compositions witness 2 Reference 2 Composition 2 Cmin (dNm) 13.0 1 1, 2 10.8
- composition 1 has a very satisfactory set of rheological properties, and especially with respect to the reference composition (reference 2) containing the same coupling agent but associated with a precipitated silica exhibiting aluminum content not in accordance with that required by the invention.
- composition 2 has a good vulcanization kinetics (TS2), especially with respect to the reference composition (reference 2) and with respect to the control composition (control 2), and without penalizing the viscosity of the raw mixture (illustrated in particular by the minimum torque).
- TS2 good vulcanization kinetics
- compositions vulcanized at the optimum that is to say at a state of vulcanization corresponding to 98% of the complete vulcanization
- the uniaxial tensile tests are carried out in accordance with the NF ISO 37 standard with type H2 specimens at a speed of 500 mm / min on an INSTRON 5564 device.
- the x% modules correspond to the stress measured at x% deformation. in tensile and are expressed, as the breaking strength in MPa. It is possible to determine a reinforcement index (IR) which is equal to the ratio between the 300% deformation modulus and the 100% deformation modulus.
- IR reinforcement index
- composition 2 has a very good compromise of mechanical properties, at least comparable to, or better than, that obtained with the reference composition (reference 2) or the control composition ( witness 2). Dynamic properties of vulcanisais
- composition 2 has very good dynamic properties (hysteretic properties at 60 ° C.), especially with respect to the reference composition (reference 2) and to the control composition (control 2).
- composition 2 has a very good compromise of properties.
- This example illustrates the use and behavior of a precipitated silica S, containing more than 0.5% by weight of aluminum and having the following characteristics, and 3-acryloxypropyltriethoxysilane in an elastomeric composition.
- the precipitated silica S has the following characteristics:
- elastomeric compositions are prepared whose constitution, expressed in part by weight per 100 parts of elastomers (phr), is shown in Table I below.
- a first phase consists in a thermomechanical work phase at high temperature. It is followed by a second phase of mechanical work at temperatures below 110 ° C; this phase allows the introduction of the vulcanization system.
- the first phase is carried out in a Haake-type internal mixer
- the initial temperature and the speed of the rotors are fixed each time so as to reach mixing temperatures of the vicinity of 150-170 ° C.
- the first phase is decomposed here in two passes. It allows to incorporate, in a first pass, the elastomer (natural rubber), then the reinforcing inorganic filler consisting of silica (fractional introduction) with the coupling agent and stearic acid; the duration of this pass is between 4 and 10 minutes.
- a second pass After cooling the mixture (temperature below 100 ° C.), a second pass makes it possible to incorporate the zinc oxide and the protective / antioxidant agents (6-PPD in particular); the duration of this pass is between 2 and 5 minutes.
- the second phase allows the introduction of the vulcanization system (sulfur and accelerators, such as CBS). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 2 and 6 minutes.
- sulfur and accelerators such as CBS
- the Mooney consistency is measured on the compositions in the uncured state at 100 ° C. by means of a MV 2000 rheometer according to the NF ISO 289 standard.
- the composition to be tested is placed in the controlled test chamber at a temperature of 150 ° C. for 30 minutes, and the resistive torque opposed by the composition is measured at a low amplitude oscillation (3 °).
- a biconical rotor included in the test chamber the composition completely filling the chamber in question.
- the roasting time TS2 corresponding to the time required to have a rise of 2 points above the minimum torque at the temperature in question (150 ° C.) and reflecting the time during which it is possible to use the raw mixtures with this temperature without initiation of vulcanization (the mixture cures from TS2).
- composition 3 The composition resulting from the invention (composition 3) leads to rather low values of Mooney consistency and minimum torque.
- the composition resulting from the invention has a satisfactory raw viscosity (Mooney consistency), lower than that of the control composition (control 3).
- this composition according to the invention has satisfactory rheological properties. She presents a good vulcanization kinetics (TS2), particularly with respect to the control composition, and without penalizing the viscosity of the raw mixture (illustrated by the minimum torque). Mechanical properties of vulcanisais
- compositions vulcanized at the optimum that is to say at a state of vulcanization corresponding to 98% of the complete vulcanization
- the uniaxial tensile tests are carried out in accordance with the NF ISO 37 standard with type H2 specimens at a speed of 500 mm / min on an INSTRON 5564 device.
- the x% modules correspond to the stress measured at x% deformation. in tension and are expressed, as the breaking strength, in MPa. It is possible to determine a reinforcement index (I.R.) which is equal to the ratio between the 300% deformation modulus and the 100% deformation modulus.
- the measurement of loss of mass by abrasion is carried out according to the indications of standard NF ISO 4649, using a Zwick abraser where the cylindrical specimen is subjected to the action of an abrasive cloth of grains P60 and fixed on the surface of a drum rotating under a contact pressure of 10 N and a stroke of 40 m.
- the measured value is a volume of loss of substance (in mm 3 ) after wear by abrasion; the lower it is, the better the resistance to abrasion.
- composition 3 the composition resulting from the invention (composition 3) has a very good compromise of mechanical properties, especially with respect to what is obtained with the control composition (control 3).
- composition resulting from the invention thus has relatively low 10% and 100% moduli and a 300% high modulus, hence a higher reinforcement index.
- this composition 3 has, in addition to a satisfactory breaking strength, a lower abrasion loss, that is to say a better resistance to abrasion, resulting in a gain in resistance to abrasion. wear, which is important in pneumatic applications, especially for heavy goods vehicles.
- Dynamic properties are measured on a viscoanalyzer (Metravib VA3000) according to ASTM D5992.
- composition 3 The composition resulting from the invention (composition 3) has very good dynamic properties (hysteretic properties at 60 ° C.), especially with respect to the control composition (control 3).
- composition 3 has a very good compromise of properties.
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Abstract
The invention relates to the joint use, in an elastomer composition comprising an isoprenic elastomer, of a precipitated silica containing aluminium, as a reinforcing inorganic filler, the aluminium content of said precipitated silica being higher than 0.5 wt. %, and 3-acryloxy-propyltriethoxysilane as an inorganic filler - elastomer coupling agent. The invention also relates to the elastomer compositions obtained and the items produced from said compositions.
Description
UTILISATION D'UNE SILICE PRECIPITEE CONTENANT DE L'ALUMINIUM USE OF PRECIPITED SILICA CONTAINING ALUMINUM
ET DE 3-ACRYLOXY-PROPYLTRIETHOXYSILANE DANS UNE COMPOSITION D'ELASTOMERE(S) ISOPRENIQUE(S) AND 3-ACRYLOXY-PROPYLTRIETHOXYSILANE IN AN ISOPRENE (S) ELASTOMER COMPOSITION
L'invention concerne l'utilisation conjointe, dans des compositions d'élastomère(s) comprenant un élastomère isoprénique, tel que le caoutchouc naturel, d'une charge inorganique renforçante particulière et d'un agent de couplage charge inorganique - élastomère particulier. The invention relates to the joint use, in elastomer compositions (s) comprising an isoprene elastomer, such as natural rubber, of a particular reinforcing inorganic filler and a particular inorganic filler - elastomer coupling agent.
Elle est également relative aux compositions d'élastomères correspondantes et aux articles, notamment des pneumatiques, comprenant de telles compositions. II est connu que les articles en élastomère(s) sont généralement soumis à des contraintes variées, par exemple telles qu'une variation de température, une variation de sollicitation de fréquence importante en régime dynamique, une contrainte statique importante et/ou une fatigue en flexion non négligeable en régime dynamique. De tels articles sont par exemple des pneumatiques, des semelles de chaussures, des revêtements de sols, des bandes de convoyeur, des courroies de transmission de puissance, des tuyaux flexibles, des joints, notamment des joints d'appareils électroménagers, des supports jouant le rôle d'extracteurs de vibrations de moteurs soit avec des armatures métalliques, soit avec un fluide hydraulique à l'intérieur de l'élastomère, des gaines de câbles, des câbles, des galets de téléphériques. It also relates to the corresponding elastomer compositions and articles, in particular tires, comprising such compositions. It is known that the elastomeric articles are generally subjected to various constraints, for example such as a temperature variation, a significant frequency stress variation in dynamic regime, a significant static stress and / or fatigue in significant bending in dynamic mode. Such articles are, for example, tires, shoe soles, floor coverings, conveyor belts, power transmission belts, hoses, seals, especially appliance seals, role of engine vibration extractors either with metal reinforcements or with a hydraulic fluid inside the elastomer, cable sheaths, cables, ropeway rollers.
Il a été alors proposé d'utiliser notamment des compositions d'élastomère(s) renforcées par des charges inorganiques spécifiques qualifiées de « renforçantes », présentant de préférence une haute dispersibilité. Ces charges, en particulier les charges blanches comme les silices précipitées, sont capables de rivaliser avec ou même de dépasser au moins du point de vue renforçant le noir de carbone employé conventionnellement, et offrent en outre à ces compositions une hystérèse généralement plus basse, synonyme notamment
d'une diminution de échauffement interne des articles en élastomère(s) lors de leur utilisation. It was then proposed to use in particular elastomer compositions (s) reinforced with specific inorganic fillers described as "reinforcing", preferably having a high dispersibility. These fillers, in particular white fillers such as precipitated silicas, are capable of competing with or even exceeding at least from the point of view reinforcing the conventionally used carbon black, and also offer these compositions a generally lower hysteresis, which is synonymous especially a decrease in internal heating of the elastomeric articles (s) during their use.
Il est connu de l'homme du métier qu'il est généralement nécessaire d'employer dans les compositions d'élastomère(s) contenant de telles charges renforçantes un agent de couplage, encore appelé agent de liaison, qui a pour fonction notamment d'assurer la connexion entre la surface des particules de charge inorganique (par exemple une silice précipitée) et l'(les) élastomère(s), tout en facilitant la dispersion de cette charge inorganique au sein de la matrice élastomérique. It is known to those skilled in the art that it is generally necessary to employ in the elastomer compositions containing such reinforcing fillers a coupling agent, also called a binding agent, whose function is, in particular, to providing the connection between the surface of the inorganic filler particles (for example a precipitated silica) and the elastomer (s), while facilitating the dispersion of this inorganic filler within the elastomeric matrix.
Par agent de couplage charge inorganique - élastomère, on entend de manière connue un agent apte à établir une connexion suffisante, de nature chimique et/ou physique, entre la charge inorganique et l'élastomère. The term "inorganic filler-elastomer coupling agent" is understood to mean an agent capable of establishing a sufficient chemical and / or physical connection between the inorganic filler and the elastomer.
Un tel agent de couplage, au moins bifonctionnel, a par exemple comme formule générale simplifiée « N-V-M », dans laquelle : Such a coupling agent, at least bifunctional, has for example as simplified general formula "N-V-M", in which:
- N représente un groupe fonctionnel (fonction "N") capable de se lier physiquement et/ou chimiquement à la charge inorganique, une telle liaison pouvant être établie, par exemple, entre un atome de silicium de l'agent de couplage et les groupes hydroxyles (OH) de la surface de la charge inorganique (par exemple les silanols de surface lorsqu'il s'agit de silice) ; N represents a functional group ("N" function) capable of binding physically and / or chemically to the inorganic filler, such a bond being able to be established, for example, between a silicon atom of the coupling agent and the groups hydroxyl (OH) on the surface of the inorganic filler (for example surface silanols when it is silica);
- M représente un groupe fonctionnel (fonction "M") capable de se lier physiquement et/ou chimiquement à l'élastomère, notamment par l'intermédiaire d'un atome ou d'un groupe d'atomes appropriés (par exemple un atome de soufre) ; M represents a functional group ("M" function) capable of binding physically and / or chemically to the elastomer, in particular via a suitable atom or group of atoms (for example an atom of sulfur);
- V représente un groupe (divalent/hydrocarboné) permettant de relier "N" et "M". - V represents a group (divalent / hydrocarbon) for connecting "N" and "M".
Les agents de couplage ne doivent pas être confondus avec de simples agents de recouvrement de charge inorganique qui, de manière connue, peuvent comporter la fonction "N" active vis-à-vis de la charge inorganique mais sont dépourvus de la fonction "M" active vis-à-vis de l'élastomère. The coupling agents should not be confused with simple inorganic filler agents which, in a known manner, may have the "N" function active with respect to the inorganic filler but lack the "M" function. active with respect to the elastomer.
Des agents de couplage, notamment (silice - élastomère), ont été décrits dans de nombreux documents de l'état de la technique, les plus connus étant des silanes (poly)sulfurés, en particulier des alkoxysilanes (poly)sulfurés. Parmi ces
silanes (poly)sulfurés, on peut citer notamment le tétrasulfure de bis- triéthoxysilylpropyle (en abrégé TESPT), qui est généralement encore considéré aujourd'hui comme un produit apportant, pour des vulcanisais comprenant une charge inorganique à titre de charge renforçante, telle que de la silice, un très bon, voire le meilleur, compromis en terme de sécurité au grillage, de facilité de mise en oeuvre et de pouvoir renforçant. Coupling agents, in particular (silica-elastomer), have been described in numerous documents of the state of the art, the best known being (poly) sulphide silanes, in particular (poly) sulphidized alkoxysilanes. Among these (Poly) sulfurized silanes, mention may in particular be made of bis-triethoxysilylpropyl tetrasulfide (abbreviated to TESPT), which is generally still considered today as a product providing, for vulcanizates comprising an inorganic filler as a reinforcing filler, such as silica, a very good, or even the best, compromised in terms of safety roasting, ease of implementation and strengthening power.
L'utilisation combinée de silice précipitée, en particulier hautement dispersible et d'un silane (ou composé organosilique fonctionnalisé) polysulfuré dans une composition d'élastomère(s) modifié(s) a permis le développement du « pneu vert » pour les véhicules tourisme (véhicules légers). Cette combinaison a permis d'atteindre une performance de résistance à l'usure comparable à celle des mélanges d'élastomères renforcés par de noir de carbone, tout en améliorant de manière significative la résistance au roulement (d'où une baisse de la consommation de carburant), et l'adhérence sur sol humide. The combined use of precipitated silica, in particular highly dispersible silica and a silane (or organosilic compound functionalized) polysulfide in a modified elastomer composition (s) allowed the development of the "green tire" for passenger vehicles (Light vehicles). This combination achieved a wear resistance performance comparable to that of carbon black-reinforced elastomer blends, while significantly improving rolling resistance (resulting in lower fuel consumption). fuel), and grip on wet ground.
II serait donc intéressant de pouvoir également utiliser une charge inorganique comme de la silice dans les pneus pour poids lourds, pneus qui sont obtenus à partir de compositions à base d'élastomère(s) isoprénique(s), principalement le caoutchouc naturel. It would therefore be interesting to also be able to use an inorganic filler such as silica in tires for trucks, tires which are obtained from compositions based on isoprene elastomer (s), mainly natural rubber.
Cependant la même combinaison silice / silane polysulfuré appliquée à un élastomère isoprénique comme le caoutchouc naturel n'a pas permis d'obtenir un niveau de renforcement (qui peut être illustré par une courbe contrainte - allongement en traction uniaxiale) suffisant par rapport à ce qui est obtenu lorsque l'on emploie du noir de carbone comme charge, ce renforcement en retrait conduisant à une médiocre résistance à l'usure. However, the same combination of polysulfurized silica and silane applied to an isoprene elastomer such as natural rubber did not make it possible to obtain a level of reinforcement (which can be illustrated by a stress-strain curve uniaxial) sufficient compared to what is obtained when carbon black is used as a filler, this backing resulting in poor wear resistance.
Le but de la présente invention est de proposer notamment l'association pour les compositions d'élastomère(s) comprenant un élastomère diénique, tel que le caoutchouc naturel, d'un agent de couplage particulier avec une charge inorganique renforçante particulière, cette combinaison consistant en une alternative à l'utilisation d'agents de couplage connus avec des charges inorganiques renforçantes connues, cette combinaison procurant de plus, auxdites compositions d'élastomère(s), un compromis de propriétés très
satisfaisant, notamment au niveau de leurs propriétés rhéologiques, mécaniques et/ou dynamiques, notamment hystérétiques. De manière avantageuse, elle permet une amélioration de la résistance à l'usure et du compromis hystérèse/renforcement. En outre, les compositions d'élastomère(s) obtenues présentent préférentiellement une très bonne adhésion à la fois à la charge inorganique renforçante employée et aux substrats auxquels elles sont ensuite appliquées. The object of the present invention is to propose in particular the combination for elastomer compositions comprising a diene elastomer, such as natural rubber, with a particular coupling agent with a particular reinforcing inorganic filler, this combination consisting of as an alternative to the use of known coupling agents with known reinforcing inorganic fillers, this combination further providing said elastomer compositions with a very favorable property compromise. satisfactory, especially in terms of their rheological properties, mechanical and / or dynamic, including hysteresis. Advantageously, it allows an improvement in the wear resistance and hysteresis / reinforcement compromise. In addition, the elastomer compositions obtained preferably have very good adhesion to both the reinforcing inorganic filler used and the substrates to which they are subsequently applied.
L'invention concerne dans son premier objet l'utilisation dans une composition d'élastomère(s), comprenant au moins un élastomère isoprénique :The invention relates in its first object to the use in an elastomer composition (s), comprising at least one isoprene elastomer:
- d'une silice précipitée contenant de l'aluminium, comme charge inorganique renforçante, la teneur en aluminium de ladite silice précipitée étant supérieure à 0,5 % en poids, avec a precipitated silica containing aluminum, as reinforcing inorganic filler, the aluminum content of said precipitated silica being greater than 0.5% by weight, with
- du 3-acryloxy-propyltriethoxysilane (ou γ-acryloxy-propyltriethoxysilane), comme agent de couplage charge inorganique - élastomère. 3-acryloxypropyltriethoxysilane (or γ-acryloxypropyltriethoxysilane), as an inorganic filler-elastomer coupling agent.
Ladite silice précipitée utilisée possède généralement une teneur en aluminium d'au plus 7,0 % en poids, de préférence d'au plus 5,0 % en poids, en particulier d'au plus 3,5 % en poids, par exemple d'au plus 3,0 % en poids. Said precipitated silica used generally has an aluminum content of at most 7.0% by weight, preferably at most 5.0% by weight, in particular at most 3.5% by weight, for example at most 3.0% by weight.
De préférence, sa teneur en aluminium est comprise entre 0,75 et 4,0 % en poids, de manière encore plus préférée entre 0,8 et 3,5 % en poids, en particulier entre 0,9 et 3,2 % en poids, notamment entre 0,9 et 2,5 % en poids ou entre 1 ,0 et 3,1 % en poids. Elle est par exemple comprise entre 1 ,0 et 3,0 % en poids, voire entre 1 ,0 et 2,0 % en poids. Preferably, its aluminum content is between 0.75 and 4.0% by weight, even more preferably between 0.8 and 3.5% by weight, in particular between 0.9 and 3.2% by weight. weight, especially between 0.9 and 2.5% by weight or between 1.0 and 3.1% by weight. It is for example between 1.0 and 3.0% by weight, or even between 1.0 and 2.0% by weight.
La quantité d'aluminium peut être mesurée par toute méthode convenable, par exemple par ICP-AES (« Inductively Coupled Plasma - Atomic Emission Spectroscopy ») après mise en solution dans l'eau en présence d'acide fluorhydrique. The amount of aluminum can be measured by any suitable method, for example by ICP-AES ("Inductively Coupled Plasma - Atomic Emission Spectroscopy") after dissolution in water in the presence of hydrofluoric acid.
L'aluminium se situe, en général, essentiellement à la surface de la silice précipitée. Aluminum is, in general, essentially on the surface of the precipitated silica.
Même si l'aluminium peut être présent à la fois sous forme tétraédrique, sous forme octaédrique et sous forme pentaédrique, en particulier sous forme
tétraédrique et sous forme octaédrique, dans la silice précipitée utilisée dans l'invention, il se trouve de préférence essentiellement sous forme tétraédrique (plus de 50 %, en particulier au moins 90 %, notamment au moins 95 %, en nombre, des espèces aluminium sont alors sous forme tétraédrique) ; les liaisons sont alors plutôt essentiellement du type SiOAI. Although aluminum may be present in both tetrahedral, octahedral and pentahedral form, particularly in the form of tetrahedral and in octahedral form, in the precipitated silica used in the invention, it is preferably essentially in tetrahedral form (more than 50%, in particular at least 90%, especially at least 95% by number, of the aluminum species are then in tetrahedral form); the links are then rather essentially of the SiOAI type.
Ladite silice précipitée contenant de l'aluminium employée dans l'invention est de manière avantageuse hautement dispersible, c'est-à-dire qu'en particulier elle présente une aptitude à la désagglomération et à la dispersion dans une matrice polymérique très importante, notamment observable par microscopie électronique ou optique, sur coupes fines. Said precipitated silica containing aluminum used in the invention is advantageously highly dispersible, that is to say that in particular it has an ability to deagglomerate and to disperse in a very important polymeric matrix, in particular observable by electron or optical microscopy, on thin sections.
De préférence, la silice précipitée utilisée selon l'invention possède une surface spécifique CTAB comprise entre 70 et 240 m2/g. Preferably, the precipitated silica used according to the invention has a CTAB specific surface area of between 70 and 240 m 2 / g.
Celle-ci peut être comprise entre 70 et 100 m2/g, par exemple entre 75 et 95 m2/g. This may be between 70 and 100 m 2 / g, for example between 75 and 95 m 2 / g.
Cependant, de manière très préférée, sa surface spécifique CTAB est comprise entre 100 et 240 m2/g, en particulier entre 140 et 200 m2/g. However, very preferably, its CTAB surface area is between 100 and 240 m 2 / g, in particular between 140 and 200 m 2 / g.
De même, de préférence, la silice précipitée utilisée selon l'invention possède une surface spécifique BET comprise entre 70 et 240 m2/g. Likewise, preferably, the precipitated silica used according to the invention has a BET specific surface area of between 70 and 240 m 2 / g.
Celle-ci peut être comprise entre 70 et 100 m2/g, par exemple entre 75 etThis can be between 70 and 100 m 2 / g, for example between 75 and
95 m2/g. 95 m 2 / g.
Cependant, de manière très préférée, sa surface spécifique BET est comprise entre 100 et 240 m2/g, en particulier entre 140 et 200 m2/g. However, very preferably, its BET surface area is between 100 and 240 m 2 / g, in particular between 140 and 200 m 2 / g.
La surface spécifique CTAB est la surface externe, pouvant être déterminée selon la méthode NF T 45007 (novembre 1987). La surface spécifique BET peut être mesurée selon la méthode de BRUNAUER - EMMETT - TELLER décrite dans "The Journal of the American Chemical Society", vol. 60, page 309 (1938) et correspondant à la norme NF T 45007 (novembre 1987). L'aptitude à la dispersion (et à la désagglomération) de la silice précipitée mise en œuvre selon l'invention peut être appréciée au moyen du test suivant, par une mesure granulométrique (par diffraction laser) effectuée sur une
suspension de silice préalablement désagglomérée par ultra-sonification (rupture des objets de 0,1 à quelques dizaines de microns). La désagglomération sous ultra-sons est effectuée à l'aide d'un sonificateur VIBRACELL BIOBLOCK (750 W), équipé d'une sonde de diamètre 19 mm. La mesure granulométrique est effectuée par diffraction laser sur un granulomère SYMPATEC, en mettant en œuvre la théorie de Fraunhofer. The CTAB specific surface area is the external surface, which can be determined according to the NF T 45007 method (November 1987). The BET surface area can be measured according to the method of BRUNAUER - EMMETT - TELLER described in "The Journal of the American Chemical Society", vol. 60, page 309 (1938) and corresponding to standard NF T 45007 (November 1987). The dispersibility (and disagglomeration) ability of the precipitated silica implemented according to the invention can be assessed by means of the following test, by a granulometric measurement (by laser diffraction) carried out on a Silica suspension previously deagglomerated by ultra-sonification (breaking objects from 0.1 to a few tens of microns). Ultrasonic deagglomeration is carried out using a VIBRACELL BIOBLOCK (750 W) sonicator equipped with a 19 mm diameter probe. The particle size measurement is carried out by laser diffraction on a SYMPATEC granulomer, using the Fraunhofer theory.
On pèse dans un pilulier (hauteur : 6 cm et diamètre : 4 cm) 2 grammes de silice et l'on complète à 50 grammes par ajout d'eau permutée : on réalise ainsi une suspension aqueuse à 4 % de silice qui est homogénéisée pendant 2 minutes par agitation magnétique. On procède ensuite à la désagglomération sous ultra-sons comme suit : la sonde étant immergée sur une longueur de 4 cm, on la met en action pendant 5 minutes et 30 secondes à 80 % de sa puissance nominale (amplitude). On réalise ensuite la mesure granulométrique en introduisant dans la cuve du granulomètre un volume V (exprimé en ml) de la suspension homogénéisée nécessaire pour obtenir une densité optique de l'ordre de 20. In a pillbox (height: 6 cm and diameter: 4 cm), 2 grams of silica are weighed and the mixture is made up to 50 grams by addition of deionized water: a 4% aqueous suspension of silica is thus obtained which is homogenized during 2 minutes by magnetic stirring. The deagglomeration is then carried out under ultrasound as follows: the probe being immersed over a length of 4 cm, it is put into action for 5 minutes and 30 seconds at 80% of its nominal power (amplitude). The particle size measurement is then carried out by introducing into the vat of the granulometer a volume V (expressed in ml) of the homogenized suspension necessary to obtain an optical density of about 20.
La valeur du diamètre médian 05O que l'on obtient selon ce test est d'autant plus faible que la silice présente une aptitude à la désagglomération élevée. The value of the median diameter 050 obtained according to this test is even lower than the silica has a high ability to deagglomerate.
Un facteur de désagglomération FD est donné par l'équation : A disaggregation factor F D is given by the equation:
FD = 10 x V / densité optique de la suspension mesurée par le granulomètreF D = 10 x V / optical density of the suspension measured by the granulometer
(cette densité optique est de l'ordre de 20). (This optical density is of the order of 20).
Ce facteur de désagglomération FD est indicatif du taux de particules de taille inférieure à 0,1 μιτι qui ne sont pas détectées par le granulomètre. Ce facteur est d'autant plus élevé que la silice présente une aptitude à la désagglomération élevée. This disaggregation factor F D is indicative of the rate of particles smaller than 0.1 μιτι which are not detected by the granulometer. This factor is all the higher as the silica has a high deagglomeration ability.
En général, la silice précipitée contenant de l'aluminium mise en œuvre selon l'invention possède un diamètre médian 05O, après désagglomération aux ultra-sons, inférieur à 5 μιτι, en particulier inférieur à 4 μιτι, notamment inférieur à 3,5 μιτι, par exemple inférieur à 3 μιτι. In general, the precipitated silica containing aluminum used according to the invention has a median diameter δ 50 , after deagglomeration with ultrasound, less than 5 μιτι, in particular less than 4 μιτι, in particular less than 3.5. μιτι, for example less than 3 μιτι.
Elle présente habituellement un facteur de désagglomération aux ultra-sons It usually has an ultrasonic deagglomeration factor
FD supérieur à 4,5 ml, en particulier supérieur à 5,5 ml, notamment supérieur à 9 ml, par exemple supérieur à 10 ml.
La prise d'huile DOP de la silice précipitée contenant de l'aluminium employée selon l'invention peut être inférieure à 300 ml/100g, par exemple comprise entre 200 et 295 ml/100g. La prise d'huile DOP peut être déterminée selon la norme ISO 787/5 en mettant en œuvre le dioctylphtalate. F D greater than 4.5 ml, in particular greater than 5.5 ml, especially greater than 9 ml, for example greater than 10 ml. The DOP oil uptake of the precipitated aluminum-containing silica used according to the invention may be less than 300 ml / 100 g, for example between 200 and 295 ml / 100 g. DOP oil uptake can be determined according to ISO 787/5 by using dioctylphthalate.
Un des paramètres de la silice précipitée mise en œuvre dans l'invention peut résider dans la distribution, ou répartition, de son volume poreux, et notamment dans la distribution du volume poreux qui est généré par les pores de diamètres inférieurs ou égaux à 400 Â. Ce dernier volume correspond au volume poreux utile des charges employées dans le renforcement des élastomères. One of the parameters of the precipitated silica implemented in the invention may reside in the distribution, or distribution, of its pore volume, and in particular in the distribution of the pore volume which is generated by pores with diameters less than or equal to 400 Å. . This latter volume corresponds to the useful pore volume of the charges used in the reinforcement of the elastomers.
Si cette silice précipitée peut posséder, selon une première variante, une distribution poreuse (et cela peut être illustré par l'analyse des porogrammes) telle que le volume poreux généré par les pores dont le diamètre est compris entre 175 et 275 Â (V2) représente moins de 50 % du volume poreux généré par les pores de diamètres inférieurs ou égaux à 400 Â (V1 ), il peut être également intéressant d'employer, selon une seconde variante, une silice précipitée possédant une distribution poreuse telle que le volume poreux généré par les pores dont le diamètre est compris entre 175 et 275 Â (V2) représente au moins 50 % (par exemple entre 50 et 60 %) du volume poreux généré par les pores de diamètres inférieurs ou égaux à 400 Â (V1 ). If this precipitated silica may have, in a first variant, a porous distribution (and this may be illustrated by the analysis of porograms) such as the pore volume generated by the pores whose diameter is between 175 and 275 Å (V2) represents less than 50% of the pore volume generated by pores with diameters less than or equal to 400 Å (V1), it may also be advantageous to use, in a second variant, a precipitated silica having a porous distribution such as the porous volume generated by the pores whose diameter is between 175 and 275 Å (V2) represents at least 50% (for example between 50 and 60%) of the pore volume generated by pores with diameters less than or equal to 400 Å (V1).
Les volumes poreux et diamètres de pores sont mesurés par porosimétrie au mercure (Hg), à l'aide d'un porosimètre MICROMERITICS Autopore 9520, et sont calculés par la relation de WASHBURN avec un angle de contact thêta égal à 130° et une tension superficielle gamma égale à 484 Dynes/cm (norme DIN 66133). The porous volumes and pore diameters are measured by mercury porosimetry (Hg), using a MICROMERITICS Autopore 9520 porosimeter, and are calculated by the WASHBURN relation with a theta contact angle of 130 ° and a voltage. superficial gamma equal to 484 Dynes / cm (DIN 66133 standard).
Le pH de la silice précipitée utilisée selon l'invention est généralement compris entre 6,3 et 8,0, par exemple entre 6,3 et 7,6. The pH of the precipitated silica used according to the invention is generally between 6.3 and 8.0, for example between 6.3 and 7.6.
Le pH est mesuré selon la méthode suivante dérivant de la norme ISO 787/9 (pH d'une suspension à 5 % dans l'eau) : The pH is measured according to the following method deriving from the ISO 787/9 standard (pH of a suspension at 5% in water):
Appareillage :
- pHmètre étalonné (précision de lecture au 1/100e) Apparatus: - calibrated pH meter (reading accuracy at 1 / 100th)
- électrode de verre combinée - combined glass electrode
- bêcher de 200 mL - 200 mL beaker
- éprouvette de 100 mL - 100 mL test tube
- balance de précision à 0,01 gramme près. - precision balance to 0.01 gram.
Mode opératoire : Operating mode:
5 grammes de silice sont pesés à 0,01 gramme près dans le bêcher de 200 mL. 95 mL d'eau mesurés à partir de l'éprouvette graduée sont ensuite ajoutés à la poudre de silice. La suspension ainsi obtenue est agitée énergiquement (agitation magnétique) pendant 10 minutes. La mesure du pH est alors effectuée. L'état physique dans lequel se présente la silice précipitée à utiliser selon l'invention peut être quelconque, c'est-à-dire qu'elle peut se présenter par exemple sous forme de microperles (billes sensiblement sphériques), de poudre ou de granulés. 5 grams of silica are weighed to the nearest 0.01 gram in the beaker of 200 ml. 95 mL of water measured from the graduated cylinder is then added to the silica powder. The suspension thus obtained is stirred vigorously (magnetic stirring) for 10 minutes. The pH measurement is then performed. The physical state in which the precipitated silica to be used according to the invention is present may be arbitrary, that is to say that it may be, for example, in the form of microbeads (substantially spherical beads), powder or granules.
Elle peut ainsi se présenter sous forme de billes sensiblement sphériques de taille moyenne d'au moins 80 μιτι, de préférence d'au moins 150 m, en particulier comprise entre 150 et 270 μιτι ; cette taille moyenne est déterminée selon la norme NF X 1 1507 (décembre 1970) par tamisage à sec et détermination du diamètre correspondant à un refus cumulé de 50 %. It can thus be in the form of substantially spherical beads of average size of at least 80 μm, preferably at least 150 μm, in particular between 150 and 270 μm; this average size is determined according to standard NF X 1 1507 (December 1970) by dry sieving and determination of the diameter corresponding to a cumulative refusal of 50%.
Elle peut se présenter sous forme de poudre de taille moyenne d'au moins 3 μιτι, en particulier d'au moins 10 μιτι, de préférence d'au moins 15 μιτι. It may be in the form of a powder of average size of at least 3 μιτι, in particular at least 10 μιτι, preferably at least 15 μιτι.
Elle peut se présenter sous forme de granulés (en général de forme sensiblement parallélépipédique) de taille d'au moins 1 mm, par exemple comprise entre 1 et 10 mm, notamment selon l'axe de leur plus grande dimension (longueur).
Selon une variante particulière non-limitative, la silice précipitée, ayant une teneur en aluminium supérieure à 0,5 % en poids, utilisée selon l'invention peut présenter : It may be in the form of granules (generally of substantially parallelepipedal shape) of size of at least 1 mm, for example between 1 and 10 mm, especially along the axis of their largest dimension (length). According to one particular nonlimiting variant, the precipitated silica, having an aluminum content greater than 0.5% by weight, used according to the invention may have:
- une surface spécifique CTAB comprise entre 140 et 200 m2/g, a CTAB specific surface area of between 140 and 200 m 2 / g,
- une surface spécifique BET comprise entre 140 et 200 m2/g, a BET specific surface area of between 140 and 200 m 2 / g,
- éventuellement, une prise d'huile DOP inférieure à 300 ml/100g, - optionally, a DOP oil intake of less than 300 ml / 100g,
- un diamètre médian 05O, après désagglomération aux ultra-sons, inférieur à 3 μιτι, et a median diameter δ 50 , after deagglomeration with ultrasound, less than 3 μιτι, and
- un facteur de désagglomération aux ultra-sons FD supérieur à 10 ml. a deagglomeration factor with ultrasound F D greater than 10 ml.
Dans cette variante particulière, la silice précipitée peut par exemple présenter une distribution poreuse telle que le volume poreux généré par les pores dont le diamètre est compris entre 175 et 275 Â (V2) représente au moins 50 %, par exemple entre 50 et 60 %, du volume poreux généré par les pores de diamètres inférieurs ou égaux à 400 Â (V1 ). In this particular variant, the precipitated silica may for example have a porous distribution such that the pore volume generated by the pores whose diameter is between 175 and 275 Å (V 2) represents at least 50%, for example between 50 and 60% of the pore volume generated by pores with diameters less than or equal to 400 Å (V1).
Selon une autre variante particulière non-limitative, la silice précipitée, ayant une teneur en aluminium supérieure à 0,5 % en poids, utilisée selon l'invention peut présenter : According to another particular nonlimiting variant, the precipitated silica having an aluminum content greater than 0.5% by weight, used according to the invention may exhibit:
- une surface spécifique CTAB comprise entre 140 et 200 m2/g, a CTAB specific surface area of between 140 and 200 m 2 / g,
- éventuellement, une prise d'huile DOP inférieure à 300 ml/100g, - optionally, a DOP oil intake of less than 300 ml / 100g,
- une distribution poreuse telle que le volume poreux constitué par les pores dont le diamètre est compris entre 175 et 275 Â (V2) représente moins de 50 % du volume poreux constitué par les pores de diamètres inférieurs ou égaux à 400 A (V1 ), et a porous distribution such that the pore volume constituted by the pores whose diameter is between 175 and 275 Å (V 2) represents less than 50% of the pore volume constituted by pores with diameters less than or equal to 400 Å (V 1), and
- un diamètre médian 05O, après désagglomération aux ultra-sons, inférieur à 5 μιτι. a median diameter δ 50 , after deagglomeration with ultrasound, less than 5 μιτι.
Selon une autre variante particulière non-limitative, la silice précipitée, ayant une teneur en aluminium supérieure à 0,5 % en poids, utilisée selon l'invention peut présenter : According to another particular nonlimiting variant, the precipitated silica having an aluminum content greater than 0.5% by weight, used according to the invention may exhibit:
- une surface spécifique CTAB comprise entre 140 et 200 m2/g, a CTAB specific surface area of between 140 and 200 m 2 / g,
- éventuellement, une prise d'huile DOP inférieure à 300 ml/100g, - optionally, a DOP oil intake of less than 300 ml / 100g,
- une distribution poreuse telle que le volume poreux constitué par les pores dont le diamètre est compris entre 175 et 275 Â (V2) représente au moins 50 %,
par exemple entre 50 et 60 %, du volume poreux constitué par les pores de diamètres inférieurs ou égaux à 400 Â (V1 ), et a porous distribution such that the pore volume constituted by the pores whose diameter is between 175 and 275 Å (V 2) represents at least 50%, for example between 50 and 60%, of the pore volume constituted by pores with diameters less than or equal to 400 Å (V1), and
- un diamètre médian 05O, après désagglomération aux ultra-sons, inférieur à 5 μιτι. a median diameter δ 50 , after deagglomeration with ultrasound, less than 5 μιτι.
La silice précipitée mise en œuvre dans le cadre de l'invention peut être préparée par exemple par un procédé tel que décrit dans les demandes de brevet EP-A-0762992, EP-A-0762993, EP-A-0983966, EP-A-1355856. The precipitated silica implemented in the context of the invention may be prepared for example by a process as described in patent applications EP-A-0762992, EP-A-0762993, EP-A-0983966, EP-A -1355856.
De préférence, la silice précipitée employée dans l'invention peut être obtenue par un procédé de préparation comprenant la réaction de précipitation entre un silicate et un agent acidifiant ce par quoi l'on obtient une suspension de silice précipitée, puis la séparation et le séchage de cette suspension, dans lequel : Preferably, the precipitated silica employed in the invention can be obtained by a preparation process comprising the precipitation reaction between a silicate and an acidifying agent whereby a suspension of precipitated silica is obtained, followed by separation and drying. of this suspension, in which:
- on réalise la réaction de précipitation de la manière suivante : the precipitation reaction is carried out as follows:
(i) on forme un pied de cuve initial comportant un silicate et un électrolyte, la concentration en silicate (exprimée en SiO2) dans ledit pied de cuve initial étant inférieure à 100 g/L et la concentration en électrolyte dans ledit pied de cuve initial étant inférieure à 17 g/L, (i) forming an initial stock having a silicate and an electrolyte, the silicate concentration (expressed as SiO 2 ) in said initial stock being less than 100 g / L and the electrolyte concentration in said stock initial value being less than 17 g / L,
(ii) on ajoute l'agent acidifiant audit pied de cuve jusqu'à l'obtention d'une valeur du pH du milieu réactionnel d'au moins 7, (ii) the acidifying agent is added to said heelstock until a pH value of the reaction medium of at least 7 is obtained,
(iii) on ajoute au milieu réactionnel simultanément de l'agent acidifiant et un silicate, (iii) acidifying agent and a silicate are added to the reaction medium simultaneously,
- on sèche une suspension présentant un taux de matière sèche d'au plus 24 % en poids, a suspension having a solids content of not more than 24% by weight is dried,
ledit procédé comprenant une des trois opérations (a), (b) ou (c) suivantes : said method comprising one of the following three operations (a), (b) or (c):
(a) on ajoute, après l'étape (iii), au milieu réactionnel au moins un composé (a) after step (iii), at least one compound is added to the reaction medium
A de l'aluminium et, ensuite ou simultanément, un agent basique, To aluminum and then, or simultaneously, a basic agent,
(b) on ajoute, après l'étape (iii) ou à la place de l'étape (iii), au milieu réactionnel simultanément un silicate et au moins un composé A de l'aluminium, (b) after step (iii) or in place of step (iii), a silicate and at least one aluminum compound A are added simultaneously to the reaction medium;
(c) l'étape (iii) est réalisée en ajoutant simultanément au milieu réactionnel de l'agent acidifiant, un silicate et au moins un composé B de l'aluminium.
Il est à noter, d'une manière générale, que ce procédé de préparation est un procédé de synthèse de silice de précipitation, c'est-à-dire que l'on fait agir, dans des conditions particulières, un agent acidifiant avec un silicate. (c) step (iii) is carried out by simultaneously adding to the reaction medium acidifying agent, a silicate and at least one compound B of aluminum. It should be noted, in general, that this preparation process is a precipitation silica synthesis process, that is to say that it is made to act, under particular conditions, an acidifying agent with a silicate.
Le choix de l'agent acidifiant et du silicate se fait d'une manière bien connue en soi. The choice of acidifying agent and silicate is in a manner well known per se.
On utilise généralement comme agent acidifiant un acide minéral fort tel que l'acide sulfurique, l'acide nitrique ou l'acide chlorhydrique, ou un acide organique tel que l'acide acétique, l'acide formique ou l'acide carbonique. The acidifying agent used is a strong mineral acid such as sulfuric acid, nitric acid or hydrochloric acid, or an organic acid such as acetic acid, formic acid or carbonic acid.
L'agent acidifiant peut être dilué ou concentré ; sa normalité peut être comprise entre 0,4 et 36 N, par exemple entre 0,6 et 1 ,5 N. The acidifying agent may be diluted or concentrated; its normality can be between 0.4 and 36 N, for example between 0.6 and 1.5 N.
En particulier, dans le cas où l'agent acidifiant est l'acide sulfurique, sa concentration peut être comprise entre 40 et 180 g/L, par exemple entre 60 et 130 g/L. In particular, in the case where the acidifying agent is sulfuric acid, its concentration may be between 40 and 180 g / l, for example between 60 and 130 g / l.
On peut par ailleurs utiliser en tant que silicate toute forme courante de silicates tels que métasilicates, disilicates et avantageusement un silicate de métal alcalin, notamment le silicate de sodium ou de potassium. It is also possible to use, as silicate, any current form of silicates such as metasilicates, disilicates and advantageously an alkali metal silicate, in particular sodium or potassium silicate.
Le silicate peut présenter une concentration (exprimée en SiO2) comprise entre 40 et 330 g/L, par exemple entre 60 et 300 g/L. The silicate may have a concentration (expressed as SiO 2 ) of between 40 and 330 g / l, for example between 60 and 300 g / l.
De manière générale, on emploie, comme agent acidifiant, l'acide sulfurique, et, comme silicate, le silicate de sodium. In general, sulfuric acid is used as acidifying agent and sodium silicate as silicate.
Dans le cas où l'on utilise le silicate de sodium, celui-ci présente, en général, un rapport pondéral SiO2/Na2O compris entre 2,5 et 4, par exemple entre 3,1 et 3,8. In the case where sodium silicate is used, it generally has a weight ratio SiO 2 / Na 2 O of between 2.5 and 4, for example between 3.1 and 3.8.
La réaction du silicate avec l'agent acidifiant se fait d'une manière spécifique selon les étapes suivantes. The reaction of the silicate with the acidifying agent is in a specific manner according to the following steps.
On forme tout d'abord un pied de cuve qui comprend du silicate ainsi qu'un électrolyte (étape (i)). La quantité de silicate présente dans le pied de cuve initial ne représente avantageusement qu'une partie de la quantité totale de silicate engagée dans la réaction. Firstly, a stock is formed which comprises silicate and an electrolyte (step (i)). The amount of silicate present in the initial stock is advantageously only a part of the total amount of silicate involved in the reaction.
Le terme électrolyte s'entend ici dans son acceptation normale, c'est-à-dire qu'il signifie toute substance ionique ou moléculaire qui, lorsqu'elle est en solution, se décompose ou se dissocie pour former des ions ou des particules
chargées. On peut citer comme électrolyte un sel du groupe des sels des métaux alcalins et alcalino-terreux, notamment le sel du métal de silicate de départ et de l'agent acidifiant, par exemple le chlorure de sodium dans le cas de la réaction d'un silicate de sodium avec l'acide chlorhydrique ou, de préférence, le sulfate de sodium dans le cas de la réaction d'un silicate de sodium avec l'acide sulfurique. The term electrolyte is understood here in its normal acceptation, that is to say that it means any ionic or molecular substance which, when in solution, decomposes or dissociates to form ions or particles. loaded. As electrolyte, mention may be made of a salt of the group of alkali and alkaline earth metal salts, in particular the salt of the starting silicate metal and of the acidifying agent, for example sodium chloride in the case of the reaction of a sodium silicate with hydrochloric acid or, preferably, sodium sulfate in the case of the reaction of a sodium silicate with sulfuric acid.
La concentration en électrolyte dans le pied de cuve initial est (supérieure à 0 g/L et) inférieure à 17 g/L, par exemple inférieure à 14 g/L. The concentration of electrolyte in the initial stock is (greater than 0 g / L and) less than 17 g / l, for example less than 14 g / l.
La concentration en silicate (exprimée en SiO2) dans le pied de cuve initial est (supérieure à 0 g/L et) inférieure à 100 g/L ; de préférence, cette concentration est inférieure à 90 g/L, notamment inférieure à 85 g/L. The silicate concentration (expressed in SiO 2 ) in the initial stock is (greater than 0 g / L and) less than 100 g / L; preferably, this concentration is less than 90 g / l, especially less than 85 g / l.
La deuxième étape consiste à ajouter l'agent acidifiant dans le pied de cuve de composition décrite plus haut (étape (ii)). The second step consists in adding the acidifying agent to the stock base composition described above (step (ii)).
Cette addition qui entraîne une baisse corrélative du pH du milieu réactionnel se fait jusqu'à ce qu'on atteigne une valeur du pH d'au moins 7, généralement comprise entre 7 et 8. This addition, which causes a correlative drop in the pH of the reaction medium, is carried out until a pH value of at least 7, generally between 7 and 8, is reached.
Une fois qu'est atteinte la valeur souhaitée de pH, on procède alors à une addition simultanée (étape (Ni)) d'agent acidifiant et de silicate. Once the desired pH value is reached, then a simultaneous addition (step (Ni)) of acidifying agent and silicate is carried out.
Cette addition simultanée est généralement réalisée de manière telle que la valeur du pH du milieu réactionnel soit constamment égale (à +/- 0,1 près) à celle atteinte à l'issue de l'étape (ii). This simultaneous addition is generally carried out in such a way that the pH value of the reaction medium is constantly equal (within +/- 0.1) to that reached at the end of step (ii).
Ce procédé de préparation comprend une des trois opérations (a), (b) ou (c) mentionnées précédemment, c'est-à-dire : This preparation method comprises one of the three operations (a), (b) or (c) mentioned above, that is to say:
(a) on ajoute, après l'étape (iii), au milieu réactionnel au moins un composé A de l'aluminium et, ensuite ou simultanément, un agent basique, la séparation, mise en œuvre dans le procédé, comportant de préférence une filtration et un délitage du gâteau issu de cette filtration, ledit délitage étant alors de préférence effectué en présence d'au moins un composé B de l'aluminium, (a) after step (iii), at least one aluminum compound A is added to the reaction medium and, subsequently or simultaneously, a basic agent, the separation, which is carried out in the process, preferably comprising filtration and disintegration of the cake resulting from this filtration, said disintegration then preferably being carried out in the presence of at least one compound B of aluminum,
(b) on ajoute, après l'étape (iii) ou à la place de l'étape (iii), au milieu réactionnel simultanément un silicate et au moins un composé A de l'aluminium, la séparation, mise en œuvre dans le procédé, comportant de préférence une filtration et un délitage du gâteau issu de cette filtration, le délitage étant alors de préférence effectué en présence d'au moins un composé B de l'aluminium, ou
(c) lors de l'étape (Ni), on ajoute au milieu réactionnel simultanément de l'agent acidifiant, un silicate et au moins un composé B de l'aluminium, la séparation, mise en œuvre dans le procédé, comportant de préférence une filtration et un délitage du gâteau issu de cette filtration, le délitage étant alors éventuellement effectué en présence d'au moins un composé B de l'aluminium. (b) after step (iii) or in place of step (iii), a silicate and at least one aluminum compound A are added to the reaction medium simultaneously, the separation, which is carried out in the process, preferably comprising a filtration and a disintegration of the cake resulting from this filtration, the disintegration then being preferably carried out in the presence of at least one compound B of aluminum, or (c) during step (Ni), acidifying agent, a silicate and at least one aluminum compound B are added to the reaction medium simultaneously, the separation, used in the process, preferably comprising filtration and disintegration of the cake resulting from this filtration, the disintegration then being optionally carried out in the presence of at least one compound B of aluminum.
Dans une première variante de ce procédé de préparation (c'est-à-dire lorsque celui-ci comprend l'opération (a)), on effectue avantageusement, après avoir réalisé la précipitation selon les étapes (i), (ii) et (iii) décrites précédemment, les étapes suivantes : In a first variant of this preparation process (that is to say when it comprises the operation (a)), it is advantageous, after carrying out the precipitation according to steps (i), (ii) and (iii) previously described, the following steps:
(iv) on ajoute au milieu réactionnel (c'est-à-dire à la suspension ou bouillie réactionnelle obtenue) au moins un composé A de l'aluminium, (iv) adding to the reaction medium (that is to say to the suspension or reaction mixture obtained) at least one aluminum compound A,
(v) on ajoute au milieu réactionnel un agent basique, de préférence jusqu'à l'obtention d'une valeur du pH du milieu réactionnel comprise entre 6,5 et 10, en particulier entre 7,2 et 8,6, puis (v) a basic agent is added to the reaction medium, preferably until a pH value of the reaction medium of between 6.5 and 10 is obtained, in particular between 7.2 and 8.6, and then
(vi) on ajoute au milieu réactionnel de l'agent acidifiant, de préférence jusqu'à l'obtention d'une valeur du pH du milieu réactionnel comprise entre 3 et 5, en particulier entre 3,4 et 4,5. (vi) acidifying agent is added to the reaction medium, preferably until a pH value of the reaction medium of between 3 and 5, in particular between 3.4 and 4.5, is obtained.
L'étape (v) peut être réalisée simultanément ou, de préférence, après l'étape (iv). Step (v) may be performed simultaneously or, preferably, after step (iv).
On peut effectuer, après l'addition simultanée de l'étape (iii), un mûrissement du milieu réactionnel, ce mûrissement pouvant par exemple durer de 1 à 60 minutes, en particulier de 3 à 30 minutes. After the simultaneous addition of step (iii), the reaction medium may be cured, this curing may for example last from 1 to 60 minutes, in particular from 3 to 30 minutes.
Dans cette première variante, il peut être souhaitable, entre l'étape (iii) et l'étape (iv), et notamment avant ledit mûrissement éventuel, d'ajouter au milieu réactionnel une quantité supplémentaire d'agent acidifiant. Cette addition se fait généralement jusqu'à l'obtention d'une valeur du pH du milieu réactionnel comprise entre 3 et 6,5, en particulier entre 4 et 6. In this first variant, it may be desirable, between step (iii) and step (iv), and in particular before said optional maturing, to add to the reaction medium an additional amount of acidifying agent. This addition is generally carried out until a pH value of the reaction medium of between 3 and 6.5, in particular between 4 and 6, is obtained.
L'agent acidifiant utilisé lors de cette addition est généralement identique à celui employé lors des étapes (ii), (iii) et (vi) de la première variante du procédé. The acidifying agent used during this addition is generally identical to that used in steps (ii), (iii) and (vi) of the first variant of the process.
Un mûrissement du milieu réactionnel est habituellement effectué entre l'étape (v) et l'étape (vi), par exemple pendant 2 à 60 minutes, en particulier pendant 5 à 45 minutes.
De même, un mûrissement du milieu réactionnel est le plus souvent effectué après l'étape (vi), par exemple pendant 2 à 60 minutes, en particulier pendant 5 à 30 minutes. Ripening of the reaction medium is usually carried out between step (v) and step (vi), for example for 2 to 60 minutes, in particular for 5 to 45 minutes. Similarly, a ripening of the reaction medium is most often carried out after step (vi), for example for 2 to 60 minutes, in particular for 5 to 30 minutes.
L'agent basique utilisé lors de l'étape (v) peut être une solution d'ammoniaque ou, de préférence, une solution d'hydroxyde de sodium (ou soude). The basic agent used in step (v) may be an ammonia solution or, preferably, a solution of sodium hydroxide (or sodium hydroxide).
Dans une deuxième variante dudit procédé (c'est-à-dire lorsque celui-ci comprend l'opération (b)), on effectue, après les étapes (i), (ii) et (iii) décrites précédemment ou à la place de l'étape (iii) décrite précédemment, une étape (iv) qui consiste à ajouter au milieu réactionnel simultanément un silicate et au moins un composé A de l'aluminium. In a second variant of said method (that is to say when it comprises operation (b)), after steps (i), (ii) and (iii) described above, or in place of of step (iii) described above, a step (iv) which consists in adding to the reaction medium simultaneously a silicate and at least one compound A of aluminum.
Seulement dans le cas où le composé A de l'aluminium est suffisamment acide (par exemple cela peut être le cas lorsque ce composé A est un sulfate d'aluminium), il est en effet possible (mais pas obligatoire) de substituer l'étape (iii) par l'étape (iv), ce qui signifie en fait que l'étape (iii) et l'étape (iv) ne forment alors plus qu'une seule étape, le composé A de l'aluminium jouant alors le rôle d'agent acidifiant. Only in the case where the compound A of aluminum is sufficiently acidic (for example this may be the case when this compound A is an aluminum sulphate), it is indeed possible (but not obligatory) to substitute the step (iii) by step (iv), which in fact means that step (iii) and step (iv) then form only one step, the compound A of aluminum then playing the role of acidifying agent.
L'addition simultanée de l'étape (iv) est généralement réalisée de manière telle que la valeur du pH du milieu réactionnel soit constamment égale (à +/- 0,1 près) à celle atteinte à l'issue de l'étape (iii) ou de l'étape (ii). The simultaneous addition of step (iv) is generally carried out in such a way that the pH value of the reaction medium is constantly equal (within +/- 0.1) to that reached at the end of the step ( iii) or step (ii).
On peut effectuer, après l'addition simultanée de l'étape (iv), un mûrissement du milieu réactionnel, ce mûrissement pouvant par exemple durer de 2 à 60 minutes, en particulier de 5 à 30 minutes. It is possible, after the simultaneous addition of step (iv), to ripen the reaction medium, which curing may for example last from 2 to 60 minutes, in particular from 5 to 30 minutes.
Dans cette deuxième variante, il peut être souhaitable, après l'étape (iv), et notamment après ce mûrissement éventuel, d'ajouter au milieu réactionnel une quantité supplémentaire d'agent acidifiant. Cette addition se fait généralement jusqu'à l'obtention d'une valeur du pH du milieu réactionnel comprise entre 3 et 6,5, en particulier entre 4 et 6. In this second variant, it may be desirable, after step (iv), and in particular after this optional ripening, to add to the reaction medium an additional quantity of acidifying agent. This addition is generally carried out until a pH value of the reaction medium of between 3 and 6.5, in particular between 4 and 6, is obtained.
L'agent acidifiant utilisé lors de cette addition est généralement identique à celui employé lors de l'étape (ii) de la deuxième variante du procédé.
Un mûrissement du milieu réactionnel est habituellement effectué après cette addition d'agent acidifiant, par exemple pendant 1 à 60 minutes, en particulier pendant 3 à 30 minutes. The acidifying agent used during this addition is generally identical to that used in step (ii) of the second variant of the process. Ripening of the reaction medium is usually carried out after this addition of acidifying agent, for example for 1 to 60 minutes, in particular for 3 to 30 minutes.
Le composé A de l'aluminium employé dans le procédé de préparation (en particulier dans les deux premières variantes mentionnées) est en général un sel organique ou inorganique de l'aluminium. The aluminum compound A used in the preparation process (especially in the first two variants mentioned) is generally an organic or inorganic salt of aluminum.
A titre d'exemples de sel organique, on peut citer notamment les sels d'acides carboxyliques ou polycarboxyliques, comme les sels d'acide acétique, citrique, tartrique ou oxalique. As examples of organic salt, mention may be made in particular of carboxylic or polycarboxylic acid salts, such as the salts of acetic, citric, tartaric or oxalic acid.
A titre d'exemples de sel inorganique, on peut citer notamment les halogénures et les oxyhalogénures (comme les chlorures, les oxychlorures), les nitrates, les phosphates, les sulfates et les oxysulfates. As examples of inorganic salt, mention may in particular be made of halides and oxyhalides (such as chlorides, oxychlorides), nitrates, phosphates, sulphates and oxysulphates.
Dans la pratique, le composé A de l'aluminium peut être utilisé sous la forme d'une solution, en général aqueuse. In practice, compound A of aluminum may be used in the form of a solution, generally aqueous.
De préférence, on emploie à titre de composé A de l'aluminium un sulfate d'aluminium. Aluminum compound A is preferably used as aluminum compound A.
Dans une troisième variante de ce procédé de préparation (c'est-à-dire lorsque celui-ci comprend l'opération (c)), on effectue avantageusement, après avoir réalisé les étapes (i) et (ii) décrites précédemment, une étape (iii) qui consiste à ajouter au milieu réactionnel simultanément de l'agent acidifiant, un silicate et au moins un composé B de l'aluminium. In a third variant of this preparation method (that is to say when it comprises the operation (c)), it is advantageous to carry out, after carrying out the steps (i) and (ii) described above, a step (iii) which consists in adding to the reaction medium simultaneously with the acidifying agent, a silicate and at least one compound B of aluminum.
Cette addition simultanée est généralement réalisée de manière telle que la valeur du pH du milieu réactionnel soit constamment égale (à +/- 0,1 près) à celle atteinte à l'issue de l'étape (ii). This simultaneous addition is generally carried out in such a way that the pH value of the reaction medium is constantly equal (within +/- 0.1) to that reached at the end of step (ii).
Dans cette troisième variante, il peut être souhaitable, après l'étape (iii), d'ajouter au milieu réactionnel une quantité supplémentaire d'agent acidifiant. Cette addition se fait généralement jusqu'à l'obtention d'une valeur du pH du milieu réactionnel comprise entre 3 et 6,9, en particulier entre 4 et 6,6. In this third variant, it may be desirable, after step (iii), to add to the reaction medium an additional amount of acidifying agent. This addition is generally done until a pH value of the reaction medium of between 3 and 6.9, in particular between 4 and 6.6, is obtained.
L'agent acidifiant utilisé lors de cette addition est généralement identique à celui employé lors des étapes (ii) et (iii).
Un mûrissement du milieu réactionnel est habituellement effectué après cette addition d'agent acidifiant, par exemple pendant 1 à 60 minutes, en particulier pendant 3 à 30 minutes. The acidifying agent used during this addition is generally identical to that used in steps (ii) and (iii). Ripening of the reaction medium is usually carried out after this addition of acidifying agent, for example for 1 to 60 minutes, in particular for 3 to 30 minutes.
Le composé B de l'aluminium employé dans la troisième variante est, en général, un aluminate de métal alcalin, notamment de potassium ou, de manière préférée, de sodium. The compound B of the aluminum employed in the third variant is, in general, an alkali metal aluminate, in particular potassium or, preferably, sodium.
La température du milieu réactionnel est généralement comprise entre 70 et 98 °C. The temperature of the reaction medium is generally between 70 and 98 ° C.
Selon une variante, la réaction est effectuée à une température constante comprise entre 75 et 96 °C. According to one variant, the reaction is carried out at a constant temperature of between 75 and 96 ° C.
Selon une autre variante (préférée), la température de fin de réaction est plus élevée que la température de début de réaction : ainsi, on maintient la température au début de la réaction de préférence entre 70 et 96 °C, puis on augmente la température en quelques minutes, de préférence jusqu'à une valeur comprise entre 80 et 98 °C, valeur à laquelle elle est maintenue jusqu'à la fin de la réaction ; les opérations (a) ou (b) sont ainsi habituellement effectuées à cette valeur constante de température. According to another (preferred) variant, the end-of-reaction temperature is higher than the reaction start temperature: thus, the temperature at the start of the reaction is preferably maintained between 70 and 96 ° C., and then the temperature is raised. in a few minutes, preferably to a value between 80 and 98 ° C, the value at which it is maintained until the end of the reaction; the operations (a) or (b) are thus usually performed at this constant temperature value.
On obtient, à l'issue des étapes qui viennent d'être décrites, une bouillie de silice qui est ensuite séparée (séparation liquide-solide). At the end of the steps which have just been described, a silica slurry is obtained which is then separated (liquid-solid separation).
En général, cette séparation comporte une filtration (suivie d'un lavage si nécessaire) et un délitage, ledit délitage pouvant être alors (de préférence dans le cas des deux premières variantes mentionnées, éventuellement dans le cas de la troisième variante) effectué en présence d'au moins un composé B de l'aluminium et, éventuellement, en présence d'un agent acidifiant tel que décrit précédemment (dans ce dernier cas, le composé B de l'aluminium et l'agent acidifiant sont avantageusement ajoutés de manière simultanée). In general, this separation comprises a filtration (followed by a washing if necessary) and a disintegration, said disintegration can be then (preferably in the case of the first two variants mentioned, possibly in the case of the third variant) carried out in the presence at least one aluminum compound B and, optionally, in the presence of an acidifying agent as described above (in the latter case, the compound B of the aluminum and the acidifying agent are advantageously added simultaneously ).
L'opération de délitage, qui peut être réalisée mécaniquement, par exemple par passage du gâteau de filtration dans un broyeur de type colloïdal ou à billes, permet notamment d'abaisser la viscosité de la suspension à sécher (en particulier à atomiser) ultérieurement.
Le composé B de l'aluminium est habituellement différent du composé A de l'aluminium mentionné précédemment et consiste, en général, en un aluminate de métal alcalin, notamment de potassium ou, de manière préférée, de sodium. The disintegration operation, which can be carried out mechanically, for example by passing the filter cake in a colloidal or ball mill, notably makes it possible to lower the viscosity of the suspension to be dried (in particular to be atomized) subsequently. The aluminum compound B is usually different from the aluminum compound A mentioned above and generally consists of an alkali metal aluminate, especially potassium or, preferably, sodium aluminate.
Les quantités de composés A et B de l'aluminium utilisées dans ce procédé de préparation sont telles que la silice précipitée obtenue possède plus de 0,5 % en poids d'aluminium, et en particulier une quantité préférée d'aluminium telle que mentionnée plus haut. The amounts of aluminum compounds A and B used in this preparation process are such that the precipitated silica obtained has more than 0.5% by weight of aluminum, and in particular a preferred amount of aluminum as mentioned above. high.
La séparation mise en œuvre dans ce procédé comprend habituellement une filtration (avec un lavage si nécessaire) effectuée au moyen de toute méthode convenable, par exemple au moyen d'un filtre à bande, d'un filtre sous vide ou, de préférence, d'un filtre presse. The separation carried out in this process usually comprises filtration (with washing if necessary) carried out using any suitable method, for example by means of a belt filter, a vacuum filter or, preferably, a filter. a filter press.
La suspension de silice précipitée ainsi récupérée (gâteau de filtration) est ensuite séchée. The precipitated silica suspension thus recovered (filter cake) is then dried.
Dans ce procédé de préparation, cette suspension doit présenter immédiatement avant son séchage un taux de matière sèche d'au plus 24 % en poids, de préférence d'au plus 22 % en poids. In this preparation process, this suspension must present immediately before drying a dry matter content of at most 24% by weight, preferably at most 22% by weight.
Ce séchage peut se faire selon tout moyen connu en soi. This drying can be done by any means known per se.
De préférence, le séchage se fait par atomisation. A cet effet, on peut utiliser tout type d'atomiseur convenable, notamment un atomiseur à turbines, à buses, à pression liquide ou à deux fluides. En général, lorsque la filtration est effectuée à l'aide d'un filtre presse, on utilise un atomiseur à buses, et, lorsque la filtration est effectuée à l'aide d'un filtre sous-vide, on utilise un atomiseur à turbines. Preferably, the drying is done by atomization. For this purpose, any suitable type of atomizer may be used, such as a turbine, nozzle, liquid pressure or two-fluid atomizer. In general, when the filtration is carried out using a filter press, a nozzle atomizer is used, and when the filtration is carried out using a vacuum filter, a turbine atomizer is used. .
Lorsque le séchage est effectué à l'aide d'un atomiseur à buses, la silice précipitée susceptible d'être alors obtenue se présente habituellement sous forme de billes sensiblement sphériques. When the drying is carried out using a nozzle atomizer, the precipitated silica that can then be obtained is usually in the form of substantially spherical beads.
A l'issue de ce séchage, on peut éventuellement procéder à une étape de broyage sur le produit récupéré ; la silice précipitée susceptible d'être alors obtenue se présente généralement sous forme d'une poudre. At the end of this drying, it may optionally proceed to a grinding step on the recovered product; the precipitated silica that can then be obtained is generally in the form of a powder.
Lorsque le séchage est effectué à l'aide d'un atomiseur à turbines, la silice précipitée susceptible d'être alors obtenue peut se présenter sous la forme d'une poudre.
Enfin, le produit séché (notamment par un atomiseur à turbines) ou broyé tel qu'indiqué précédemment peut éventuellement être soumis à une étape d'agglomération, qui consiste par exemple en une compression directe, une granulation voie humide (c'est-à-dire avec utilisation d'un liant tel que eau, suspension de silice ...), une extrusion ou, de préférence, un compactage à sec. Lorsque l'on met en œuvre cette dernière technique, il peut s'avérer opportun, avant de procéder au compactage, de désaérer (opération appelée également pré-densification ou dégazage) les produits pulvérulents de manière à éliminer l'air inclus dans ceux-ci et assurer un compactage plus régulier. When the drying is carried out using a turbine atomizer, the precipitated silica that may then be obtained may be in the form of a powder. Finally, the dried product (in particular by a turbine atomizer) or milled as indicated above may optionally be subjected to an agglomeration step, which consists, for example, of a direct compression, a wet-path granulation (that is, with the use of a binder such as water, silica suspension, etc.), extrusion or, preferably, dry compaction. When the latter technique is used, it may be advisable, before compacting, to deaerate (operation also called pre-densification or degassing) the pulverulent products so as to eliminate the air included in these products. ci and ensure a more regular compaction.
La silice précipitée susceptible d'être alors obtenue par cette étape d'agglomération se présente généralement sous la forme de granulés. The precipitated silica that can then be obtained by this agglomeration step is generally in the form of granules.
Le 3-acryloxy-propyltriethoxysilane (ou γ-acryloxy-propyltriethoxysilane), employé dans l'invention comme agent de couplage charge inorganique - élastomère, peut être préparé par un procédé tel que décrit dans US-A-3179612, à partir de l'acrylate d'allyle et du triethoxysilane. The 3-acryloxypropyltriethoxysilane (or γ-acryloxypropyltriethoxysilane) used in the invention as an inorganic filler-elastomer coupling agent can be prepared by a process as described in US-A-3179612, starting from US Pat. allyl acrylate and triethoxysilane.
La silice précipitée contenant de l'aluminium utilisée selon la présente invention comme charge inorganique renforçante et le 3-acryloxy- propyltriethoxysilane utilisé selon la présente invention comme agent de couplage charge inorganique renforçante - élastomère peuvent être mélangés ensemble préalablement à leur utilisation. Une première variante consiste en ce que le 3-acryloxy-propyltriethoxysilane ne soit pas greffé sur ladite silice précipitée ; une seconde variante consiste en ce que le 3-acryloxy- propyltriethoxysilane soit greffé sur ladite silice précipitée qui se retrouvera ainsi « précouplée » avant son mélange avec la composition d'élastomère(s). The aluminum-containing precipitated silica used according to the present invention as the reinforcing inorganic filler and the 3-acryloxypropyltriethoxysilane used according to the present invention as the reinforcing inorganic filler-elastomer coupling agent may be mixed together prior to their use. A first variant is that the 3-acryloxypropyltriethoxysilane is not grafted onto said precipitated silica; a second variant is that the 3-acryloxypropyltriethoxysilane is grafted onto said precipitated silica which will thus be "pre-coupled" before mixing with the elastomer composition (s).
Il est possible d'employer tout ou partie du 3-acryloxy-propyltriethoxysilane utilisé selon l'invention à titre d'agent de couplage sous forme supportée (la mise sur support étant réalisée préalablement à son utilisation) sur un solide compatible avec sa structure chimique, ce support solide pouvant être par
exemple du noir de carbone ou, de préférence, de la silice précipitée contenant de l'aluminium utilisée selon la présente invention. It is possible to use all or part of the 3-acryloxypropyltriethoxysilane used according to the invention as a coupling agent in supported form (the setting is carried out prior to its use) on a solid compatible with its chemical structure. , this solid support that can be for example, carbon black or, preferably, precipitated aluminum-containing silica used in accordance with the present invention.
Les compositions d'élastomère(s) dans lesquelles est employé selon l'invention le 3-acryloxy-propyltriethoxysilane peuvent contenir au moins un agent de recouvrement de la silice précipitée utilisée à titre de charge renforçante. Cet agent de recouvrement est susceptible, de manière connue, d'améliorer la faculté de mise en œuvre des compositions d'élastomère(s) à l'état cru. The elastomer compositions in which 3-acryloxypropyltriethoxysilane is used according to the invention may contain at least one precipitated silica covering agent used as a reinforcing filler. This covering agent is capable, in a known manner, of improving the processability of the elastomer compositions in the green state.
Un tel agent de recouvrement peut consister par exemple en un alkylalkoxysilane (en particulier un alkyltriéthoxysilane), un polyol, un polyéther (notamment un polyéthylèneglycol), un polyétheramine, une aminé primaire, secondaire ou tertiaire (en particulier une trialcanol-amine), un polydiméthylsiloxane α,ω-dihydroxylé ou un polydiméthylsiloxane α,ω-diaminé. Such a coating agent may consist, for example, of an alkylalkoxysilane (in particular an alkyltriethoxysilane), a polyol, a polyether (in particular a polyethylene glycol), a polyetheramine, a primary, secondary or tertiary amine (in particular a trialkanol amine), a α, ω-dihydroxylated polydimethylsiloxane or an α, ω-diamine polydimethylsiloxane.
Cet agent de recouvrement peut éventuellement être mélangé avec ladite silice précipitée et le 3-acryloxy-propyltriethoxysilane préalablement à leur utilisation. This coating agent may optionally be mixed with said precipitated silica and 3-acryloxypropyltriethoxysilane prior to their use.
Les compositions d'élastomère(s) dans lesquelles sont utilisés selon l'invention le 3-acryloxy-propyltriethoxysilane et la silice précipitée décrits ci- dessus peuvent éventuellement comprendre au moins un autre agent de couplage charge inorganique - élastomère, en particulier un silane sulfuré ou polysulfuré. The elastomer compositions in which the 3-acryloxypropyltriethoxysilane and the precipitated silica described above are used according to the invention may optionally comprise at least one other inorganic filler-elastomer coupling agent, in particular a sulphurised silane. or polysulfide.
On peut citer comme exemples d'un tel agent de couplage : Examples of such a coupling agent are:
- le disulfure de bis-triéthoxysilylpropyle (en abrégé TESPD) de formule : bis-triethoxysilylpropyl disulphide (abbreviated TESPD) of formula:
(C2H5O)3Si-(CH2)3-S2-(CH2)3-Si(OC2H5)3 (C2H5O) 3Si- (CH 2 ) 3 -S 2 - (CH 2 ) 3 -Si (OC 2 H 5 ) 3
- le tétrasulfure de bis-triéthoxysilylpropyle (en abrégé TESPT) de formule : bis-triethoxysilylpropyl tetrasulfide (abbreviated TESPT) of formula:
(C2H5O)3Si-(CH2)3-S4-(CH2)3-Si(OC2H5)3 (C 2 H 5 O) 3Si- (CH 2 ) 3 -S 4 - (CH 2 ) 3 -Si (OC 2 H 5 ) 3
- le tétrasulfure de bis- monohydroxydiméthylsilylpropyle de formule : bis-monohydroxydimethylsilylpropyl tetrasulfide of formula:
(HO)(CH3)2Si-(CH2)3-S4-(CH2)3-Si(CH3)2(OH) (HO) (CH 3 ) 2 Si- (CH 2 ) 3 -S 4 - (CH 2 ) 3 -Si (CH 3 ) 2 (OH)
- le disulfure de bis-monoéthoxydiméthylsilylpropyle (en abrégé MESPD) de formule : bis-monoethoxydimethylsilylpropyl disulfide (abbreviated as MESPD) of formula:
(C2H5O)(CH3)2Si-(CH2)3-S2-(CH2)3-Si(CH3)2(OC2H5)
- le tétrasulfure de bis-monoéthoxydinnéthylsilylpropyle (en abrégé MESPT) de formule : (C 2 H 5 O) (CH 3) 2 Si- (CH 2 ) 3 -S 2 - (CH 2 ) 3 -Si (CH 3) 2 (OC 2 H 5 ) bis-monoethoxydinethylsilylpropyl tetrasulfide (abbreviated as MESPT) of formula:
(C2H5O)(CH3)2Si-(CH2)3-S4-(CH2)3-Si(CH3)2(OC2H5) (C2H5O) (CH3) 2Si- (CH 2 ) 3 -S 4 - (CH 2 ) 3 -Si (CH 3) 2 (OC 2 H 5)
- le tétrasulfure de bis-monoéthoxydiméthylsilylisopropyle (en abrégé MESiPrT) de formule : bis-monoethoxydimethylsilylisopropyl tetrasulfide (abbreviated to MESiPrT) of formula:
(C2H5O)(CH3)2Si-CH2-CH-(CH3)-S4-(CH3)-CH-CH2-Si(CH3)2(OC2H5) (C 2 H 5 O) (CH 3) 2 Si-CH 2 -CH- (CH 3) -S 4 - (CH 3) -CH-CH 2 -Si (CH 3) 2 (OC 2 H 5 )
Cependant, de manière préférée, lesdites compositions d'élastomère(s) ne contiennent pas d'autre agent de couplage charge inorganique - élastomère que le 3-acryloxy-propyltriethoxysilane. However, preferably, said elastomer compositions (s) do not contain any other inorganic filler-elastomer coupling agent other than 3-acryloxypropyltriethoxysilane.
L'utilisation selon l'invention peut éventuellement être réalisée en présence d'un initiateur de radicaux libres (par exemple de 0,02 à 5 %, notamment de 0,05 à 0;5 %, en poids par rapport à la quantité en poids d'élastomère(s)), c'est-à-dire d'un composé (notamment organique) susceptible, notamment suite à une activation énergétique, de générer des radicaux libres in situ, dans son milieu environnant, en l'occurrence dans l'(les) élastomère(s). L'initiateur de radicaux libres est alors ici un initiateur du type à amorçage thermique, c'est-à-dire que l'apport d'énergie, pour la création de radicaux libres, se fait sous forme thermique. Sa température de décomposition doit généralement être inférieure à 180 °C, en particulier inférieure à 160 °C. The use according to the invention may optionally be carried out in the presence of a free radical initiator (for example from 0.02 to 5%, in particular from 0.05 to 0.5%, by weight relative to the amount in question. weight of elastomer (s)), that is to say of a compound (especially organic compound) susceptible, in particular following energetic activation, to generate free radicals in situ, in its surrounding environment, in this case in the elastomer (s). The initiator of free radicals is here an initiator of the type with thermal initiation, that is to say that the energy supply, for the creation of free radicals, is in thermal form. Its decomposition temperature should generally be below 180 ° C, in particular below 160 ° C.
Il est par exemple choisi dans le groupe constitué par les péroxydes organiques, les hydropéroxydes organiques, les composés azido, les composés bis(azo), les peracides, les peresters ou un mélange d'au moins deux de ces composés. C'est en particulier un péroxyde organique, par exemple le péroxyde de benzoyie, le péroxyde d'acétyle, le péroxyde de lauryle, le péroxyde de 1 ,1 bis(t-butyl)-3,3,5-triméthylcyclohexane, le péroxyde étant éventuellement mis sur un support solide, tel que le carbonate de calcium. It is for example chosen from the group consisting of organic peroxides, organic hydroperoxides, azido compounds, bis (azo) compounds, peracids, peresters or a mixture of at least two of these compounds. It is in particular an organic peroxide, for example benzoyl peroxide, acetyl peroxide, lauryl peroxide, peroxide of 1, 1 bis (t-butyl) -3,3,5-trimethylcyclohexane, peroxide optionally being placed on a solid support, such as calcium carbonate.
Cependant, de manière préférée, l'invention est mise en œuvre en l'absence de tout initiateur de radicaux libres.
La composition d'élastomère(s) employée dans l'invention peut, de manière avantageuse, ne pas comprendre d'autres élastomères que l'(les) élastomère(s) isoprénique(s) qu'elle contient. However, preferably, the invention is implemented in the absence of any free radical initiator. The elastomer composition (s) employed in the invention may advantageously not comprise other elastomers than the isoprene elastomer (s) it contains.
Elle peut éventuellement (variante non préférée) comprendre au moins un élastomère autre qu'isoprénique. En particulier, elle peut éventuellement comprendre au moins un élastomère isoprénique (par exemple du caoutchouc naturel) et au moins un élastomère diénique autre qu'isoprénique, la quantité d'élastomère(s) isoprénique(s) par rapport à la quantité totale d'élastomère(s) étant alors, de préférence, supérieure à 50 % (en général inférieure à 99,5 %, et par exemple comprise entre 70 et 99 %) en poids. It may optionally (non-preferred variant) comprise at least one elastomer other than isoprene. In particular, it may optionally comprise at least one isoprene elastomer (for example natural rubber) and at least one diene elastomer other than isoprene, the amount of isoprene elastomer (s) relative to the total amount of elastomer (s) then being preferably greater than 50% (generally less than 99.5%, and for example between 70 and 99%) by weight.
La composition d'élastomère(s) mise en œuvre selon l'invention comprend généralement au moins un élastomère isoprénique (naturel ou synthétique) choisi parmi : The elastomer composition (s) used according to the invention generally comprises at least one isoprene elastomer (natural or synthetic) chosen from:
(1 ) les polyisoprènes de synthèse obtenus par homopolymérisation de l'isoprène ou méthyl-2 butadiène-1 ,3 ; (1) synthetic polyisoprenes obtained by homopolymerization of isoprene or 2-methyl-1,3-butadiene;
(2) les polyisoprènes de synthèse obtenus par copolymérisation de l'isoprène avec un ou plusieurs monomères insaturés éthyléniquement choisis parmi : (2) synthetic polyisoprenes obtained by copolymerization of isoprene with one or more ethylenically unsaturated monomers chosen from:
(2.1 ) les monomères diènes conjuguées, autres que l'isoprène, ayant de 4 à 22 atomes de carbone, tels que par exemple le butadiène-1 ,3, le diméthyl-2,3 butadiène-1 ,3, le chloro-2 butadiène-1 ,3 (ou chloroprène), le phényl-1 butadiène- 1 ,3, le pentadiène-1 ,3, l'hexadiène-2,4 ; (2.1) conjugated diene monomers, other than isoprene, having from 4 to 22 carbon atoms, such as, for example, butadiene-1,3, 2,3-dimethyl-1,3-butadiene, 2-chloro butadiene-1,3 (or chloroprene), 1-phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene;
(2.2) les monomères vinyles aromatiques ayant de 8 à 20 atomes de carbone, tels que par exemple le styrène, l'ortho-, méta- ou paraméthylstyrène, le mélange commercial "vinyl-toluène", le paratertiobutylstyrène, les méthoxystyrènes, les chlorostyrènes, le vinylmésitylène, le divinylbenzène, le vinylnaphtalène ; (2.2) aromatic vinyl monomers having 8 to 20 carbon atoms, such as, for example, styrene, ortho-, meta- or paramethylstyrene, the commercial "vinyl-toluene" mixture, paratertiobutylstyrene, methoxystyrenes, chlorostyrenes vinylmesitylene, divinylbenzene, vinylnaphthalene;
(2.3) les monomères nitriles vinyliques ayant de 3 à 12 atomes de carbone, tels que par exemple l'acrylonitrile, le méthacrylonitrile ; (2.3) vinyl nitrile monomers having 3 to 12 carbon atoms, such as, for example, acrylonitrile, methacrylonitrile;
(2.4) les monomères esters acryliques dérivés de l'acide acrylique ou de l'acide méthacrylique avec des alcanols ayant de 1 à 12 atomes de carbone, tels que par exemple l'acrylate de méthyle, l'acrylate d'éthyle, l'acrylate de propyle,
l'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate d'éthyl-2 hexyle, le méthacrylate de méthyle, le méthacrylate d'éthyle, le méthacrylate de n-butyle, le méthacrylate d'isobutyle ; (2.4) acrylic ester monomers derived from acrylic acid or methacrylic acid with alkanols having from 1 to 12 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate;
(2.5) un mélange d'au moins deux des monomères précités (2.1 ) à (2.4) ; les polyisoprènes copolymères contenant entre 20 et 99 % en poids d'unités isopréniques et entre 80 et 1 % en poids d'unités diéniques, vinyles aromatiques, nitriles vinyliques et/ou esters acryliques, et consistant par exemple dans le poly(isoprène-butadiène), le poly(isoprène-styrène) et le poly(isoprène- butadiène-styrène) ; (2.5) a mixture of at least two of the aforementioned monomers (2.1) to (2.4); the copolymeric polyisoprenes containing between 20 and 99% by weight of isoprenic units and between 80 and 1% by weight of diene units, aromatic vinyls, vinyl nitriles and / or acrylic esters, and consisting, for example, in poly (isoprene-butadiene) ), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene);
(3) le caoutchouc naturel ; (3) natural rubber;
(4) les copolymères obtenus par copolymérisation d'isobutène et d'isoprène, ainsi que les versions halogénées, en particulier chlorées ou bromées, de ces copolymères ; (4) copolymers obtained by copolymerization of isobutene and isoprene, as well as the halogenated versions, in particular chlorinated or brominated, of these copolymers;
(5) un mélange d'au moins deux des élastomères précités (1 ) à (4) ; (5) a mixture of at least two of the aforementioned elastomers (1) to (4);
(6) un mélange contenant plus de 50 % (de préférence moins de 99,5 %, et par exemple entre 70 et 99 %) en poids d'élastomère précité (1 ) ou (3) et moins de 50 % (de préférence plus de 0,5 %, et par exemple entre 1 et 30 %) en poids d'un ou plusieurs élastomères diéniques autres qu'isopréniques. Par élastomère diénique autre qu'isoprénique, on entend de manière connue en soi notamment : les homopolymères obtenus par polymérisation d'un des monomères diènes conjugués définis ci-dessus au point (2.1 ), comme par exemple le polybutadiène et le polychloroprène ; les copolymères obtenus par copolymérisation d'au moins deux des diènes conjugués précités (2.1 ) entre eux ou par copolymérisation d'un ou plusieurs des diènes conjugués précités (2.1 ) avec un ou plusieurs monomères insaturés précités (2.2), (2.3) et/ou (2.4), comme par exemple le poly(butadiène-styrène) et le poly(butadiène-acrylonitrile) ; les copolymères ternaires obtenus par copolymérisation d'éthylène, d'une cc- oléfine ayant de 3 à 6 atomes de carbone avec un monomère diène non conjugué ayant de 6 à 12 atomes de carbone, comme par exemple les élastomères obtenus à partir d'éthylène, de propylène avec un monomère diène
non conjugué du type précité tel que notamment l'hexadiène-1 ,4, l'héthylidène- norbornène, le dicyclopentadiène (élastomère EPDM). (6) a mixture containing more than 50% (preferably less than 99.5%, and for example 70-99%) by weight of the aforementioned elastomer (1) or (3) and less than 50% (preferably more than 0.5%, and for example between 1 and 30% by weight of one or more diene elastomers other than isoprenic. By diene elastomer other than isoprene, is meant in a manner known per se including: homopolymers obtained by polymerization of one of the conjugated diene monomers defined above in (2.1), such as polybutadiene and polychloroprene; copolymers obtained by copolymerization of at least two of the abovementioned conjugated dienes (2.1) with one another or by copolymerization of one or more of the abovementioned conjugated dienes (2.1) with one or more unsaturated monomers mentioned above (2.2), (2.3) and / or or (2.4), such as poly (butadiene-styrene) and poly (butadiene-acrylonitrile); ternary copolymers obtained by copolymerization of ethylene, a α-olefin having from 3 to 6 carbon atoms with a non-conjugated diene monomer containing from 6 to 12 carbon atoms, for example elastomers obtained from ethylene propylene with a diene monomer unconjugated of the aforementioned type, such as in particular hexadiene-1,4, ethylidene norbornene, dicyclopentadiene (elastomer EPDM).
A titre préférentiel, la composition d'élastomère(s) comprend au moins un élastomère isoprénique choisi parmi : Preferably, the elastomer composition (s) comprises at least one isoprene elastomer chosen from:
(1 ) les polyisoprènes de synthèse homopolymères ; (1) homopolymeric synthetic polyisoprenes;
(2) les polyisoprènes de synthèse copolymères consistant dans le poly(isoprène-butadiène), le poly(isoprène-styrène) et le poly(isoprène- butadiène-styrène) ; (2) the synthetic polyisoprenes copolymers consisting of poly (isoprene-butadiene), poly (isoprene-styrene) and poly (isoprene-butadiene-styrene);
(3) le caoutchouc naturel ; (3) natural rubber;
(4) le caoutchouc butyle ; (4) butyl rubber;
(5) un mélange d'au moins deux des élastomères précités (1 ) à (4) ; (5) a mixture of at least two of the aforementioned elastomers (1) to (4);
(6) un mélange contenant plus de 50 % (de préférence moins de 99,5 %, et par exemple entre 70 et 99 %) en poids d'élastomère précité (1 ) ou (3) et moins de 50 % (de préférence plus de 0,5 %, et par exemple entre 1 et 30 %) en poids d'élastomère diénique autre qu'isoprénique consistant dans le polybutadiène, le polychloroprène, le poly(butadiène-styrène), le poly(butadiène-acrylonitrile) ou un terpolymère (éthylène - propylène - diène monomère non conjugué). (6) a mixture containing more than 50% (preferably less than 99.5%, and for example 70-99%) by weight of the aforementioned elastomer (1) or (3) and less than 50% (preferably more than 0.5%, and for example from 1 to 30% by weight of non-isoprene diene elastomer consisting of polybutadiene, polychloroprene, polybutadiene-styrene, polybutadiene-acrylonitrile or a terpolymer (ethylene - propylene - nonconjugated monomeric diene).
A titre plus préférentiel, la composition d'élastomère(s) comprend au moins un élastomère isoprénique choisi parmi : (1 ) les polyisoprènes de synthèse homopolymères ; (3) le caoutchouc naturel ; (5) un mélange des élastomères précités (1 ) et (3) ; (6) un mélange contenant plus de 50 % (de préférence moins de 99,5 %, et par exemple entre 70 et 99 %) en poids d'élastomère précité (1 ) ou (3) et moins de 50 % (de préférence plus de 0,5 %, et par exemple entre 1 et 30 %) en poids d'élastomère diénique autre qu'isoprénique consistant dans le polybutadiène ou le poly(butadiène-styrène). More preferentially, the elastomer composition (s) comprises at least one isoprene elastomer chosen from: (1) homopolymeric synthetic polyisoprenes; (3) natural rubber; (5) a mixture of the aforementioned elastomers (1) and (3); (6) a mixture containing more than 50% (preferably less than 99.5%, and for example 70-99%) by weight of the aforementioned elastomer (1) or (3) and less than 50% (preferably more than 0.5%, for example from 1 to 30% by weight of diene elastomer other than isoprene, consisting of polybutadiene or polybutadiene-styrene.
Selon une variante très préférée de l'invention, la composition d'élastomère(s) comprend à titre d'élastomère isoprénique au moins du caoutchouc naturel, voire uniquement du caoutchouc naturel. According to a very preferred variant of the invention, the elastomer composition (s) comprises as isoprene elastomer at least natural rubber, or even only natural rubber.
Selon une variante encore plus préférée, la composition d'élastomère(s) comprend à titre d'élastomère(s) uniquement du caoutchouc naturel.
En général, la composition d'élastomère(s) mise en œuvre selon l'invention comprend en outre tout ou partie des autres constituants et additifs auxiliaires habituellement employés dans le domaine des compositions élastomériques. According to an even more preferred variant, the elastomer composition (s) comprises as elastomer (s) only natural rubber. In general, the elastomer composition (s) used according to the invention also comprises all or part of the other constituents and auxiliary additives usually employed in the field of elastomeric compositions.
Ainsi, généralement, elle comprend au moins un composé choisi parmi les agents de vulcanisation (par exemple le soufre ou un composé donneur de soufre (tel qu'un dérivé de thiurame)), les accélérateurs de vulcanisation (par exemple un dérivé de guanidine ou un dérivé de thiazoles), les activateurs de vulcanisation (par exemple l'acide stéarique, le stéarate de zinc et l'oxyde de zinc, qui peut éventuellement être introduit de manière fractionnée au cours de la préparation de la composition), le noir de carbone, les agents protecteurs (notamment les agents antioxydants et/ou les agents antiozonants, tels que par exemple la N-phényl-N'-(diméthyl-1 ,3 butyl)-p-phénylène-diamine), les agents antireversions (tels que par exemple l'hexaméthylène-1 ,6-bis(thiosulfate), le 1 ,3- bis(citraconimidométhyl)benzène), les agents de plastification. Thus, generally, it comprises at least one compound chosen from vulcanizing agents (for example sulfur or a sulfur-donor compound (such as a thiuram derivative)), vulcanization accelerators (for example a guanidine derivative or a thiazole derivative), vulcanization activators (for example, stearic acid, zinc stearate and zinc oxide, which may optionally be introduced in a fractional manner during the preparation of the composition), carbon, protective agents (especially antioxidants and / or antiozonants, such as, for example, N-phenyl-N '- (1,3-dimethylbutyl) -p-phenylenediamine), antireversions (such as for example hexamethylene-1,6-bis (thiosulfate), 1,3-bis (citraconimidomethyl) benzene), plasticizers.
L'utilisation conjointe selon l'invention de la silice précipitée contenant de l'aluminium décrite dans l'exposé précédent et du 3-acryloxy- propyltriethoxysilane peut se faire plus particulièrement dans les semelles de chaussures, les revêtements de sols, les barrières aux gaz, les matériaux ignifugeants, les galets de téléphériques, les joints d'appareils électroménagers, les joints de conduites de liquides ou de gaz, les joints de système de freinage, les tuyaux (flexibles), les gaines (notamment les gaines de câbles), les câbles, les supports de moteur, les bandes de convoyeur, les courroies de transmissions ou, de préférence, les pneumatiques (notamment les bandes de roulement de pneumatiques), de manière avantageuse dans les pneumatiques pour les véhicules poids lourds, en particulier pour les camions. The combined use according to the invention of the aluminum-containing precipitated silica described in the preceding discussion and of 3-acryloxypropyltriethoxysilane can be done more particularly in shoe soles, floor coverings, gas barriers. , fire-retardant materials, ropeway rollers, appliance joints, liquid or gas line joints, braking system joints, hoses, ducts (especially cable ducts), cables, engine supports, conveyor belts, transmission belts or, preferably, tires (in particular tire treads), advantageously in tires for heavy goods vehicles, in particular for trucks.
La composition d'élastomère(s) obtenue selon l'utilisation conforme à l'invention contient une quantité efficace de 3-acryloxy-propyltriethoxysilane. The elastomer composition (s) obtained according to the use according to the invention contains an effective amount of 3-acryloxypropyltriethoxysilane.
Plus particulièrement, les compositions d'élastomères issues de l'invention peuvent comprendre (parties en poids), pour 100 parties d'élastomère(s) isoprénique(s) :
10 à 200 parties, en particulier 20 à 150 parties, notamment 30 à 1 10 parties, par exemple 30 à 75 parties, de silice précipitée contenant de l'aluminium telle que décrite ci-dessus et utilisée comme charge inorganique renforçante ; More particularly, the elastomer compositions resulting from the invention may comprise (parts by weight), per 100 parts of isoprene elastomer (s): 10 to 200 parts, in particular 20 to 150 parts, especially 30 to 10 parts, for example 30 to 75 parts, of precipitated silica containing aluminum as described above and used as reinforcing inorganic filler;
1 à 20 parties, en particulier 2 à 20 parties, notamment 2 à 12 parties, par exemple 2 à 10 parties, de 3-acryloxy-propyltriethoxysilane utilisé comme agent de couplage charge inorganique renforçante - élastomère. 1 to 20 parts, in particular 2 to 20 parts, especially 2 to 12 parts, for example 2 to 10 parts, of 3-acryloxypropyltriethoxysilane used as reinforcing inorganic filler-elastomer coupling agent.
De préférence, la quantité utilisée de 3-acryloxy-propyltriethoxysilane, choisie notamment dans les plages précitées, est déterminée de manière à qu'elle représente en général 1 à 20 %, en particulier 2 à 15 %, par exemple 4 à 12 %, en poids par rapport à la quantité utilisée de la silice précipitée contenant de l'aluminium telle que décrite ci-dessus. Preferably, the amount of 3-acryloxypropyltriethoxysilane used, chosen especially in the abovementioned ranges, is determined so that it generally represents 1 to 20%, in particular 2 to 15%, for example 4 to 12%, by weight relative to the amount used of the precipitated silica containing aluminum as described above.
En général, les quantités totales d'agents de couplage + éventuel agent de recouvrement sont identiques à celles mentionnées ci-dessus lorsque l'on emploie, en plus de l'agent de couplage (3-acryloxy-propyltriethoxysilane) utilisé selon l'invention, un autre agent de couplage (notamment sulfuré ou polysulfuré) et/ou un agent de recouvrement. In general, the total amounts of coupling agents + optional coating agent are identical to those mentioned above when using, in addition to the coupling agent (3-acryloxypropyltriethoxysilane) used according to the invention. another coupling agent (especially sulphide or polysulfide) and / or a covering agent.
La présente invention a pour deuxième objet les compositions d'élastomère(s) décrites ci-dessus, et comprenant donc : The present invention has the second object the elastomer compositions (s) described above, and thus comprising:
- au moins un élastomère isoprénique, at least one isoprene elastomer,
- au moins une charge inorganique renforçante, at least one reinforcing inorganic filler,
- au moins un agent de couplage charge inorganique - élastomère, at least one inorganic filler - elastomer coupling agent,
caractérisée en ce que ladite charge inorganique renforçante et ledit agent de couplage charge inorganique - élastomère sont tels que définis précédemment selon le premier objet de l'invention, c'est-à-dire que ladite charge inorganique renforçante est la silice précipitée contenant de l'aluminium telle que décrite dans l'exposé ci-dessus et ledit agent de couplage charge inorganique - élastomère est le 3-acryloxy-propyltriethoxysilane. characterized in that said reinforcing inorganic filler and said inorganic filler-elastomer coupling agent are as defined above according to the first subject of the invention, that is to say that said reinforcing inorganic filler is precipitated silica containing aluminum as described in the above discussion and said inorganic filler-elastomer coupling agent is 3-acryloxypropyltriethoxysilane.
Tout ce qui a été décrit précédemment dans le cadre de l'utilisation selon le premier objet de l'invention s'applique à ces compositions d'élastomère(s).
Les compositions d'élastomère(s) selon l'invention peuvent être préparées selon tout mode opératoire classique en deux phases. Une première phase (dite non-productive) est une phase de travail thermomécanique à haute température. Elle est suivie d'une seconde phase de travail mécanique (dite productive) à des températures généralement inférieures à 1 10 °C dans laquelle on introduit le système de vulcanisation. All that has been previously described in the context of the use according to the first subject of the invention applies to these elastomer compositions (s). The elastomer compositions according to the invention may be prepared according to any conventional two-phase procedure. A first phase (called non-productive) is a thermomechanical work phase at high temperature. It is followed by a second mechanical working phase (so-called productive) at temperatures generally below 110 ° C. in which the vulcanization system is introduced.
L'invention, prise dans son deuxième objet, concerne les compositions d'élastomère(s) tant à l'état cru (c'est-à-dire avant cuisson) qu'à l'état cuit (c'est- à-dire après réticulation ou vulcanisation). The invention, taken in its second subject, relates to elastomer compositions (s) both in the raw state (that is to say before cooking) and in the cooked state (that is to say before cooking). say after crosslinking or vulcanization).
Les compositions d'élastomère(s) selon l'invention peuvent servir à fabriquer des articles, finis ou semi-finis, comprenant lesdites compositions. The elastomer compositions according to the invention can be used to manufacture finished or semi-finished articles comprising said compositions.
La présente invention a ainsi pour troisième objet des articles comprenant au moins une composition d'élastomère(s) telle que définie ci-dessus, ces articles consistant dans des semelles de chaussures, des revêtements de sols, des barrières aux gaz, des matériaux ignifugeants, des galets de téléphériques, des joints d'appareils électroménagers, des joints de conduites de liquides ou de gaz, des joints de système de freinage, des tuyaux (flexibles), des gaines (notamment des gaines de câbles), des câbles, des supports de moteur, des bandes de convoyeur, des courroies de transmissions, ou, de préférence, des pneumatiques (notamment des bandes de roulement de pneumatiques), avantageusement des pneumatiques pour les véhicules poids lourds, en particulier pour les camions. The present invention thus has for third object articles comprising at least one elastomer composition (s) as defined above, these articles consisting of shoe soles, floor coverings, gas barriers, flame retardant materials , ropeway rollers, appliance gaskets, liquid or gas line joints, braking system seals, hoses (hoses), ducts (especially cable ducts), cables, motor mounts, conveyor belts, transmission belts, or, preferably, tires (especially tire treads), advantageously tires for heavy goods vehicles, in particular for trucks.
Enfin, l'invention a pour quatrième objet les compositions (ou kits) comprenant au moins une charge inorganique renforçante pour élastomère et au moins un agent de couplage charge inorganique - élastomère, caractérisées en ce que ladite charge inorganique renforçante et ledit agent de couplage charge inorganique - élastomère sont tels que définis précédemment selon le premier objet de l'invention, c'est-à-dire que ladite charge inorganique renforçante est la silice précipitée contenant de l'aluminium telle que décrite dans
l'exposé ci-dessus et ledit agent de couplage charge inorganique - élastomère est le 3-acryloxy-propyltriethoxysilane. Finally, the fourth subject of the invention is compositions (or kits) comprising at least one reinforcing inorganic filler for elastomer and at least one inorganic filler-elastomer coupling agent, characterized in that said reinforcing inorganic filler and said coupling agent charge inorganic - elastomer are as defined above according to the first subject of the invention, that is to say that said reinforcing inorganic filler is precipitated silica containing aluminum as described in the above disclosure and said inorganic filler-elastomer coupling agent is 3-acryloxypropyltriethoxysilane.
Tout ce qui a été mentionné précédemment dans le cadre de l'utilisation selon le premier objet de l'invention ou dans le cadre du deuxième ou du troisième objet de l'invention s'applique à ces compositions (ou kits) et à leurs utilisations. All that has been mentioned previously in the context of the use according to the first subject of the invention or in the context of the second or third subject of the invention applies to these compositions (or kits) and their uses. .
En particulier, ces compositions peuvent comprendre en outre au moins un agent de recouvrement de ladite silice précipitée utilisée à titre de charge renforçante. In particular, these compositions may further comprise at least one covering agent for said precipitated silica used as a reinforcing filler.
De même, ces compositions trouvent une application particulièrement intéressante dans des compositions d'élastomère(s) comprenant au moins un élastomère isoprénique, notamment dans celles comprenant (par exemple comme unique élastomère) du caoutchouc naturel. Une application préférée réside dans leur utilisation dans les pneumatiques (notamment les bandes de roulement de pneumatiques), de manière avantageuse dans les pneumatiques pour les véhicules poids lourds, en particulier pour les camions. Similarly, these compositions find a particularly advantageous application in elastomer compositions (s) comprising at least one isoprene elastomer, especially in those comprising (for example as sole elastomer) natural rubber. A preferred application lies in their use in tires (especially tire treads), advantageously in tires for heavy goods vehicles, in particular for trucks.
Les exemples suivants illustrent l'invention sans toutefois en limiter la portée. The following examples illustrate the invention without, however, limiting its scope.
EXEMPLES EXAMPLES
EXEMPLE 1 (comparatif) Dans un réacteur en acier inoxydable muni d'un système d'agitation par hélices et d'un chauffage électrique externe, on introduit : EXAMPLE 1 (Comparative) In a stainless steel reactor equipped with a propeller stirring system and external electric heating, the following are introduced:
- 29,335 kg d'eau - 29,335 kg of water
- 509 g de Na2SO4 - 509 g of Na 2 SO 4
- 17,3 kg de silicate de sodium aqueux, présentant un rapport pondéral SiO2/Na2O égal à 3,47 et une densité à 20 °C égale à 1 ,230. 17.3 kg of aqueous sodium silicate, having a weight ratio SiO 2 / Na 2 O equal to 3.47 and a density at 20 ° C. equal to 1. 230.
La concentration en silicate (exprimée en SiO2) dans le pied de cuve initial est alors de 76,5 g/L.
Le mélange est alors porté à une température de 83 °C tout en le maintenant sous agitation. On y introduit ensuite 17470 g d'acide sulfurique dilué de densité à 20 °C égale à 1 ,050 afin d'obtenir dans le milieu réactionnel une valeur de pH (mesurée à sa température) égale à 8. La température de la réaction est de 83 °C pendant les 20 premières minutes ; elle est ensuite portée de 83 à 92 °C en 30 minutes environ, ce qui correspond à la fin de l'acidification. The silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l. The mixture is then heated to a temperature of 83 ° C while maintaining stirring. 17470 g of dilute sulfuric acid having a density at 20 ° C. of 1.050 are then introduced in order to obtain a pH value (measured at its temperature) of 8. The temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
On introduit ensuite conjointement dans le milieu réactionnel 4120 g de silicate de sodium aqueux du type décrit ci-avant et 4830 g d'acide sulfurique, également du type décrit ci-avant, cette introduction simultanée d'acide et de silicate étant réalisée de manière telle que le pH du milieu réactionnel, pendant la période d'introduction, soit constamment égal à 8,0 ± 0,1 . Après introduction de la totalité de ce silicate, on continue à introduire de l'acide dilué pendant 7 minutes de manière à amener le pH du milieu réactionnel à une valeur égale à 5,2. Après cette introduction d'acide, on maintient la bouillie réactionnelle obtenue pendant 5 minutes sous agitation. 4120 g of aqueous sodium silicate of the type described above and 4830 g of sulfuric acid, also of the type described above, are then introduced together into the reaction medium, this simultaneous introduction of acid and silicate being carried out in a manner such that the pH of the reaction medium, during the period of introduction, is constantly equal to 8.0 ± 0.1. After introduction of all of this silicate, dilute acid is continued for 7 minutes to bring the pH of the reaction medium to a value of 5.2. After this introduction of acid, the reaction mixture obtained is stirred for 5 minutes.
La durée totale de la réaction est de 85 minutes. The total reaction time is 85 minutes.
On obtient ainsi une bouillie ou suspension de silice précipitée qui est ensuite filtrée et lavée au moyen d'un filtre plan. A slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
Le gâteau obtenu est ensuite fluidifié par action mécanique et chimique (ajout simultané d'acide sulfurique et d'une quantité d'aluminate de sodium correspondant à un rapport pondéral AI/SiO2 de 0,3 %). Après cette opération de délitage, la bouillie résultante, de pH égal à 6,5 et de perte au feu égale à 85,5 % (donc un taux de matière sèche de 14,5 % en poids), est séchée par atomisation. Les caractéristiques de la silice obtenue A1 sous forme de poudre sont alors les suivantes : The cake obtained is then fluidized by mechanical and chemical action (simultaneous addition of sulfuric acid and a quantity of sodium aluminate corresponding to an Al / SiO 2 weight ratio of 0.3%). After this disintegration operation, the resulting slurry, with a pH equal to 6.5 and a loss on ignition equal to 85.5% (thus a solids content of 14.5% by weight), is spray-dried. The characteristics of the silica obtained A1 in the form of powder are then as follows:
surface spécifique CTAB 163 m2/g CTAB surface area 163 m 2 / g
surface spécifique BET 164 m2/g BET specific surface 164 m 2 / g
teneur pondéral en alumin 0,26 % 0.26% aluminum content by weight
rapport V2/V1 51 % V2 / V1 ratio 51%
PH 6,7
On soumet la silice A1 au test de désagglomération tel que défini précédemment dans la description. PH 6.7 Silica A1 is subjected to the disagglomeration test as defined above in the description.
Après désagglomération aux ultra-sons, elle présente un diamètre médian (05O) de 2,9 pm. After deagglomeration with ultrasound, it has a median diameter ( 050 ) of 2.9 .mu.m.
EXEMPLE 2 EXAMPLE 2
Dans un réacteur en acier inoxydable muni d'un système d'agitation par hélices et d'un chauffage électrique externe, on introduit : In a stainless steel reactor equipped with a propeller stirring system and external electric heating, the following are introduced:
- 29,335 kg d'eau - 29,335 kg of water
- 509 g de Na2SO4 - 509 g of Na 2 SO 4
- 17,3 kg de silicate de sodium aqueux, présentant un rapport pondéral 17.3 kg of aqueous sodium silicate, having a weight ratio
SiO2/Na2O égal à 3,47 et une densité à 20 °C égale à 1 ,230. SiO 2 / Na 2 O equal to 3.47 and a density at 20 ° C equal to 1. 230.
La concentration en silicate (exprimée en SiO2) dans le pied de cuve initial est alors de 76,5 g/L. The silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l.
Le mélange est alors porté à une température de 83 °C tout en le maintenant sous agitation. On y introduit ensuite 18050 g d'acide sulfurique dilué de densité à 20 °C égale à 1 ,050 afin d'obtenir dans le milieu réactionnel une valeur de pH (mesurée à sa température) égale à 8. La température de la réaction est de 83 °C pendant les 20 premières minutes ; elle est ensuite portée de 83 à 92 °C en 30 minutes environ, ce qui correspond à la fin de l'acidification. The mixture is then heated to a temperature of 83 ° C while maintaining stirring. 18050 g of dilute sulfuric acid having a density at 20 ° C. of 1.050 are then introduced in order to obtain in the reaction medium a pH value (measured at its temperature) equal to 8. The temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
On introduit ensuite conjointement dans le milieu réactionnel 1850 g de silicate de sodium aqueux du type décrit ci-avant et 2230 g d'acide sulfurique, également du type décrit ci-avant, cette introduction simultanée d'acide et de silicate étant réalisée de manière telle que le pH du milieu réactionnel, pendant la période d'introduction, soit constamment égal à 8,0 ± 0,1 . 1850 g of aqueous sodium silicate of the type described above and 2230 g of sulfuric acid, also of the type described above, are then introduced together into the reaction medium, this simultaneous introduction of acid and silicate being carried out in a manner such that the pH of the reaction medium, during the period of introduction, is constantly equal to 8.0 ± 0.1.
Cette étape est suivie d'une addition simultanée de 4520 g d'une solution de sulfate d'aluminium de densité 20 °C égale à 1 ,056 et de 2260 g de silicate de sodium aqueux du type décrit ci-avant de telle manière que le pH du milieu réactionnel, pendant la période d'introduction, soit constamment égal à 8,0 ± 0,1 . This step is followed by a simultaneous addition of 4520 g of a solution of aluminum sulphate with a density of 20 ° C. equal to 1.056 and of 2260 g of aqueous sodium silicate of the type described above in such a way that the pH of the reaction medium, during the period of introduction, is constantly equal to 8.0 ± 0.1.
Après cette addition conjointe, on introduit dans le milieu réactionnel, pendant
5 minutes, de l'acide sulfunque du type décrit ci-avant de manière à amener le pH du milieu réactionnel à une valeur égale à 5,2. Après cette introduction d'acide, on maintient la bouillie réactionnelle obtenue pendant 5 minutes sous agitation. After this joint addition, it is introduced into the reaction medium, during 5 minutes, sulfunic acid of the type described above so as to bring the pH of the reaction medium to a value equal to 5.2. After this introduction of acid, the reaction mixture obtained is stirred for 5 minutes.
La durée totale de la réaction est de 85 minutes. The total reaction time is 85 minutes.
On obtient ainsi une bouillie ou suspension de silice précipitée qui est ensuite filtrée et lavée au moyen d'un filtre plan. A slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
Le gâteau obtenu est ensuite fluidifié par action mécanique et chimique (ajout simultané d'acide sulfurique et d'une quantité d'aluminate de sodium correspondant à un rapport pondéral AI/SiO2 de 0,3 %). Après cette opération de délitage, la bouillie résultante, de pH égal à 6,5 et de perte au feu égale à 86,0 % (donc un taux de matière sèche de 14,0 % en poids), est séchée par atomisation. The cake obtained is then fluidized by mechanical and chemical action (simultaneous addition of sulfuric acid and a quantity of sodium aluminate corresponding to an Al / SiO 2 weight ratio of 0.3%). After this disintegration operation, the resulting slurry, with a pH equal to 6.5 and a loss on ignition equal to 86.0% (thus a solids content of 14.0% by weight), is spray-dried.
Les caractéristiques de la silice obtenue P1 sous forme de poudre sont alors les suivantes : The characteristics of the silica obtained P1 in powder form are then as follows:
- surface spécifique CTAB 161 m2/g - CTAB surface area 161 m 2 / g
- surface spécifique BET 161 m2/g - BET specific surface area 161 m 2 / g
- teneur pondéral en aluminium 1 ,2 % - aluminum weight content 1, 2%
- rapport V2/V1 45 % - V2 / V1 ratio 45%
- pH 7,4 - pH 7.4
On soumet la silice P1 au test de désagglomération tel que défini précédemment dans la description. The silica P1 is subjected to the disagglomeration test as defined above in the description.
Après désagglomération aux ultra-sons, elle présente un diamètre médian (05O) de 2,5 μηη. After deagglomeration with ultrasound, it has a median diameter (0 50 ) of 2.5 μηη.
EXEMPLE 3 EXAMPLE 3
Dans un réacteur en acier inoxydable muni d'un système d'agitation par hélices et d'un chauffage électrique externe, on introduit : In a stainless steel reactor equipped with a propeller stirring system and external electric heating, the following are introduced:
- 29,335 kg d'eau - 29,335 kg of water
- 509 g de Na2SO4
- 17,3 kg de silicate de sodium aqueux, présentant un rapport pondéral SiO2/Na2O égal à 3,44 et une densité à 20 °C égale à 1 ,232. - 509 g of Na 2 SO 4 17.3 kg of aqueous sodium silicate, having a weight ratio SiO 2 / Na 2 O equal to 3.44 and a density at 20 ° C. equal to 1, 232.
La concentration en silicate (exprimée en SiO2) dans le pied de cuve initial est alors de 76,5 g/L. The silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l.
Le mélange est alors porté à une température de 83 °C tout en le maintenant sous agitation. On y introduit ensuite 17180 g d'acide sulfurique dilué de densité à 20 °C égale à 1 ,050 afin d'obtenir dans le milieu réactionnel une valeur de pH (mesurée à sa température) égale à 8. La température de la réaction est de 83 °C pendant les 20 premières minutes ; elle est ensuite portée de 83 à 92 °C en 30 minutes environ, ce qui correspond à la fin de l'acidification. The mixture is then heated to a temperature of 83 ° C while maintaining stirring. 17180 g of dilute sulfuric acid having a density at 20 ° C. of 1.050 are then introduced in order to obtain in the reaction medium a pH value (measured at its temperature) equal to 8. The temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
On introduit ensuite conjointement dans le milieu réactionnel 4100 g de silicate de sodium aqueux du type décrit ci-avant et 7540 g d'une solution de sulfate d'aluminium de densité 20 °C égale à 1 ,056, cette introduction simultanée de sulfate d'aluminium (acide) et de silicate étant réalisée de manière telle que le pH du milieu réactionnel, pendant la période d'introduction, soit constamment égal à 8,0 ± 0,1 . Après cette addition conjointe, on introduit dans le milieu réactionnel, pendant 5 minutes, de l'acide sulfurique du type décrit ci-avant de manière à amener le pH du milieu réactionnel à une valeur égale à 5,2. Après cette introduction d'acide, on maintient la bouillie réactionnelle obtenue pendant 5 minutes sous agitation. 4100 g of aqueous sodium silicate of the type described above and 7540 g of a solution of aluminum sulphate with a density of 20 ° C. of 1.056 are then added together in the reaction medium, this simultaneous introduction of sodium sulphate. aluminum (acid) and silicate being carried out in such a way that the pH of the reaction medium, during the period of introduction, is constantly equal to 8.0 ± 0.1. After this joint addition, sulfuric acid of the type described above is introduced into the reaction medium for 5 minutes in order to bring the pH of the reaction medium to a value of 5.2. After this introduction of acid, the reaction mixture obtained is stirred for 5 minutes.
La durée totale de la réaction est de 85 minutes. The total reaction time is 85 minutes.
On obtient ainsi une bouillie ou suspension de silice précipitée qui est ensuite filtrée et lavée au moyen d'un filtre plan. A slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
Le gâteau obtenu est ensuite fluidifié par action mécanique et chimique (ajout simultané d'acide sulfurique et d'une quantité d'aluminate de sodium correspondant à un rapport pondéral AI/SiO2 de 0,3 %). Après cette opération de délitage, la bouillie résultante, de pH égal à 6,5 et de perte au feu égale à 85,0 % (donc un taux de matière sèche de 15,0 % en poids), est séchée par atomisation. The cake obtained is then fluidized by mechanical and chemical action (simultaneous addition of sulfuric acid and a quantity of sodium aluminate corresponding to an Al / SiO 2 weight ratio of 0.3%). After this disintegration operation, the resulting slurry, with a pH equal to 6.5 and a loss on ignition equal to 85.0% (thus a solids content of 15.0% by weight), is spray-dried.
Les caractéristiques de la silice obtenue P2 sous forme de poudre sont alors les suivantes : The characteristics of the silica obtained P2 in powder form are then as follows:
- surface spécifique CTAB 158 m2/g
- surface spécifique BET 178 m2/g CTAB surface area 158 m 2 / g - BET specific surface area 178 m 2 / g
- teneur pondéral en aluminium 1 ,5 % - weight content of aluminum 1, 5%
- rapport V2/V1 47 % - V2 / V1 ratio 47%
- pH 7,5 - pH 7.5
On soumet la silice P2 au test de désagglomération tel que défini précédemment dans la description. Silica P2 is subjected to the disagglomeration test as defined previously in the description.
Après désagglomération aux ultra-sons, elle présente un diamètre médian (05O) de 2,9 pm. EXEMPLE 4 After deagglomeration with ultrasound, it has a median diameter ( 050 ) of 2.9 .mu.m. EXAMPLE 4
Dans un réacteur en acier inoxydable muni d'un système d'agitation par hélices et d'un chauffage électrique externe, on introduit : In a stainless steel reactor equipped with a propeller stirring system and external electric heating, the following are introduced:
- 29,35 kg d'eau - 29.35 kg of water
- 509 g de Na2SO4 - 509 g of Na 2 SO 4
- 17,2 kg de silicate de sodium aqueux, présentant un rapport pondéral SiO2/Na2O égal à 3,44 et une densité à 20 °C égale à 1 ,230. 17.2 kg of aqueous sodium silicate, having a weight ratio SiO 2 / Na 2 O equal to 3.44 and a density at 20 ° C. equal to 1. 230.
La concentration en silicate (exprimée en SiO2) dans le pied de cuve initial est alors de 76,5 g/L. The silicate concentration (expressed as SiO 2 ) in the initial stock is then 76.5 g / l.
Le mélange est alors porté à une température de 83 °C tout en le maintenant sous agitation. On y introduit ensuite 16900 g d'acide sulfurique dilué de densité à 20 °C égale à 1 ,050 afin d'obtenir dans le milieu réactionnel une valeur de pH (mesurée à sa température) égale à 8. La température de la réaction est de 83 °C pendant les 20 premières minutes ; elle est ensuite portée de 83 à 92 °C en 30 minutes environ, ce qui correspond à la fin de l'acidification. The mixture is then heated to a temperature of 83 ° C while maintaining stirring. It then introduces 16900 g of dilute sulfuric acid of density at 20 ° C equal to 1.050 in order to obtain in the reaction medium a pH value (measured at its temperature) equal to 8. The temperature of the reaction is 83 ° C for the first 20 minutes; it is then increased from 83 to 92 ° C. in approximately 30 minutes, which corresponds to the end of the acidification.
On introduit ensuite conjointement dans le milieu réactionnel 4100 g de silicate de sodium aqueux du type décrit ci-avant, 2150 g d'aluminate de sodium dilué de densité à 20 °C égale à 1 ,237 et 6000 g d'acide sulfurique du type décrit ci-avant, cette introduction simultanée d'acide, de silicate et d'aluminate de sodium étant réalisée de manière telle que le pH du milieu réactionnel, pendant la période d'introduction, soit constamment égal à 8,0 ± 0,1 .
Après cette addition conjointe, on continue à introduire dans le milieu réactionnel, pendant 3,5 minutes, de l'acide sulfurique du type décrit ci-avant de manière à amener le pH du milieu réactionnel à une valeur égale à 6,5. Après cette introduction d'acide, on maintient la bouillie réactionnelle obtenue pendant 5 minutes sous agitation. 4100 g of aqueous sodium silicate of the type described above are then introduced together into the reaction medium, 2150 g of dilute sodium aluminate with a density at 20 ° C. of 1, 237 and 6000 g of sulfuric acid of the type described above. described above, this simultaneous introduction of acid, of silicate and of sodium aluminate being carried out in such a way that the pH of the reaction medium, during the period of introduction, is constantly equal to 8.0 ± 0.1 . After this joint addition, sulfuric acid of the type described above is introduced into the reaction medium for 3.5 minutes so as to bring the pH of the reaction medium to a value equal to 6.5. After this introduction of acid, the reaction mixture obtained is stirred for 5 minutes.
La durée totale de la réaction est de 87 minutes. The total reaction time is 87 minutes.
On obtient ainsi une bouillie ou suspension de silice précipitée qui est ensuite filtrée et lavée au moyen d'un filtre plan. A slurry or suspension of precipitated silica is thus obtained which is then filtered and washed by means of a plane filter.
Le gâteau obtenu est ensuite fluidifié par action mécanique. Après cette opération de délitage, la bouillie résultante, de perte au feu égale à 84,5 % (donc un taux de matière sèche de 15,5 % en poids), est séchée par atomisation. The cake obtained is then fluidified by mechanical action. After this disintegration operation, the resulting slurry, with a loss on ignition equal to 84.5% (thus a solids content of 15.5% by weight), is spray-dried.
Les caractéristiques de la silice obtenue P3 sous forme de poudre sont alors les suivantes : The characteristics of the silica obtained P3 in powder form are then as follows:
- surface spécifique CTAB 135 m2/g - CTAB surface area 135 m 2 / g
- surface spécifique BET 160 m2/g - BET specific surface 160 m 2 / g
- teneur pondéral en aluminium 2,7 % - 2.7% aluminum content by weight
- rapport V2/V1 40 % - V2 / V1 ratio 40%
- pH 6,7 - pH 6.7
On soumet la silice P3 au test de désagglomération tel que défini précédemment dans la description. The silica P3 is subjected to the disagglomeration test as defined previously in the description.
Après désagglomération aux ultra-sons, elle présente un diamètre médian (05O) de 2,9 pm. EXEMPLE 5 After deagglomeration with ultrasound, it has a median diameter ( 050 ) of 2.9 .mu.m. EXAMPLE 5
Cet exemple illustre l'utilisation et le comportement de la silice précipitée contenant de l'aluminium préparée dans l'exemple 3 avec le 3-acryloxy- propyltriethoxysilane dans une composition élastomérique.
Dans un mélangeur interne de type Haake, on prépare des compositions élastomériques dont la constitution, exprimée en partie en poids pour 100 parties d'élastomères (pce), est indiquée dans le tableau I ci-dessous. This example illustrates the use and behavior of the precipitated aluminum-containing silica prepared in Example 3 with 3-acryloxypropyltriethoxysilane in an elastomeric composition. In an internal Haake-type mixer, elastomeric compositions are prepared whose constitution, expressed in part by weight per 100 parts of elastomers (phr), is given in Table I below.
Tableau I : Formulations utilisées pour les mélanges Table I: Formulations used for blends
(1 ) Caoutchouc naturel SMR 5 L (fourni par la société Safic-Alcan)
(2) Silice A1 (exemple 1 ) (1) SMR 5 L natural rubber (supplied by Safic-Alcan) (2) Silica A1 (Example 1)
(3) Silice P2 (exemple 3) (3) Silica P2 (Example 3)
(4) TESPT (Z-6940 de la société Dow Corning) (4) TESPT (Z-6940 from Dow Corning Company)
(5) 3-acryloxy-propyltriethoxysilane (5) 3-acryloxypropyltriethoxysilane
(6) N-1 ,3-diméthylbutyl-N-phényl-para-phénylènediamine (Santoflex (6) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine (Santoflex
6-PPD de la société Flexsys) 6-PPD from Flexsys)
(7) 2,2,4-trimethyl-l H-quinoline (Permanax TQ de la société Flexsys) (7) 2,2,4-trimethyl-1H-quinoline (Permanax TQ from Flexsys)
(8) N-cyclohexyl-2-benzothiazyl-sulfénamide (Rhénogran CBS-80 de la (8) N-cyclohexyl-2-benzothiazyl sulfenamide (Rhenogran CBS-80 from
société RheinChemie) RheinChemie company)
(9) Disulfure de tetrabenzylthiurame (Rhénogran TBzTD-70 de la société (9) Tetrabenzylthiuram Disulfide (Rhenogran TBzTD-70 Company)
RheinChemie) RheinChemie)
(10) Diphénylguanidine (Rhénogran DPG-80 de la société RheinChemie) (10) Diphenylguanidine (Rhenogran DPG-80 from RheinChemie)
Procédé de préparation des compositions élastomériques Process for the preparation of elastomeric compositions
Le procédé de préparation des compositions est conduit en deux phases de préparation successives. Une première phase consiste dans une phase de travail thermomécanique à haute température. Elle est suivie d'une seconde phase de travail mécanique à des températures inférieures à 1 10 °C ; cette phase permet l'introduction du système de vulcanisation. The process for preparing the compositions is conducted in two successive preparation phases. A first phase consists in a thermomechanical work phase at high temperature. It is followed by a second phase of mechanical work at temperatures below 110 ° C; this phase allows the introduction of the vulcanization system.
La première phase est réalisée dans un mélangeur interne de type Haake (capacité de 300 mL). Le coefficient de remplissage est de 0,75. La température initiale et la vitesse des rotors sont fixées à chaque fois de manière à atteindre des températures de tombée de mélange voisines de 140-160 °C. The first phase is carried out in a Haake type internal mixer (capacity of 300 mL). The fill factor is 0.75. The initial temperature and the speed of the rotors are fixed each time so as to reach mixing drop temperatures of about 140-160 ° C.
La première phase est décomposée ici en deux passes. The first phase is decomposed here in two passes.
Elle permet d'incorporer, dans une première passe, l'élastomère (caoutchouc naturel), puis la charge inorganique renforçante constituée par la silice (introduction fractionnée) avec l'agent de couplage et l'acide stéarique ; la durée de cette passe est comprise entre 4 et 10 minutes.
Après refroidissement du mélange (température inférieure à 100 °C), une second passe permet d'incorporer l'oxyde de zinc et les agents protecteurs/antioxydants (6-PPD notamment) ; la durée de cette passe est comprise entre 2 et 5 minutes. It allows to incorporate, in a first pass, the elastomer (natural rubber), then the reinforcing inorganic filler consisting of silica (fractional introduction) with the coupling agent and stearic acid; the duration of this pass is between 4 and 10 minutes. After cooling the mixture (temperature below 100 ° C.), a second pass makes it possible to incorporate the zinc oxide and the protective / antioxidant agents (6-PPD in particular); the duration of this pass is between 2 and 5 minutes.
Après refroidissement du mélange (température inférieure à 100 °C), la seconde phase permet l'introduction du système de vulcanisation (soufre et accélérateurs, comme le CBS). Elle est réalisée sur un mélangeur à cylindres, préchauffé à 50 °C. La durée de cette phase est comprise entre 2 et 6 minutes. After cooling the mixture (temperature below 100 ° C), the second phase allows the introduction of the vulcanization system (sulfur and accelerators, such as CBS). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 2 and 6 minutes.
Chaque mélange final est ensuite calandré sous la forme de plaques d'épaisseur 2-3 mm. Each final mixture is then calendered in the form of plates 2-3 mm thick.
Sur ces mélanges obtenus dits crus, une évaluation de leurs propriétés rhéologiques permet d'optimiser la durée et la température de vulcanisation. On these so-called raw mixtures obtained, an evaluation of their rheological properties makes it possible to optimize the duration and the vulcanization temperature.
Ensuite, les propriétés mécaniques et dynamiques des mélanges vulcanisés à l'optimum sont mesurées. Then, the mechanical and dynamic properties of the optimum vulcanized mixtures are measured.
Propriétés rhéologiques Rheological properties
- Viscosité des mélanges crus - Viscosity of raw mixtures
La consistance Mooney est mesurée sur les compositions à l'état cru à 100 °C au moyen d'un rhéomètre MV 2000 selon la norme NF ISO 289. The Mooney consistency is measured on the compositions in the uncured state at 100 ° C. by means of a MV 2000 rheometer according to the NF ISO 289 standard.
La valeur du couple lue au bout de 4 minutes après un préchauffage d'une minute (Mooney Large (1 +4) à 100 °C) est indiquée dans le tableau II. The value of the torque read after 4 minutes after preheating for one minute (Mooney Large (1 +4) at 100 ° C) is shown in Table II.
Tableau II
Table II
On constate que la composition issue de l'invention (composition 1 ) présente une viscosité à crue satisfaisante, et surtout plus faible que celle de la
composition de référence (référence 1 ) contenant le même agent de couplage mais associé à une silice précipitée présentant une teneur en aluminium non conforme à celle requise par l'invention . - Rhéométrie des compositions It is found that the composition resulting from the invention (composition 1) has a satisfactory viscosity at raw water, and especially lower than that of the reference composition (reference 1) containing the same coupling agent but associated with a precipitated silica having an aluminum content that does not conform to that required by the invention. - Rheometry of the compositions
Les mesures sont réalisées sur les compositions à l'état cru. On a porté dans le tableau III les résultats concernant le test de rhéologie qui est conduit à 150 °C au moyen d'un rhéomètre ODR Monsanto selon la norme NF ISO 3417. The measurements are performed on the compositions in the green state. The results relating to the rheology test, which is conducted at 150 ° C. using a Monsanto ODR rheometer according to the NF ISO 3417 standard, are shown in Table III.
Selon ce test, la composition à tester est placée dans la chambre d'essai régulée à une température de 150 °C durant 30 minutes, et on mesure le couple résistant, opposé par la composition, à une oscillation de faible amplitude (3°) d'un rotor biconique inclus dans la chambre d'essai, la composition remplissant complètement la chambre considérée. According to this test, the composition to be tested is placed in the controlled test chamber at a temperature of 150 ° C. for 30 minutes, and the resistive torque opposed by the composition is measured at a low amplitude oscillation (3 °). a biconical rotor included in the test chamber, the composition completely filling the chamber in question.
A partir de la courbe de variation du couple en fonction du temps, on détermine : From the curve of variation of the torque as a function of time, we determine:
- le couple minimum (Cmin), qui reflète la viscosité de la composition à la température considérée ; the minimum torque (Cmin), which reflects the viscosity of the composition at the temperature considered;
- le couple maximum (Cmax) ; - the maximum torque (Cmax);
- le delta-couple (AC = Cmax - Cmin) ; - the delta torque (AC = Cmax - Cmin);
- le temps T98 nécessaire pour obtenir un état de vulcanisation correspondant à 98 % de la vulcanisation complète (ce temps est pris comme optimum de vulcanisation) ; the time T98 necessary to obtain a state of vulcanization corresponding to 98% of the complete vulcanization (this time is taken as the vulcanization optimum);
- le temps de grillage TS2 correspondant au temps nécessaire pour avoir une remontée de 2 points au-dessus du couple minimum à la température considérée (150 °C) et reflétant le temps pendant lequel il est possible de mettre en œuvre les mélanges crus à cette température sans avoir d'initiation de la vulcanisation (le mélange durcit à partir de TS2). the roasting time TS2 corresponding to the time required to have a rise of 2 points above the minimum torque at the temperature in question (150 ° C.) and reflecting the time during which it is possible to use the raw mixtures with this temperature without initiation of vulcanization (the mixture cures from TS2).
Les résultats obtenus sont indiqués dans le tableau I II. The results obtained are shown in Table I II.
Tableau III Table III
Compositions Témoin 1 Référence 1 Composition 1
Cmin (dN.m) 12,8 13,5 13,0 Compositions Witness 1 Reference 1 Composition 1 Cmin (dNm) 12.8 13.5 13.0
Cmax (dN.m) 83,5 81 ,4 76,5 Cmax (dNm) 83.5 81, 76.5
Delta couple (dN.m) 70,7 67,9 63,5 Delta torque (dN.m) 70.7 67.9 63.5
TS2 (min) 5,55 6,65 6,85 TS2 (min) 5.55 6.65 6.85
T98 (min) 10,0 10,3 9,98 T98 (min) 10.0 10.3 9.98
On constate que la composition issue de l'invention (composition 1 ) présente un ensemble très satisfaisant de propriétés rhéologiques, et notamment par rapport à la composition de référence (référence 1 ) contenant le même agent de couplage mais associé à une silice précipitée présentant une teneur en aluminium non conforme à celle requise par l'invention. It is found that the composition resulting from the invention (composition 1) has a very satisfactory set of rheological properties, and especially with respect to the reference composition (reference 1) containing the same coupling agent but associated with a precipitated silica exhibiting aluminum content not in accordance with that required by the invention.
En particulier, elle présente des valeurs de couples minimum et maximum plus faibles que celles de la composition de référence (référence 1 ), et voisins (Cmin) voire plus faibles (Cmax) que celles de la composition témoin (témoin 1 ), ce qui traduit une plus grande facilité de mise en œuvre du mélange préparé. In particular, it has values of minimum and maximum couples lower than those of the reference composition (reference 1), and neighboring (Cmin) or even lower (Cmax) than those of the control composition (control 1), which translates a greater ease of implementation of the prepared mixture.
Et surtout la composition 1 issue de l'invention (composition 1 ) présente une bonne cinétique de vulcanisation (TS2, T98), notamment par rapport à la composition de référence (référence 1 ) et même par rapport à la composition témoin (témoin 1 ), et ce sans pénaliser la viscosité du mélange cru (illustrée notamment par le couple minimum). And especially the composition 1 resulting from the invention (composition 1) has a good vulcanization kinetics (TS2, T98), especially with respect to the reference composition (reference 1) and even compared to the control composition (control 1) , without penalizing the viscosity of the raw mixture (illustrated in particular by the minimum torque).
Propriétés mécaniques des vulcanisais Mechanical properties of vulcanisais
Les mesures sont réalisées sur les compositions vulcanisées à l'optimum (T98) pour une température de 150 °C. The measurements are carried out on the optimally vulcanized compositions (T98) for a temperature of 150 ° C.
Les essais de traction uniaxiale sont réalisés conformément aux indications de la norme NF ISO 37 avec des éprouvettes de type H2 à une vitesse de 500 mm/min sur un appareil INSTRON 5564. Les modules x % correspondent à la contrainte mesurée à x % de déformation en traction et sont exprimés, comme la résistance à la rupture en MPa. Il est possible de déterminer un indice de renforcement (I.R.) qui est égal au rapport entre le module à 300 % de déformation et le module à 100% de déformation.
Les propriétés mesurées sont rassemblées dans le tableau IV. The uniaxial tensile tests are carried out in accordance with the NF ISO 37 standard with type H2 specimens at a speed of 500 mm / min on an INSTRON 5564 device. The x% modules correspond to the stress measured at x% deformation. in tensile and are expressed, as the breaking strength in MPa. It is possible to determine a reinforcement index (IR) which is equal to the ratio between the 300% deformation modulus and the 100% deformation modulus. The measured properties are collated in Table IV.
Tableau IV Table IV
On constate que la composition issue de l'invention (composition 1 ) présente un très bon compromis de propriétés mécaniques, au moins comparable à, voire meilleure que, ce qui est obtenu avec la composition de référence (référence 1 ) ou même la composition témoin (témoin 1 ). Propriétés dynamiques des vulcanisais It is found that the composition resulting from the invention (composition 1) has a very good compromise of mechanical properties, at least comparable to, or better than, what is obtained with the reference composition (reference 1) or even the control composition (witness 1). Dynamic properties of vulcanisais
Les propriétés dynamiques sont mesurées sur un viscoanalyseur (Metravib VA3000), selon la norme ASTM D5992. Dynamic properties are measured on a viscoanalyzer (Metravib VA3000) according to ASTM D5992.
Dans une première série de mesures, les valeurs de facteur de perte (tan δ) et de module complexe en compression dynamique (E*) sont enregistrées sur des échantillons vulcanisés (éprouvette cylindrique de section 95 mm2 et de hauteur 14 mm). L'échantillon est soumis au départ à une prédéformation de 10 %, puis à une déformation sinusoïdale en compression alternée de +/- 2 %. Les mesures sont réalisées à 60 °C et à une fréquence de 10 Hz. In a first series of measurements, the values of loss factor (tan δ) and complex modulus in dynamic compression (E * ) are recorded on vulcanized samples (cylindrical specimen of section 95 mm 2 and height 14 mm). The sample is initially subjected to a predeformation of 10%, then to a sinusoidal deformation in alternating compression of +/- 2%. The measurements are carried out at 60 ° C. and at a frequency of 10 Hz.
Les résultats, présentés dans le tableau V, sont le module complexe en compression (E* - 60 °C - 10 Hz) et le facteur de perte (tan δ - 60 °C - 10 Hz). The results, presented in Table V, are the complex modulus in compression (E * - 60 ° C - 10 Hz) and the loss factor (tan δ - 60 ° C - 10 Hz).
Dans une seconde série de mesures, les valeurs du facteur de perte (tan δ) et de module élastique en cisaillement dynamique (G') sont enregistrées sur des échantillons vulcanisés (éprouvette parallélépipédique de section 8 mm2 et de hauteur 7 mm). L'échantillon est soumis à une déformation sinusoïdale en double cisaillement alternée à une température de 40 °C et à une fréquence de 10 Hz.
Les processus de balayage en amplitude de déformations s'effectuent selon un cycle aller-retour, allant de 0,1 à 50 % puis retour de 50 à 0,1 %. In a second series of measurements, the values of the loss factor (tan δ) and elastic modulus in dynamic shear (G ') are recorded on vulcanized samples (parallelepipedal specimen of section 8 mm 2 and height 7 mm). The sample is subjected to alternating double shear sine wave deformation at a temperature of 40 ° C and a frequency of 10 Hz. The scanning processes in amplitude of deformations are carried out according to a round-trip cycle, ranging from 0.1 to 50% and then from 50 to 0.1%.
Les résultats, présentés dans le tableau V, sont issus du balayage en amplitude de déformations au retour et concernent la valeur maximale du facteur de perte (tan δ max retour - 40 °C - 10 Hz) ainsi que l'amplitude du module élastique (ΔΘ' - 40 °C - 10 Hz) entre les valeurs à 0,1 % et 50 % de déformation (effet Payne). The results, presented in Table V, are derived from the amplitude sweep of the return strains and relate to the maximum value of the loss factor (tan δ max return - 40 ° C - 10 Hz) as well as the amplitude of the elastic modulus ( ΔΘ '- 40 ° C - 10 Hz) between the values at 0.1% and 50% deformation (Payne effect).
Tableau V Table V
La composition issue de l'invention (composition 1 ) présente de très bonnes propriétés dynamiques (propriétés hystérétiques à 60 °C), notamment par rapport à la composition de référence (référence 1 ) et également par rapport à la composition témoin (témoin 1 ). The composition resulting from the invention (composition 1) has very good dynamic properties (hysteretic properties at 60 ° C.), especially with respect to the reference composition (reference 1) and also with respect to the control composition (control 1) .
On constate, à la lecture des résultats des tableaux II à V, que la composition issue de l'invention (composition 1 ) présente un très bon compromis de propriétés. EXEMPLE 6 It can be seen from the results of Tables II to V that the composition resulting from the invention (composition 1) has a very good compromise of properties. EXAMPLE 6
Cet exemple illustre l'utilisation et le comportement de la silice précipitée contenant de l'aluminium préparée dans l'exemple 2 avec le 3-acryloxy- propyltriethoxysilane dans une composition élastomérique.
Dans un mélangeur interne de type Haake, on prépare des compositions élastomériques dont la constitution, exprimée en partie en poids pour 100 parties d'élastomères (pce), est indiquée dans le tableau VI ci-dessous. This example illustrates the use and behavior of the aluminum-containing precipitated silica prepared in Example 2 with 3-acryloxypropyltriethoxysilane in an elastomeric composition. In an internal Haake-type mixer, elastomeric compositions are prepared whose constitution, expressed in part by weight per 100 parts of elastomers (phr), is given in Table VI below.
Tableau VI : Formulations utilisées pour les mélanges Table VI: Formulations used for blends
(1 ) Caoutchouc naturel SMR - CV60 (fourni par la société Safic-Alcan)(1) Natural rubber SMR - CV60 (supplied by Safic-Alcan)
(2) Silice A1 (exemple 1 ) (2) Silica A1 (Example 1)
(3) Silice P1 (exemple 2) (3) Silica P1 (Example 2)
(4) TESPT (Z-6940 de la société Dow Corning) (4) TESPT (Z-6940 from Dow Corning Company)
(5) 3-acryloxy-propyltriethoxysilane (5) 3-acryloxypropyltriethoxysilane
(6) N-1 ,3-diméthylbutyl-N-phényl-para-phénylènediamine (Santoflex (6) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine (Santoflex
6-PPD de la société Flexsys) 6-PPD from Flexsys)
(7) 2,2,4-trimethyl-1 H-quinoline (Permanax TQ de la société Flexsys) (8) N-cyclohexyl-2-benzothiazyl-sulfénamide (Rhénogran CBS-80 de la (7) 2,2,4-trimethyl-1H-quinoline (Permanax TQ from Flexsys) (8) N-cyclohexyl-2-benzothiazyl-sulfenamide (Rhenogran CBS-80 from
société RheinChemie) RheinChemie company)
(9) Disulfure de tetrabenzylthiurame (Rhénogran TBzTD-70 de la société
RheinChemie) (9) Tetrabenzylthiuram Disulfide (Rhenogran TBzTD-70 Company) RheinChemie)
(10) Diphénylguanidine (Rhénogran DPG-80 de la société RheinChemie) (10) Diphenylguanidine (Rhenogran DPG-80 from RheinChemie)
Procédé de préparation des compositions élastomériques Process for the preparation of elastomeric compositions
Le procédé de préparation des compositions est conduit en deux phases de préparation successives. Une première phase consiste dans une phase de travail thermomécanique à haute température. Elle est suivie d'une seconde phase de travail mécanique à des températures inférieures à 1 10 °C ; cette phase permet l'introduction du système de vulcanisation. The process for preparing the compositions is conducted in two successive preparation phases. A first phase consists in a thermomechanical work phase at high temperature. It is followed by a second phase of mechanical work at temperatures below 110 ° C; this phase allows the introduction of the vulcanization system.
La première phase est réalisée dans un mélangeur interne de type Haake (capacité de 300 mL). Le coefficient de remplissage est de 0,75. La température initiale et la vitesse des rotors sont fixées à chaque fois de manière à atteindre des températures de tombée de mélange voisines de 140-160 °C. The first phase is carried out in a Haake type internal mixer (capacity of 300 mL). The fill factor is 0.75. The initial temperature and the speed of the rotors are fixed each time so as to reach mixing drop temperatures of about 140-160 ° C.
La première phase est décomposée ici en deux passes. The first phase is decomposed here in two passes.
Elle permet d'incorporer, dans une première passe, l'élastomère (caoutchouc naturel), puis la charge inorganique renforçante constituée par la silice (introduction fractionnée) avec l'agent de couplage et l'acide stéarique ; la durée de cette passe est comprise entre 4 et 10 minutes. It allows to incorporate, in a first pass, the elastomer (natural rubber), then the reinforcing inorganic filler consisting of silica (fractional introduction) with the coupling agent and stearic acid; the duration of this pass is between 4 and 10 minutes.
Après refroidissement du mélange (température inférieure à 100 °C), une second passe permet d'incorporer l'oxyde de zinc et les agents protecteurs/antioxydants (6-PPD notamment) ; la durée de cette passe est comprise entre 2 et 5 minutes. After cooling the mixture (temperature below 100 ° C.), a second pass makes it possible to incorporate the zinc oxide and the protective / antioxidant agents (6-PPD in particular); the duration of this pass is between 2 and 5 minutes.
Après refroidissement du mélange (température inférieure à 100 °C), la seconde phase permet l'introduction du système de vulcanisation (soufre et accélérateurs, comme le CBS). Elle est réalisée sur un mélangeur à cylindres, préchauffé à 50 °C. La durée de cette phase est comprise entre 2 et 6 minutes. After cooling the mixture (temperature below 100 ° C), the second phase allows the introduction of the vulcanization system (sulfur and accelerators, such as CBS). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 2 and 6 minutes.
Chaque mélange final est ensuite calandré sous la forme de plaques d'épaisseur 2-3 mm. Each final mixture is then calendered in the form of plates 2-3 mm thick.
Sur ces mélanges obtenus dits crus, une évaluation de leurs propriétés rhéologiques permet d'optimiser la durée et la température de vulcanisation.
Ensuite, les propriétés mécaniques et dynamiques des mélanges vulcanisés à l'optimum sont mesurées. On these so-called raw mixtures obtained, an evaluation of their rheological properties makes it possible to optimize the duration and the vulcanization temperature. Then, the mechanical and dynamic properties of the optimum vulcanized mixtures are measured.
Propriétés rhéologiques Rheological properties
- Viscosité des mélanges crus - Viscosity of raw mixtures
La consistance Mooney est mesurée comme dans l'exemple 5. The Mooney consistency is measured as in Example 5.
La valeur du couple lue au bout de 4 minutes après un préchauffage d'une minute (Mooney Large (1 +4) à 100 °C) est indiquée dans le tableau VII. The value of the torque read after 4 minutes after preheating for 1 minute (Mooney Large (1 +4) at 100 ° C) is shown in Table VII.
Tableau VII
Table VII
On constate que la composition issue de l'invention (composition 2) présente une viscosité à crue très satisfaisante, plus faible que celle de la composition de référence (référence 2) contenant le même agent de couplage mais associé à une silice précipitée présentant une teneur en aluminium non conforme à celle requise par l'invention, ou que celle de la composition témoin (témoin 2) contenant la même silice précipitée mais associée à un autre agent de couplage. It is found that the composition resulting from the invention (composition 2) has a very good flood viscosity, lower than that of the reference composition (reference 2) containing the same coupling agent but associated with a precipitated silica having a content aluminum not conforming to that required by the invention, or that of the control composition (control 2) containing the same silica precipitated but associated with another coupling agent.
- Rhéométrie des compositions - Rheometry of the compositions
Les mesures sont réalisées comme dans l'exemple 5. The measurements are carried out as in Example 5.
Les résultats obtenus sont indiqués dans le tableau VIII. The results obtained are shown in Table VIII.
Tableau VIII Table VIII
Compositions Témoin 2 Référence 2 Composition 2
Cmin (dN.m) 13,0 1 1 ,2 10,8 Compositions Witness 2 Reference 2 Composition 2 Cmin (dNm) 13.0 1 1, 2 10.8
Cmax (dN.m) 70,1 75,9 72,8 Cmax (dNm) 70.1 75.9 72.8
Delta couple (dN.m) 57,1 64,7 62,0 Delta torque (dNm) 57.1 64.7 62.0
TS2 (min) 5,68 7,10 7,77 TS2 (min) 5.68 7.10 7.77
On constate que la composition issue de l'invention (composition 1 ) présente un ensemble très satisfaisant de propriétés rhéologiques, et notamment par rapport à la composition de référence (référence 2) contenant le même agent de couplage mais associé à une silice précipitée présentant une teneur en aluminium non conforme à celle requise par l'invention. It is found that the composition resulting from the invention (composition 1) has a very satisfactory set of rheological properties, and especially with respect to the reference composition (reference 2) containing the same coupling agent but associated with a precipitated silica exhibiting aluminum content not in accordance with that required by the invention.
En particulier, elle présente des valeurs de couples minimum et maximum plus faibles que celles de la composition de référence (référence 2), voire plus faibles (Cmin) que celles de la composition témoin (témoin 2), ce qui traduit une grande facilité de mise en œuvre du mélange préparé. In particular, it has values of minimum and maximum couples lower than those of the reference composition (reference 2), or even lower (Cmin) than those of the control composition (control 2), which reflects a great ease of implementation of the prepared mixture.
La composition 1 issue de l'invention (composition 2) présente une bonne cinétique de vulcanisation (TS2), notamment par rapport à la composition de référence (référence 2) et par rapport à la composition témoin (témoin 2), et ce sans pénaliser la viscosité du mélange cru (illustrée notamment par le couple minimum). The composition 1 resulting from the invention (composition 2) has a good vulcanization kinetics (TS2), especially with respect to the reference composition (reference 2) and with respect to the control composition (control 2), and without penalizing the viscosity of the raw mixture (illustrated in particular by the minimum torque).
Propriétés mécaniques des vulcanisais Mechanical properties of vulcanisais
Les mesures sont réalisées sur les compositions vulcanisées à l'optimum (c'est-à-dire à un état de vulcanisation correspondant à 98 % de la vulcanisation complète) pour une température de 150 °C. The measurements are carried out on the compositions vulcanized at the optimum (that is to say at a state of vulcanization corresponding to 98% of the complete vulcanization) for a temperature of 150 ° C.
Les essais de traction uniaxiale sont réalisés conformément aux indications de la norme NF ISO 37 avec des éprouvettes de type H2 à une vitesse de 500 mm/min sur un appareil INSTRON 5564. Les modules x % correspondent à la contrainte mesurée à x % de déformation en traction et sont exprimés, comme la résistance à la rupture en MPa. Il est possible de déterminer un indice de renforcement (I.R.) qui est égal au rapport entre le module à 300 % de déformation et le module à 100% de déformation.
Les propriétés mesurées sont rassemblées dans le tableau IX. The uniaxial tensile tests are carried out in accordance with the NF ISO 37 standard with type H2 specimens at a speed of 500 mm / min on an INSTRON 5564 device. The x% modules correspond to the stress measured at x% deformation. in tensile and are expressed, as the breaking strength in MPa. It is possible to determine a reinforcement index (IR) which is equal to the ratio between the 300% deformation modulus and the 100% deformation modulus. The measured properties are collated in Table IX.
Tableau IX Table IX
On constate que la composition issue de l'invention (composition 2) présente un très bon compromis de propriétés mécaniques, au moins comparable à, voire meilleure, que ce qui est obtenu avec la composition de référence (référence 2) ou la composition témoin (témoin 2). Propriétés dynamiques des vulcanisais It is found that the composition resulting from the invention (composition 2) has a very good compromise of mechanical properties, at least comparable to, or better than, that obtained with the reference composition (reference 2) or the control composition ( witness 2). Dynamic properties of vulcanisais
Les propriétés dynamiques sont mesurées comme dans l'exemple 5. Dynamic properties are measured as in Example 5.
Les résultats sont présentés dans le tableau X. The results are shown in Table X.
Tableau X Paintings
La composition issue de l'invention (composition 2) présente de très bonnes propriétés dynamiques (propriétés hystérétiques à 60 °C), notamment par rapport à la composition de référence (référence 2) et à la composition témoin (témoin 2). The composition resulting from the invention (composition 2) has very good dynamic properties (hysteretic properties at 60 ° C.), especially with respect to the reference composition (reference 2) and to the control composition (control 2).
On constate, à la lecture des résultats des tableaux VII à X, que la composition issue de l'invention (composition 2) présente un très bon compromis de propriétés.
EXEMPLE 7 It can be seen from the results of Tables VII to X that the composition resulting from the invention (Composition 2) has a very good compromise of properties. EXAMPLE 7
Cet exemple illustre l'utilisation et le comportement d'une silice précipitée S, contenant plus de 0,5 % en poids d'aluminium et présentant les caractéristiques ci-après, et du 3-acryloxy-propyltriethoxysilane dans une composition élastomérique. This example illustrates the use and behavior of a precipitated silica S, containing more than 0.5% by weight of aluminum and having the following characteristics, and 3-acryloxypropyltriethoxysilane in an elastomeric composition.
1 - La silice précipitée S présente les caractéristiques ci-dessous : 1 - The precipitated silica S has the following characteristics:
- surface spécifique CTAB 160 m2/g - CTAB specific surface 160 m 2 / g
- surface spécifique BET 164 m2/g - BET specific surface 164 m 2 / g
- teneur pondérale en aluminium 1 ,6 % - weight content of aluminum 1, 6%
- rapport V2/V1 56 % - V2 / V1 ratio 56%
On la soumet au test de désagglomération tel que défini précédemment dans la description. It is subjected to the disagglomeration test as defined above in the description.
Après désagglomération aux ultra-sons, elle présente un diamètre médian (05o) de 3,1 μιτι et un facteur de désagglomération aux ultra-sons (FD) de 9,4 ml. After deagglomeration with ultrasound, it has a median diameter (05o) of 3.1 μιτι and an ultrasonic disaggregation factor (F D ) of 9.4 ml.
2- Dans un mélangeur interne de type Haake, on prépare des compositions élastomériques dont la constitution, exprimée en partie en poids pour 100 parties d'élastomères (pce), est indiquée dans le tableau I ci-dessous. 2- In an internal mixer of the Haake type, elastomeric compositions are prepared whose constitution, expressed in part by weight per 100 parts of elastomers (phr), is shown in Table I below.
Tableau I : Formulations utilisées pour les mélanges Table I: Formulations used for blends
Compositions Témoin 3 Composition 3 Compositions Witness 3 Composition 3
NR (1 ) 100 100 NR (1) 100 100
Silice 1 (2) 50 50 Silica 1 (2) 50 50
Agent de couplage 1 (3) 4,0 - Coupling Agent 1 (3) 4.0 -
Agent de couplage 2 (4) - 4,5
ZnO 3,0 3,0 Coupling Agent 2 (4) - 4.5 ZnO 3.0 3.0
Acide stéarique 2,5 2,5 Stearic acid 2.5 2.5
Antioxydant 1 (5) 1 ,5 1 ,5 Antioxidant 1 (5) 1, 5 1, 5
Antioxydant 2 (6) 1 ,0 1 ,0 Antioxidant 2 (6) 1, 0 1, 0
Noir de carbone (N330) 3,0 3,0 Carbon black (N330) 3.0 3.0
CBS (7) 1 ,5 1 ,5 CBS (7) 1, 5 1, 5
DPG (8) 0,5 0,5 DPG (8) 0.5 0.5
Soufre 1 ,5 2,0 Sulfur 1, 5 2.0
(1 ) Caoutchouc naturel SMR 5 - CV60 (fourni par la société Safic-Alcan)(1) Natural rubber SMR 5 - CV60 (supplied by Safic-Alcan)
(2) Silice S (2) Silica S
(3) TESPT (Z-6940 de la société Dow Corning) (3) TESPT (Z-6940 from Dow Corning Company)
(4) 3-acryloxy-propyltriethoxysilane (4) 3-acryloxypropyltriethoxysilane
(5) N-1 ,3-diméthylbutyl-N-phényl-para-phénylènediamine (Santoflex (5) N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine (Santoflex
6-PPD de la société Flexsys) 6-PPD from Flexsys)
(6) 2,2,4-trimethyl-1 H-quinoline (Permanax TQ de la société Flexsys) (6) 2,2,4-trimethyl-1H-quinoline (Permanax TQ from Flexsys)
(7) N-cyclohexyl-2-benzothiazyl-sulfénamide (Rhénogran CBS-80 de la (7) N-cyclohexyl-2-benzothiazyl sulfenamide (Rhenogran CBS-80 from
société RheinChemie) RheinChemie company)
(8) Diphénylguanidine (Rhénogran DPG-80 de la société RheinChemie) (8) Diphenylguanidine (Rhenogran DPG-80 from RheinChemie)
Procédé de préparation des compositions élastomériques Le procédé de préparation des compositions est conduit en deux phases de préparation successives. Une première phase consiste dans une phase de travail thermomécanique à haute température. Elle est suivie d'une seconde phase de travail mécanique à des températures inférieures à 1 10 °C ; cette phase permet l'introduction du système de vulcanisation. Process for the Preparation of the Elastomeric Compositions The process for the preparation of the compositions is carried out in two successive preparation phases. A first phase consists in a thermomechanical work phase at high temperature. It is followed by a second phase of mechanical work at temperatures below 110 ° C; this phase allows the introduction of the vulcanization system.
La première phase est réalisée dans un mélangeur interne de type Haake The first phase is carried out in a Haake-type internal mixer
(capacité de 300 mL). Le coefficient de remplissage est de 0,75. La température initiale et la vitesse des rotors sont fixées à chaque fois de manière à atteindre des températures de tombée de mélange voisines de 150-170 °C. (300 mL capacity). The fill factor is 0.75. The initial temperature and the speed of the rotors are fixed each time so as to reach mixing temperatures of the vicinity of 150-170 ° C.
La première phase est décomposée ici en deux passes.
Elle permet d'incorporer, dans une première passe, l'élastomère (caoutchouc naturel), puis la charge inorganique renforçante constituée par la silice (introduction fractionnée) avec l'agent de couplage et l'acide stéarique ; la durée de cette passe est comprise entre 4 et 10 minutes. The first phase is decomposed here in two passes. It allows to incorporate, in a first pass, the elastomer (natural rubber), then the reinforcing inorganic filler consisting of silica (fractional introduction) with the coupling agent and stearic acid; the duration of this pass is between 4 and 10 minutes.
Après refroidissement du mélange (température inférieure à 100 °C), une second passe permet d'incorporer l'oxyde de zinc et les agents protecteurs/antioxydants (6-PPD notamment) ; la durée de cette passe est comprise entre 2 et 5 minutes. After cooling the mixture (temperature below 100 ° C.), a second pass makes it possible to incorporate the zinc oxide and the protective / antioxidant agents (6-PPD in particular); the duration of this pass is between 2 and 5 minutes.
Après refroidissement du mélange (température inférieure à 100 °C), la seconde phase permet l'introduction du système de vulcanisation (soufre et accélérateurs, comme le CBS). Elle est réalisée sur un mélangeur à cylindres, préchauffé à 50 °C. La durée de cette phase est comprise entre 2 et 6 minutes. After cooling the mixture (temperature below 100 ° C), the second phase allows the introduction of the vulcanization system (sulfur and accelerators, such as CBS). It is carried out on a roll mill, preheated to 50 ° C. The duration of this phase is between 2 and 6 minutes.
Chaque mélange final est ensuite calandré sous la forme de plaques d'épaisseur 2-3 mm. Each final mixture is then calendered in the form of plates 2-3 mm thick.
Sur ces mélanges obtenus dits crus, une évaluation de leurs propriétés rhéologiques permet d'optimiser la durée et la température de vulcanisation. On these so-called raw mixtures obtained, an evaluation of their rheological properties makes it possible to optimize the duration and the vulcanization temperature.
Ensuite, les propriétés mécaniques et dynamiques des mélanges vulcanisés à l'optimum sont mesurées. Propriétés rhéologiques Then, the mechanical and dynamic properties of the optimum vulcanized mixtures are measured. Rheological properties
- Viscosité des mélanges crus - Viscosity of raw mixtures
La consistance Mooney est mesurée sur les compositions à l'état cru à 100 °C au moyen d'un rhéomètre MV 2000 selon la norme NF ISO 289. The Mooney consistency is measured on the compositions in the uncured state at 100 ° C. by means of a MV 2000 rheometer according to the NF ISO 289 standard.
La valeur du couple lue au bout de 4 minutes après un préchauffage d'une minute (Mooney Large (1 +4) à 100 °C) est indiquée dans le tableau II. The value of the torque read after 4 minutes after preheating for one minute (Mooney Large (1 +4) at 100 ° C) is shown in Table II.
- Rhéométrie des compositions
Les mesures sont réalisées sur les compositions à l'état cru. On a porté dans le tableau III les résultats concernant le test de rhéologie qui est conduit à 150 °C au moyen d'un rhéomètre ODR Monsanto selon la norme NF ISO 3417. - Rheometry of the compositions The measurements are performed on the compositions in the green state. The results relating to the rheology test, which is conducted at 150 ° C. using a Monsanto ODR rheometer according to the NF ISO 3417 standard, are shown in Table III.
Selon ce test, la composition à tester est placée dans la chambre d'essai régulée à une température de 150 °C durant 30 minutes, et on mesure le couple résistant, opposé par la composition, à une oscillation de faible amplitude (3°) d'un rotor biconique inclus dans la chambre d'essai, la composition remplissant complètement la chambre considérée. According to this test, the composition to be tested is placed in the controlled test chamber at a temperature of 150 ° C. for 30 minutes, and the resistive torque opposed by the composition is measured at a low amplitude oscillation (3 °). a biconical rotor included in the test chamber, the composition completely filling the chamber in question.
A partir de la courbe de variation du couple en fonction du temps, on détermine : From the curve of variation of the torque as a function of time, we determine:
- le couple minimum (Cmin), qui reflète la viscosité de la composition à la température considérée ; the minimum torque (Cmin), which reflects the viscosity of the composition at the temperature considered;
- le temps de grillage TS2 correspondant au temps nécessaire pour avoir une remontée de 2 points au-dessus du couple minimum à la température considérée (150 °C) et reflétant le temps pendant lequel il est possible de mettre en œuvre les mélanges crus à cette température sans avoir d'initiation de la vulcanisation (le mélange durcit à partir de TS2). the roasting time TS2 corresponding to the time required to have a rise of 2 points above the minimum torque at the temperature in question (150 ° C.) and reflecting the time during which it is possible to use the raw mixtures with this temperature without initiation of vulcanization (the mixture cures from TS2).
Les résultats obtenus sont indiqués dans le tableau II. The results obtained are shown in Table II.
Tableau II Table II
La composition issue de l'invention (composition 3) conduit à des valeurs plutôt faibles de consistance Mooney et de couple minimum. The composition resulting from the invention (composition 3) leads to rather low values of Mooney consistency and minimum torque.
Ainsi, on constate que la composition issue de l'invention présente une viscosité à crue satisfaisante (consistance Mooney), plus faible que celle de la composition témoin (témoin 3). Thus, it is found that the composition resulting from the invention has a satisfactory raw viscosity (Mooney consistency), lower than that of the control composition (control 3).
On constate également que cette composition conforme à l'invention possède des propriétés rhéologiques satisfaisantes. Elle présente une bonne
cinétique de vulcanisation (TS2), notamment par rapport à la composition témoin, et ce sans pénaliser la viscosité du mélange cru (illustrée par le couple minimum). Propriétés mécaniques des vulcanisais It is also noted that this composition according to the invention has satisfactory rheological properties. She presents a good vulcanization kinetics (TS2), particularly with respect to the control composition, and without penalizing the viscosity of the raw mixture (illustrated by the minimum torque). Mechanical properties of vulcanisais
Les mesures sont réalisées sur les compositions vulcanisées à l'optimum (c'est-à-dire à un état de vulcanisation correspondant à 98 % de la vulcanisation complète) pour une température de 150 °C. The measurements are carried out on the compositions vulcanized at the optimum (that is to say at a state of vulcanization corresponding to 98% of the complete vulcanization) for a temperature of 150 ° C.
Les essais de traction uniaxiale sont réalisés conformément aux indications de la norme NF ISO 37 avec des éprouvettes de type H2 à une vitesse de 500 mm/min sur un appareil INSTRON 5564. Les modules x % correspondent à la contrainte mesurée à x % de déformation en traction et sont exprimés, comme la résistance à la rupture, en MPa. Il est possible de déterminer un indice de renforcement (I.R.) qui est égal au rapport entre le module à 300 % de déformation et le module à 100% de déformation. The uniaxial tensile tests are carried out in accordance with the NF ISO 37 standard with type H2 specimens at a speed of 500 mm / min on an INSTRON 5564 device. The x% modules correspond to the stress measured at x% deformation. in tension and are expressed, as the breaking strength, in MPa. It is possible to determine a reinforcement index (I.R.) which is equal to the ratio between the 300% deformation modulus and the 100% deformation modulus.
La mesure de perte de masse par abrasion est effectuée selon les indications de la norme NF ISO 4649, en utilisant un abrasimètre Zwick où l'éprouvette cylindrique est soumise à l'action d'une toile abrasive de grains P60 et fixée sur la surface d'un tambour tournant sous une pression de contact de 10 N et pour une course de 40 m. La valeur mesurée est un volume de perte de substance (en mm3) après usure par abrasion ; plus elle est faible et meilleure est la résistance à l'abrasion. The measurement of loss of mass by abrasion is carried out according to the indications of standard NF ISO 4649, using a Zwick abraser where the cylindrical specimen is subjected to the action of an abrasive cloth of grains P60 and fixed on the surface of a drum rotating under a contact pressure of 10 N and a stroke of 40 m. The measured value is a volume of loss of substance (in mm 3 ) after wear by abrasion; the lower it is, the better the resistance to abrasion.
Les propriétés mesurées sont rassemblées dans le tableau III.
The measured properties are collated in Table III.
Tableau III Table III
On constate que la composition issue de l'invention (composition 3) présente un très bon compromis de propriétés mécaniques, notamment par rapport à ce qui est obtenu avec la composition témoin (témoin 3). It is found that the composition resulting from the invention (composition 3) has a very good compromise of mechanical properties, especially with respect to what is obtained with the control composition (control 3).
La composition issue de l'invention présente ainsi des modules 10 % et 100 % relativement faibles et un module 300 % élevé, d'où un indice de renforcement supérieur. The composition resulting from the invention thus has relatively low 10% and 100% moduli and a 300% high modulus, hence a higher reinforcement index.
En outre, cette composition 3 présente, en plus d'une résistance à la rupture satisfaisante, une perte par abrasion inférieure, c'est-à-dire une meilleure résistance à l'abrasion, d'où un gain en résistance à l'usure, ce qui est important en application pneumatique, en particulier pour les véhicules poids lourds. In addition, this composition 3 has, in addition to a satisfactory breaking strength, a lower abrasion loss, that is to say a better resistance to abrasion, resulting in a gain in resistance to abrasion. wear, which is important in pneumatic applications, especially for heavy goods vehicles.
Propriétés dynamiques des vulcanisais Dynamic properties of vulcanisais
Les propriétés dynamiques sont mesurées sur un viscoanalyseur (Metravib VA3000), selon la norme ASTM D5992. Dynamic properties are measured on a viscoanalyzer (Metravib VA3000) according to ASTM D5992.
Dans une première série de mesures, les valeurs de facteur de perte (tan δ) et de module complexe en compression dynamique (E*) sont enregistrées sur des échantillons vulcanisés (éprouvette cylindrique de section 95 mm2 et de hauteur 14 mm). L'échantillon est soumis au départ à une prédéformation de 10 %, puis à une déformation sinusoïdale en compression alternée de +/- 2 %. Les mesures sont réalisées à 60 °C et à une fréquence de 10 Hz. In a first series of measurements, the values of loss factor (tan δ) and complex modulus in dynamic compression (E * ) are recorded on vulcanized samples (cylindrical specimen of section 95 mm 2 and height 14 mm). The sample is initially subjected to a predeformation of 10%, then to a sinusoidal deformation in alternating compression of +/- 2%. The measurements are carried out at 60 ° C. and at a frequency of 10 Hz.
Les résultats, présentés dans le tableau IV, sont le module complexe en compression (E* - 60 °C - 10 Hz) et le facteur de perte (tan δ - 60 °C - 10 Hz).
Dans une seconde série de mesures, les valeurs du facteur de perte (tan δ) et de module élastique en cisaillement dynamique (G') sont enregistrées sur des échantillons vulcanisés (éprouvette parallélépipédique de section 8 mm2 et de hauteur 7 mm). L'échantillon est soumis à une déformation sinusoïdale en double cisaillement alternée à une température de 40 °C et à une fréquence de 10 Hz. Les processus de balayage en amplitude de déformations s'effectuent selon un cycle aller-retour, allant de 0,1 à 50 % puis retour de 50 à 0,1 %. The results, presented in Table IV, are the complex modulus in compression (E * - 60 ° C - 10 Hz) and the loss factor (tan δ - 60 ° C - 10 Hz). In a second series of measurements, the values of the loss factor (tan δ) and elastic modulus in dynamic shear (G ') are recorded on vulcanized samples (parallelepipedal specimen of section 8 mm 2 and height 7 mm). The sample is subjected to an alternating double shear sinusoidal deformation at a temperature of 40 ° C. and at a frequency of 10 Hz. The amplitude-deformation sweep processes are carried out in a round-trip cycle, ranging from 0.degree. 1 to 50% then return 50 to 0.1%.
Les résultats, présentés dans le tableau IV, sont issus du balayage en amplitude de déformations au retour et concernent la valeur maximale du facteur de perte (tan δ max retour - 40 °C - 10 Hz) ainsi que l'amplitude du module élastique (ΔΘ' - 40 °C - 10 Hz) entre les valeurs à 0,1 % et 50 % de déformation (effet Payne). The results, presented in Table IV, are derived from the amplitude sweep of the return strains and relate to the maximum value of the loss factor (tan δ max return - 40 ° C - 10 Hz) as well as the amplitude of the elastic modulus ( ΔΘ '- 40 ° C - 10 Hz) between the values at 0.1% and 50% deformation (Payne effect).
Tableau IV Table IV
La composition issue de l'invention (composition 3) présente de très bonnes propriétés dynamiques (propriétés hystérétiques à 60 °C), notamment par rapport à la composition témoin (témoin 3). The composition resulting from the invention (composition 3) has very good dynamic properties (hysteretic properties at 60 ° C.), especially with respect to the control composition (control 3).
On constate, à la lecture des résultats des tableaux II à IV, que la composition issue de l'invention (composition 3) présente un très bon compromis de propriétés.
It can be seen from the results of Tables II to IV that the composition resulting from the invention (composition 3) has a very good compromise of properties.
Claims
(1 ) les polyisoprènes de synthèse homopolymères ; (1) homopolymer synthetic polyisoprenes;
(2) les polyisoprènes de synthèse copolymères consistant dans le poly(isoprène-butadiène), le poly(isoprène-styrène) et le poly(isoprène- butadiène-styrène) ; (2) synthetic polyisoprene copolymers consisting of poly(isoprene-butadiene), poly(isoprene-styrene) and poly(isoprene-butadiene-styrene);
(3) le caoutchouc naturel ; (3) natural rubber;
(4) le caoutchouc butyle ; (4) butyl rubber;
(5) un mélange d'au moins deux des élastomères précités (1 ) à (4) ; (5) a mixture of at least two of the aforementioned elastomers (1) to (4);
(6) un mélange contenant plus de 50 % en poids d'élastomère précité (1 ) ou (3) et moins de 50 % en poids d'élastomère diénique autre qu'isoprénique consistant dans le polybutadiène, le polychloroprène, le poly(butadiène-styrène), le poly(butadiène-acrylonitrile) ou un terpolymère. 33- Composition selon l'une des revendications 23 à 32, caractérisée en ce que ladite composition comprend à titre d'élastomère isoprénique au moins du caoutchouc naturel, de préférence ladite composition d'élastomère(s) comprenant à titre d'élastomère(s) uniquement du caoutchouc naturel. 34- Composition selon l'une des revendications 23 à 33, caractérisée en ce que ladite composition comprend en outre au moins un composé choisi parmi les agents de vulcanisation, les accélérateurs de vulcanisation, les activateurs de vulcanisation, du noir de carbone, les agents protecteurs, les agents antireversions, les agents de plastification. (6) a mixture containing more than 50% by weight of the aforementioned elastomer (1) or (3) and less than 50% by weight of diene elastomer other than isoprene consisting of polybutadiene, polychloroprene, poly(butadiene -styrene), poly(butadiene-acrylonitrile) or a terpolymer. 33- Composition according to one of claims 23 to 32, characterized in that said composition comprises, as isoprene elastomer, at least natural rubber, preferably said composition of elastomer(s) comprising, as elastomer(s), ) only natural rubber. 34- Composition according to one of claims 23 to 33, characterized in that said composition further comprises at least one compound chosen from vulcanization agents, vulcanization accelerators, vulcanization activators, carbon black, agents protectors, anti-reversion agents, plasticizing agents.
35- Article comprenant au moins une composition selon l'une des revendications 23 à 34, cet article consistant en une semelle de chaussures, un revêtement de sols, une barrière aux gaz, un matériau ignifugeant, un galet de téléphérique, un joint d'appareils électroménagers, un joint de conduites de liquides ou de gaz, un joint de système de freinage, un tuyau, une gaine, un câble, un support de moteur, une bande de convoyeur, une courroie de transmissions ou, de préférence, un pneumatique.
36- Pneumatique selon la revendication 35 pour les véhicules poids lourds, en particulier pour les camions. 37- Composition comprenant au moins une charge inorganique renforçante pour élastomère et au moins un agent de couplage charge inorganique - élastomère, caractérisée en ce que ledit agent de couplage charge inorganique - élastomère est le 3-acryloxy-propyltriethoxysilane, ladite charge inorganique renforçante et ledit agent de couplage charge inorganique - élastomère étant tels que définis dans l'une des revendications 1 à 12. 35- Article comprising at least one composition according to one of claims 23 to 34, this article consisting of a shoe sole, a floor covering, a gas barrier, a flame retardant material, a cable car roller, a gasket household appliances, a liquid or gas pipe joint, a braking system joint, a pipe, a sheath, a cable, a motor support, a conveyor belt, a transmission belt or, preferably, a tire . 36- Tire according to claim 35 for heavy goods vehicles, in particular for trucks. 37- Composition comprising at least one reinforcing inorganic filler for elastomer and at least one inorganic filler - elastomer coupling agent, characterized in that said inorganic filler - elastomer coupling agent is 3-acryloxy-propyltriethoxysilane, said reinforcing inorganic filler and said inorganic filler - elastomer coupling agent being as defined in one of claims 1 to 12.
38- Composition selon la revendication 37, caractérisée en ce qu'il comprend en outre au moins un agent de recouvrement de ladite charge inorganique renforçante. 38- Composition according to claim 37, characterized in that it further comprises at least one covering agent for said reinforcing inorganic filler.
39- Utilisation de la composition selon l'une des revendications 37 et 38 dans une composition d'élastomère(s) comprenant au moins un élastomère 39- Use of the composition according to one of claims 37 and 38 in an elastomer composition comprising at least one elastomer
isoprénique, en particulier du caoutchouc naturel. 40- Utilisation selon la revendication 39 dans un pneumatique, en particulier pour les véhicules poids lourds, notamment pour les camions.
isoprene, especially natural rubber. 40- Use according to claim 39 in a tire, in particular for heavy goods vehicles, in particular for trucks.
Applications Claiming Priority (3)
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FR1001368A FR2958294B1 (en) | 2010-04-01 | 2010-04-01 | USE OF A PRECIPITATED SILICA CONTAINING ALUMINUM AND 3-ACRYLOXY-PROPYLTRIETHOXYSILANE IN AN ISOPRENE (S) ELASTOMERIC COMPOSITION |
FR1004309A FR2966829B1 (en) | 2010-11-03 | 2010-11-03 | USE OF A PRECIPITED SILICA CONTAINING ALUMINUM AND HAVING A PARTICULAR POROUS DISTRIBUTION AND 3-ACRYLOXY-PROPYLTRIETHOXYSILANE IN AN ISOPRENE (S) ELASTOMERIC COMPOSITION |
PCT/EP2011/055141 WO2011121129A2 (en) | 2010-04-01 | 2011-04-01 | Use of precipitated silica containing aluminium and 3-acryloxy-propyltriethoxysilane in an isoprenic elastomer composition |
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2011
- 2011-04-01 KR KR1020127025669A patent/KR20120130241A/en not_active Application Discontinuation
- 2011-04-01 WO PCT/EP2011/055141 patent/WO2011121129A2/en active Application Filing
- 2011-04-01 CN CN2011800165583A patent/CN102869521A/en active Pending
- 2011-04-01 EP EP11712249A patent/EP2552713A2/en not_active Withdrawn
- 2011-04-01 RU RU2012146510/05A patent/RU2541066C2/en not_active IP Right Cessation
- 2011-04-01 US US13/638,861 patent/US20130178569A1/en not_active Abandoned
- 2011-04-01 JP JP2013501868A patent/JP2013523934A/en not_active Ceased
Non-Patent Citations (1)
Title |
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See references of WO2011121129A2 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110139876A (en) * | 2016-12-05 | 2019-08-16 | 戴科欧洲研究科学实验室 | Dynamic conveyor belt |
CN110139876B (en) * | 2016-12-05 | 2021-11-26 | 戴科欧洲研究科学实验室 | Power transmission belt |
Also Published As
Publication number | Publication date |
---|---|
RU2012146510A (en) | 2014-05-10 |
JP2013523934A (en) | 2013-06-17 |
WO2011121129A3 (en) | 2012-10-26 |
KR20120130241A (en) | 2012-11-29 |
RU2541066C2 (en) | 2015-02-10 |
CN102869521A (en) | 2013-01-09 |
US20130178569A1 (en) | 2013-07-11 |
WO2011121129A2 (en) | 2011-10-06 |
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