EP3328903A1 - Procede de fabrication d'un agent anti-retrait pour le moulage d'un polyester insature en presence d'un diluant reactif, agent anti-retrait susceptible d'etre obtenu par ledit procede de fabrication - Google Patents
Procede de fabrication d'un agent anti-retrait pour le moulage d'un polyester insature en presence d'un diluant reactif, agent anti-retrait susceptible d'etre obtenu par ledit procede de fabricationInfo
- Publication number
- EP3328903A1 EP3328903A1 EP16750953.8A EP16750953A EP3328903A1 EP 3328903 A1 EP3328903 A1 EP 3328903A1 EP 16750953 A EP16750953 A EP 16750953A EP 3328903 A1 EP3328903 A1 EP 3328903A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- olefin
- unsaturated polyester
- polyolefin
- equal
- function
- 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- Withdrawn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
- 239000012753 anti-shrinkage agent Substances 0.000 title claims abstract description 86
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 54
- 239000003085 diluting agent Substances 0.000 title claims abstract description 33
- 238000000465 moulding Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000008569 process Effects 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 229920000098 polyolefin Polymers 0.000 claims abstract description 75
- 239000000178 monomer Substances 0.000 claims abstract description 63
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 20
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000001336 alkenes Chemical class 0.000 claims description 71
- 239000000203 mixture Substances 0.000 claims description 57
- 239000002253 acid Substances 0.000 claims description 48
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 46
- 150000008065 acid anhydrides Chemical class 0.000 claims description 39
- 238000007306 functionalization reaction Methods 0.000 claims description 37
- -1 polyethylene Polymers 0.000 claims description 27
- 238000002844 melting Methods 0.000 claims description 25
- 230000008018 melting Effects 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 150000004820 halides Chemical class 0.000 claims description 19
- 239000004698 Polyethylene Substances 0.000 claims description 18
- 229920000573 polyethylene Polymers 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 150000003141 primary amines Chemical class 0.000 claims description 7
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 230000003014 reinforcing effect Effects 0.000 claims description 5
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001721 transfer moulding Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 2
- 239000011159 matrix material Substances 0.000 description 27
- 229920006337 unsaturated polyester resin Polymers 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 240000002234 Allium sativum Species 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 235000004611 garlic Nutrition 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000002787 reinforcement Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 229920002689 polyvinyl acetate Polymers 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000004412 Bulk moulding compound Substances 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000007572 expansion measurement Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JNBVLGDICHLLTN-DZUOILHNSA-N (2s)-2-acetamido-n-[(2s,3s)-4-[[[(2s)-2-acetamido-3-methylbutanoyl]amino]-(cyclohexylmethyl)amino]-3-hydroxy-1-phenylbutan-2-yl]-3-methylbutanamide Chemical compound C([C@H](NC(=O)[C@@H](NC(C)=O)C(C)C)[C@@H](O)CN(CC1CCCCC1)NC(=O)[C@@H](NC(C)=O)C(C)C)C1=CC=CC=C1 JNBVLGDICHLLTN-DZUOILHNSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- LQVYKEXVMZXOAH-OWOJBTEDSA-N (e)-oct-4-enedioic acid Chemical compound OC(=O)CC\C=C\CCC(O)=O LQVYKEXVMZXOAH-OWOJBTEDSA-N 0.000 description 1
- VSSAADCISISCOY-UHFFFAOYSA-N 1-(4-furo[3,4-c]pyridin-1-ylphenyl)furo[3,4-c]pyridine Chemical compound C1=CN=CC2=COC(C=3C=CC(=CC=3)C3=C4C=CN=CC4=CO3)=C21 VSSAADCISISCOY-UHFFFAOYSA-N 0.000 description 1
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- HVVPYFQMCGANJX-UHFFFAOYSA-N 2-methylprop-2-enyl prop-2-enoate Chemical compound CC(=C)COC(=O)C=C HVVPYFQMCGANJX-UHFFFAOYSA-N 0.000 description 1
- UYCICMIUKYEYEU-ZHACJKMWSA-N 3-[(e)-dodec-2-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCC\C=C\CC1CC(=O)OC1=O UYCICMIUKYEYEU-ZHACJKMWSA-N 0.000 description 1
- CIMXGTDNUHWJCZ-BQYQJAHWSA-N 3-[(e)-non-2-enyl]oxolane-2,5-dione Chemical compound CCCCCC\C=C\CC1CC(=O)OC1=O CIMXGTDNUHWJCZ-BQYQJAHWSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- XAMCLRBWHRRBCN-UHFFFAOYSA-N 5-prop-2-enoyloxypentyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCOC(=O)C=C XAMCLRBWHRRBCN-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000002512 anti-withdrawal effect Effects 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical class C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007571 dilatometry Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical class [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
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- 230000019612 pigmentation Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 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
- 230000009257 reactivity Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920006135 semi-crystalline thermoplastic polymer Polymers 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
Definitions
- the present invention relates to the anti-shrinkage agents used in liquid resinous compositions comprising an unsaturated polyester and a monomer copolymerizable with said polyester in order to limit the shrinkage of the matrices resulting from said polymerizable compositions.
- Unsaturated polyester resins are used in many fields of application, in particular for the molding of composite parts comprising an organic matrix and reinforcements, such as glass fibers.
- the organic matrix ensures the maintenance and protection of reinforcements.
- the chemical nature of the organic matrix may vary, and may be for example of the epoxy, acrylic or polyester type.
- These composite parts are widely used for the manufacture of automobile or aircraft parts, furniture parts, building parts, such as partition elements, and housings for electronic devices.
- the organic matrices have the disadvantage of all having compared to their initial volumes in the uncrosslinked state, a certain shrinkage, which is unacceptable because very pronounced in the case of unsaturated polyester resins.
- This shrinkage phenomenon is generated during the crosslinking of the unsaturated polyester with its comonomer (s), in particular during the passage of van der Waals bonds to covalent bonds.
- the overall shrinkage observed is of the order of 7% to 10% which generates surface defects which render the composite parts unusable.
- the volume shrinkage causes, in fact, rough surfaces that reveal reinforcements, such as glass fibers, protruding from the surface of the molded composite parts.
- these composite parts require surfaces having a clean and smooth appearance.
- polyesters resins top coats, gel coats
- PVACs polyvinyl acetate
- the unsaturated polyester resin as an anti-shrinkage agent to decrease removal of the organic matrix and improve the surface appearance of the piece. composite.
- PVAC has the drawback of creating micro-voids within the organic matrix, which are detrimental to the mechanical properties of the composite part.
- the composite parts thus treated also have the disadvantage of presenting a "blistering" phenomenon when they are painted. Thus, many non-recyclable parts are always put to rebus because of surface defects, or even insufficient mechanical properties.
- Copolymers or other homopolymers such as polyurethanes, poly (methyl methacrylate) and polystyrene can also be used as an anti-shrinkage agent. They have a withdrawal compensation mode similar to that of PVAC.
- anti-shrinkage agents are soluble in the liquid resinous composition comprising the unsaturated polyester and the monomer copolymerizable with said unsaturated polyester, and generate micro-voids in the cross-linked organic matrix to compensate for shrinkage.
- the anti-shrinkage agent shifts, generating a phase rich in anti-shrinkage agent, such as in PVAC, and a phase that is poor in anti-shrinkage, such as in PVAC.
- a phase rich in anti-shrinkage agent such as in PVAC
- a phase that is poor in anti-shrinkage such as in PVAC.
- US 5,589,539 relates to a soluble anti-shrinkage agent comprising an esterified polyurethane to improve the pigmentation properties of organic matrices.
- This anti-shrink agent is dissolved at 50% in styrene.
- the functionalized polyurethanes are prepared in the presence of amines as catalyst and vinyl compounds such as styrene. This agent has the disadvantage that it forms micro-voids in the organic matrix as explained above.
- EP 0,274,273 relates to a non-thermoplastic anti-shrinkage agent which is liquid at ambient temperature and has a low crystallinity.
- This anti-shrinkage agent is the product of the reaction between a copolymer of ethylene and alphaolefin and a carboxylic acid or its corresponding anhydride in the presence of a radical initiator, such as an organic peroxide.
- US 4,258,143 relates to an anti-shrink agent comprising a polyethylene modified with carboxyl groups.
- This anti-shrinkage agent is obtained by the reaction between a polyolefin, such as polyethylene, with a polycarboxylic acid in the presence of a source of radicals, such as hydrogen peroxide.
- a source of radicals such as hydrogen peroxide.
- the unsaturations of the carboxylic acid will react with the peroxides to functionalize the polyolefin to form a antiretrait agent which will no longer have carbon-carbon double bonds capable of reacting with the unsaturated polyester.
- FR 2.170.221 relates to an anti-shrinkage agent comprising a polyolefin polymerized or graft copolymerized with an unsaturated monomer, such as styrene, having affinity for the unsaturated polyester resin so that the anti-shrink agent is soluble or swells in the saturated monomer and / or in the unsaturated polyester resin.
- the degree of grafting of the unsaturated monomer on the polyolefin is determined so that the (re) crystallization of the graft copolymer is prevented during molding and curing in order to avoid the phenomena of agglomeration or oozing of the anti-shrinkage agent. on the surface of the organic matrix.
- this anti-shrinkage agent has no reactive radical function allowing it to copolymerize with the unsaturated polyester.
- the above-mentioned anti-shrinkage agents make it possible to reduce the volume shrinkage observed on organic polyester matrices by creating micro-voids. Nevertheless, these micro-voids reduce the mechanical performance of the composite parts. In addition, the molded parts always have surface defects making them often unusable. Indeed, there is a phenomenon of "blistering" making the painting of the organic matrix problematic.
- the aforementioned anti-shrinkage agents also have the disadvantages that they compensate for the shrinkage by de-phasing and thus generating a phase rich in anti-shrinkage agents and a phase that is poor in anti-shrinkage agents. The organic matrix obtained is therefore not homogeneous, and is opaque thus making it impossible to shade the mass.
- the subject of the present invention is thus an improved anti-shrinkage agent making it possible to reduce the shrinkage of the polyester organic matrices significantly without affecting the mechanical performance of the molded parts comprising said matrices while at the same time offering surfaces of net appearance, in particular allowing painting without "blistering" phenomenon.
- the present invention also relates to an anti-removal agent easy to use, stable and does not prevent the hue in the mass of the organic matrix.
- the subject of the present invention is therefore, in a first aspect, a process for producing an anti-shrinkage agent for molding an unsaturated polyester in the presence of a reactive diluent, said reactive diluent comprising one or more copolymerizable monomer (s). (s) with the unsaturated polyester, said process advantageously comprising the following steps:
- an anti-shrinkage agent comprising a polyolefin (a1) and / or an olefin copolymer (s) and of one or more monomers other than an olefin (a2), with at least one carbon-carbon double bond reactive in radical polymerization, insoluble in the unsaturated polyester and in its reactive diluent, which is semi-crystalline and thermofusible, in particular at a temperature less than or equal to the temperature of setting
- the use of the unsaturated polyester resin in order to obtain its polymerization advantageously makes it possible to reduce the removal of the organic matrix from the molded part, to ensure a clean surface appearance while improving the mechanical performance of the molded part.
- unsaturated polyester resin means a resin comprising the unsaturated polyester and one or more monomer (s) copolymerizable with said unsaturated polyester, at least one of said monomer (s) acting as reactive diluent.
- the anti-shrinkage agent according to the invention is not soluble in the unsaturated polyester resin so that the latter, once added to the unsaturated polyester resin, retains its crystallinity to compensate for the subsequent removal of the polyester resin. during its crosslinking.
- the inventors have demonstrated that during the radical polymerization reaction of the unsaturated polyester with its copolymerization monomer (reactive diluent), the liquid resinous composition is subjected to a processing temperature, causing the partial or total melting of the anti-shrinkage agent, and thus the passage of the crystalline phase of the anti-shrinkage agent to an amorphous phase thus generating a large volume increase to compensate for shrinkage.
- polymer is intended to mean any polymer comprising at least two repeating units (or monomeric units), and therefore the oligomers.
- the polyolefin (a1), the functionalized polyolefin (Al), the olefin copolymer (s) and one or more monomer (s) different from an olefin (a2), and the olefin copolymer ( s) and one or more monomers other than one functionalized olefin (A2) comprise at least two repeating units (n> 2), more preferably at least ten repeating units (n> 10). ), in particular at least fifteen repetition patterns (n> 15).
- said polyolefin (a) or said olefin copolymer (s) is reacted with one or more monomers other than an olefin (a2), each having at its end chain a reactive function X, by mixing them and heating them to a temperature greater than or equal to 60 ° C, preferably greater than or equal to 80 ° C, still more preferably lower than or equal to 150 ° C, especially lower or equal to 120 ° C, for at least 5 minutes, preferably for at least 30 minutes, even more preferably at least 45 minutes, particularly at least 60 minutes, more particularly at most 120 minutes.
- the mixture in step ii) comprises, in addition to the functionalization compound (b), an acid other than a carboxylic acid.
- the acid may be sulfuric acid.
- the mixing is carried out under vacuum in order to extract the water possibly formed as a by-product of the reaction between the polyolefin (al) or the olefin copolymer (s) and a or a different monomer (s) of an olefin (a2) with the functionalizing compound (b).
- the anti-shrinkage agent is insoluble in any reactive diluent of the unsaturated polyester and non-reactive solvent of the unsaturated polyester, especially in apolar solvents, at room temperature, ie at a temperature of between 0 ° C and 35 ° C, upper and lower terminals included.
- the diluents reactive with the unsaturated polyester include styrene; substituted styrenes, such as vinyl toluene, tert-butylstyrene; lower alkyl (C1 to C4) esters; acrylic acid esters; methacrylic acid esters; alpha-methylstyrene; cyclic acrylates and methacrylates, such as aromatic cyclohexyl acrylates, benzyl acrylates; bi-cyclic methacrylates and acrylates, such as isobornyl acrylates; halogenated styrenes, such as chlorostyrene and dichlorostyrene; 1,3-butanediol dimethacrylate; diallyl phthalate, etc.
- styrene substituted styrenes, such as vinyl toluene, tert-butylstyrene
- lower alkyl (C1 to C4) esters acrylic acid esters
- the anti-shrinkage agent according to the invention may also be insoluble at temperatures above 35 ° C.
- the term "anti-removal agent insoluble in the unsaturated polyester and the reactive diluent (ie unsaturated polyester resin)” means that said anti-shrink agent is soluble to less than 1 % by weight relative to the total weight of unsaturated polyester, optionally mixed with its copolymerization monomer at ambient temperature, that is to say at a temperature greater than or equal to 10 ° C. and less than or equal to 35 ° C. C, optionally at a temperature greater than or equal to 10 ° C and less than or equal to 150 ° C, in particular less than or equal to 110 ° C.
- the measurement of the solubility and therefore the insolubility of the anti-shrinkage agent according to the invention can be determined by means of the ISO 25179: 2010 "Adhesives - Determination of the Solubility of Soluble Pressure-Sensitive Adhesives". water or in alkalis.
- the anti-shrink agent retain its insoluble character at least during storage in the unsaturated polyester resin, especially at room temperature, so that it retains its semi-crystalline character and can change state during the crosslinking of the unsaturated polyester resin (volume expansion of the anti-shrinkage agent due to the melting of the crystalline zones).
- the anti-shrinkage agent according to the invention is a semi-crystalline thermoplastic polymer and therefore has a melting temperature.
- the temperature (° C) from which the anti-shrinkage agent begins to become liquid is understood as the melting temperature.
- the melting temperature Tf (° C) is greater than the glass transition temperature Tg (° C) and lower than the thermal decomposition temperature of the anti-shrinkage agent.
- the melting temperature Tf (° C) of the anti-shrinkage agent is greater than or equal to about 35 ° C, more preferably greater than or equal to about 45 ° C.
- the melting temperature Tf (° C) of the anti-shrinkage agent is less than or equal to 160 ° C, more preferably less than or equal to 135 ° C, more preferably less than or equal to 125 ° C, particularly lower than or equal to 105 ° C, more particularly less than or equal to 90 ° C, even more particularly less than or equal to 80 ° C.
- micro-crystalline polymer is understood to mean any polymer comprising two phases, that is to say a crystalline phase and an amorphous phase, a crystalline phase is formed of several crystallites dispersed in a matrix, the amorphous phase.
- the anti-shrinkage agent according to the invention has a degree of crystallinity greater than or equal to 30%, more preferably greater than or equal to 35%, even more preferably greater than or equal to 40%, particularly greater than or equal to 45%, more particularly greater than or equal to 50%, even more particularly greater than or equal to 55%, especially greater than or equal to 60%.
- Crystallinity ratio is understood to mean the ratio of the proportion by weight or by volume of the crystalline phase of the anti-shrinkage agent relative to the total volume or mass (e) of the crystalline phases and amorphous, that is to say the volume or the total mass of the anti-shrinkage agent.
- the anti-shrinkage agent according to the invention is a functionalized polyethylene
- the density p c of the perfect crystalline anti-shrinkage agent will be based on the polyethylene.
- the mass of the crystalline phase of the anti-shrinkage agent is greater than the mass of the amorphous phase.
- the structure of the carbon chain ensures the crystallinity of the polyolefin, or the copolymer of olefin (s) and of one or more monomer (s) different (s) of an olefin, and the length of the carbon chain allows to adjust the melting temperature.
- polyolefin is understood to mean a homopolymer of an olefin monomer, or a copolymer of at least two different olefin monomers.
- copolymer of olefin (s) and of one or more monomers other than (s) of an olefin is understood to mean a copolymer comprising one or more olefin monomer (s). different and one or more monomer (s) different from an olefin and different from each other.
- the anti-shrinkage agent comprises a polyolefin.
- Said at least one reactive carbon-carbon double bond in radical polymerization can be found at the chain end of the anti-shrinkage agent formed (A1, A2) and / or between two monomers of the carbon chain of the anti-shrinkage agent .
- This arrangement depends on the number of moles of polyolefin (a1) and / or copolymer (a2) relative to the number of moles of functionalization compound (b).
- invention with respect to the total number of monomer units of said copolymer is greater than or equal to more than 50%, more preferably greater than or equal to 60%, still more preferably greater than or equal to 70%, particularly greater than or equal to 80% more particularly greater than or equal to 85%, even more particularly greater than or equal to 90%.
- the polyolefin according to the invention is a polyethylene or a copolymer of ethylene and an olefin (different from ethylene) or of several olefins different from each other (and different from ethylene).
- the polyolefins according to the invention are saturated aliphatic polymers.
- an olefin polymer according to the invention is especially of formula - (CH 2 -CRiR 2 ) n - in which R 1 and R 2 represent, each independently of one another: a hydrogen atom or an alkyl group, preferably an alkyl group comprising from one to ten carbon atoms, more preferably from one to six carbon atoms, especially from one to four carbon atoms.
- the alkyl groups are preferably: a methyl group -CH 3 ; an ethyl group -CH 2 -CH 3 or a butyl group, such as n-butyl, sec-butyl, isobutyl or tert-butyl groups.
- the polyolefins according to the present invention are chosen from the list comprising: low density or high density polyethylenes, copolymers of ethylene and of an olefin (different from ethylene) or of several olefins different from each other (and different from ethylene), polypropylene, copolymers of propylene and an olefin (different from propylene) or several olefins different from each other (and different from propylene).
- Ethylene and 1-butene are preferred, especially ethylene.
- alpha-olefins can be polymerized alone or in combination with two or more.
- the olefin copolymer and a monomer other than an olefin (a2) is chosen from the list comprising: copolymers of ethylene and of vinyl esters, copolymers of ethylene and of ester of acrylic acid or methacrylic acid, copolymers of ethylene and acrylonitrile.
- the unsaturated polyesters suitable for the implementation of the invention are prepared by the condensation of a dicarboxylic acid having an ethylenic unsaturation alpha, beta or a corresponding anhydride or mixtures thereof with a dihydric alcohol, or a mixture of dialcohol or their oxides.
- unsaturated dicarboxylic acids or anhydrides examples include maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and chloromaleic acid. It is possible to replace a small proportion of the unsaturated dicarboxylic acid (up to 25 mole percent) with saturated dicarboxylic acids, such as ortho-phthalic, isophthalic, terephthalic, succinic, adipic, sebacic and methyl acids. succinic, etc.
- dialcohols or their oxides used with the dicarboxylic acids are in a known manner: 1,2-propanediol (propylene glycol), dipropylene glycol, diethylene glycol, ethylene glycol, 1,3-butanediol, , 4-butanediol, neopentyl glycol, triethylene glycol, tripropylene glycol, ethylene oxide.
- the monomers copolymerizable with the unsaturated polyester are, in known manner, styrene, substituted styrenes such as vinyl toluene, tert-butylstyrene.
- Other ethylenically unsaturated monomers which may, where appropriate, be used in combination with the above monomers, in amounts of less than 50% by weight, include lower alkyl (Cl-C4) esters, esters acrylic acid and methacrylic acid, alpha-methylstyrene, cyclic acrylates and methacrylates, such as those of cyclohexyl, aromatic, such as those of benzyl, bi-cyclic methacrylates and acrylates such as those of isobornyl, halogenated styrenes such as chlorostryene and dichlorostyrene, 1,3-butanediol dimethacrylate, diallyl phthalate, etc.
- the reactive group X is chosen from the list comprising: a monoalcohol, a primary amine, a secondary amine, a mono or poly carboxylic acid or the corresponding acid halide or its corresponding acid anhydride, or a mixture of these.
- the functionalization compound (b) is chosen from the list comprising or comprises a reactive function chosen from the list comprising: a mono or polycarboxylic acid or its corresponding acid anhydride or its corresponding acid halide, an isocyanate , an epoxy, a primary amine, a secondary amine, an acrylate, a monoalcohol, or a mixture thereof.
- the determination of the reactive function X and of the functionalization compound (b) is carried out so that the latter react chemically together and graft a carbon-carbon double bond to the polyolefin (a l) or to the polyolefin copolymer (a 2) so that it is capable of copolymerizing with the unsaturated polyester and / or the reactive diluent.
- the reactive function X is a monoalcohol (-OH)
- the functionalization compound (b) is mono or polycarboxylic acid or its corresponding acid halide or its corresponding acid anhydride or an isocyanate or an epoxy
- the functionalization compound (b) comprises one or more carboxylic acid function (s) or its corresponding acid halide function (s) or its function (s) ( s) corresponding acid anhydride (s) or an isocyanate function or epoxy function (option 1);
- the reactive function X is a primary amine or a secondary amine
- the reactive function X is a carboxylic acid function (-COOH)
- the functionalization compound (b) is an epoxy, an isocyanate, an amine, an alcohol
- the functionalization compound (b) comprises an epoxy function, an isocyanate function, an amine function, a hydroxyl function (-OH) (option 3).
- the reactive function X and the functionalization compound (b) are determined according to option 1 and option 2, preferably under option 1, more particularly the functionalization compound (b) is a mono acid. or polycarboxylic acid or its corresponding acid anhydride or its corresponding acid halide.
- R i; R ,,, (3 ⁇ 43 ⁇ 4 Riv are each independently chosen from: a hydrogen atom, a linear or branched alkyl chain, saturated or unsaturated, a cycloalkyl, an alkenyl, an aryl, an ether or a polyether.
- the above mentioned is preferably C 1 to C 10, still more preferably C 1 to C 6, still more preferably C 1 to C 3, and the abovementioned cycloalkyl is preferably C 3 to C 10, and more preferably C 3 to C 6.
- epoxy function is understood to mean any -O-CH 2 -C 2 H 3 O or -C 2 H 3 O (or oxirane) or C (-O-) C function.
- the term "primary amine” denotes any group of formula R a NH 2 , for secondary amine any group of formula R b R c NH, in which R a , R b and R c are saturated or unsaturated alkyl groups. linear or branched, preferably C 1 -C 20, or cycloalkyl, or alkenyl, or aryl, or ether, or polyether.
- the abovementioned alkyl chain is preferably C 1 to C 10, still more preferably C 1 to C 6, still more preferably C 1 to C 3, and the abovementioned cycloalkyl is preferably C 3 to C 10, and even more preferably C 3 to C 6.
- the term "primary amine function” means any -NH 2 function, and "secondary amine function” any -NH- function.
- mono carboxylic acid means an acid comprising a function -COOH.
- carboxylic acid function is understood to mean the -COOH function.
- the term "acid halide” means an acid comprising a function -COA in which A is an atom of the halogen family.
- polycarboxylic acid is understood to mean an acid comprising several functions -COOH, and by its “corresponding anhydride”, an acid comprising at least one -COO-CO- function.
- the (poly) (mono) carboxylic acids or their corresponding acid anhydrides according to the invention can be: maleic acid, itaconic acid, methacrylic acid, acrylic acid, (2-nonen-1 -yl) succinic anhydride, (2-Dodecen-1-yl) succinic anhydride, maleic anhydride, itaconic anhydride, methacrylic anhydride, e-oct-4-ene-1,8-dioic acid.
- the acrylates that may be suitable for the invention are: allyl acrylate, methallyl acrylate, allyloxypropyl acrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate , trimethylolpropane acrylate, ... or mixtures thereof.
- R d is a hydrogen atom saturated or unsaturated alkyl, linear or branched, preferably C1 to C20, or cycloalkyl, or alkenyl, or aryl, or an ether, or a polyether.
- the abovementioned alkyl chain is preferably C 1 to C 10, still more preferably C 1 to C 6, still more preferably C 1 to C 3, and the abovementioned cycloalkyl is preferably C 3 to C 10 and still more preferably C 3 to C 6.
- the isocyanates that may be suitable for the invention are: 3-isopropenyl- ⁇ -dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, allyl isocyanate, vinyl isocyanate, or mixtures thereof.
- the total number of moles of functionalization compound (s) (b) is between 1 and 2 for a total number of moles of polyolefin (a1) or copolymer of olefin (s) and one or more monomer (s) different from an olefin (a2), between 1 and 2.
- the carbon double bond reactive carbon radical polymerization can be arranged between two polyolefin chains (Al) or said copolymer (A2) according to the invention.
- the total number of moles of functionalization compound (s) (b) is 1 for a total number of moles of polyolefin (a1) or of olefin copolymer (s) and of one or more other monomer (s) different from an olefin (a2) of 1
- the carbon-carbon double bond is arranged at the chain end of the functionalized polyolefin (Al) or of the olefin copolymer (s) and one or more different monomers of a functionalized olefin (A2).
- the reactive function X is a monoalcohol function (a single hydroxyl function -OH) and the functionalization compound (b) is a mono or polycarboxylic acid or its corresponding acid anhydride or its corresponding acid halide or comprises one or more carboxylic acid function (s) or its corresponding acid halide (s) function (s) or anhydride function (s) thereof corresponding acid (s).
- the functionalization reaction of the polyolefin al or the copolyolefin a2 does not implement toxic reagents, compared to the isocyanate.
- the reactivity of the copolymerization reaction with the polyester resin is improved in this case.
- the functionalization reaction is furthermore better controlled than the amine-epoxy or amine-acrylate reactions.
- Acid halides are not preferred in order to avoid releases of halogenated compounds.
- the mono or polycarboxylic acid or its corresponding acid anhydride or its corresponding acid halide is chosen from the list comprising: maleic anhydride, itaconic anhydride, methacrylic anhydride and acrylic acid or their mixtures.
- the object of the present invention is, according to a second aspect, a anti-shrinkage agent for molding an unsaturated polyester in the presence of a reactive diluent, said reactive diluent comprising a monomer copolymerizable with the unsaturated polyester, obtainable by the implementation of the method described by reference according to a first aspect of the invention.
- the functionalized polyolefin (Al) and / or the olefin copolymer (s) and one or more monomers other than one functionalized olefin (A2) are insoluble in the unsaturated polyester and in the diluent. reagent, and is thermoplastic and semi-crystalline.
- the functionalized polyolefin (Al) is a polyethylene comprising, at the chain end, a monoalcohol function esterified with a mono or polycarboxylic acid, or its corresponding acid halide or its corresponding acid anhydride, or the mixture thereof.
- the functionalized polyolefin (Al) or the olefin copolymer (s) and of one or more monomers different (s) from a functionalized olefin (A2) has a melting temperature Tf (° C. ) less than or equal to the processing temperature Tw (° C) of the unsaturated polyester to obtain its radical polymerization.
- the processing temperature Tw thus corresponds in practice to the crosslinking temperature of the unsaturated polyester.
- the melt temperature of the anti-shrinkage agent Tf is less than about 10 ° C, more preferably less than about 15 ° C, particularly lower about 20 ° C, more preferably about 30 ° C, at the processing temperature Tw.
- the processing temperature Tw is greater than or equal to approximately 60 ° C, more preferably greater than or equal to approximately 80 ° C, particularly greater than or equal to approximately 100 ° C.
- the functionalized polyolefin (Al) or its olefin copolymer (s) and one or more monomers other than one functionalized olefin (A2) has a higher average molecular weight or equal to 170 g / mol, preferably greater than or equal to 350 g / mol.
- the functionalized polyolefin (Al) or the olefin copolymer (s) and one or more monomers other than one functionalized olefin (A2) have a melting temperature Tf of less than or equal to at 200 ° C, preferably less than or equal to 180 ° C, more preferably less than or equal to 150 ° C.
- the anti-shrinkage agent is in the form of a powder at a temperature of less than or equal to 45 ° C., preferably at a temperature of less than or equal to 35 ° C., in particular greater than or equal to 0 ° C.
- the anti-shrinkage agent is in the form of a powder at atmospheric pressure.
- the subject of the present invention is, according to a third aspect, a liquid resinous composition comprising an unsaturated polyester, a reactive diluent comprising at least one monomer copolymerizable with the unsaturated polyester, and at least one anti-shrinkage agent according to any one of the variants.
- a liquid resinous composition comprising an unsaturated polyester, a reactive diluent comprising at least one monomer copolymerizable with the unsaturated polyester, and at least one anti-shrinkage agent according to any one of the variants.
- the proportion by weight of anti-shrinkage agent with respect to the total mass of said composition is less than or equal to 50%, preferably less than or equal to 40%, more preferably less than or equal to 30%, still more preferably less than or equal to 20%.
- the proportions of various components of the polymerizable resinous composition of the present invention vary greatly depending on the intended applications and performance of the resinous composition.
- the unsaturated polyester may be present in the resinous composition in proportions ranging from 20% inclusive to 80% inclusive, preferably from 25% inclusive to 60% inclusive, and even from 30% inclusive to 50% inclusive, by weight relative to total weight of the resinous composition.
- the copolymerizable monomer (s), such as the reactive diluent may be present in amounts of between about 20% inclusive and about 80% inclusive, preferably between 25% inclusive and About 75% inclusive, particularly from about 30% to about 65% by weight based on the total weight of the resinous composition.
- the resinous composition according to the present invention may comprise one or more curing agent (s).
- the resinous composition may also comprise fillers such as kaolin, alumina trihydrate, silica, calcium carbonate, or other fillers known as such in the state of the art.
- the resinous composition according to the present invention may further comprise at least one release agent, such as a salt of fatty acid and alkali metal or alkaline earth metal or zinc.
- a salt of fatty acid and alkali metal or alkaline earth metal or zinc examples include zinc, calcium, lithium, barium and magnesium stearates, as well as calcium salts of montanic acid. This latter salt is made from a natural product, montan wax, which is extracted from lignites.
- the release agent is preferably used in an amount in the range [1%; 8%] by weight relative to the total weight of the resinous composition.
- the resinous composition further comprises fillers and an initiator, for example an organic peroxide.
- the subject of the present invention is, according to a fourth aspect, the use of the anti-shrinkage agent according to any one of the variants previously described indifferently with reference to a first or second aspect according to the invention or of the resinous composition according to any of the variants described above with reference to a third aspect according to the invention, in compositions for mass molding, sheet molding, injection molding or transfer molding, preferably for sheet molding.
- the resinous compositions according to the present invention can be used in bulk molding compounds (BMC).
- BMC bulk molding compounds
- These resinous mass-molding compositions comprise unsaturated polyester resins with a copolymerizable monomer, added with an initiator, for example an organic peroxide as a polymerization initiator, optionally fillers such as calcium carbonate, optionally from 10% to 30% inclusive. included by weight of fibrous reinforcement, in particular of a release agent, and of the anti-shrinkage agent according to the invention.
- the moldable liquid resinous composition is introduced into a suitably shaped mold; the mold is then closed and heated to polymerize the composition.
- the molding can be carried out using the techniques known in this technology: contact molding, compression molding, liquid resin composition transfer molding (referred to as Resin Tranfer Molding / RTM), injection / compression molding, injection molding sheet molding (referred to as Sheet Molding Compound / SMC).
- the mold, and optionally the counter-mold are maintained at a temperature of between about 80 ° C. and 180 ° C., in particular between about 100 ° C. and 150 ° C., and at a pressure of 5 bar. at about 100 bar or more, for at least two minutes.
- the subject of the present invention is, according to a fifth aspect, a method of manufacturing a composite part advantageously comprising the following steps: a- providing a liquid resinous composition according to any of the embodiments described above with reference to a third aspect according to the invention;
- the reinforcements especially the reinforcing fibers, such as glass fibers, possibly present for molding reinforced parts, are used in proportions of up to about 98% by weight relative to the total weight of the composition. resinous.
- the reinforcements represent from 10% by weight to 60% by weight of the reinforced parts (comprising an organic matrix resulting from the resinous composition according to the thermoset invention), more preferably from 10% by weight to 50% by weight, still more preferably from 10% by weight to 35% by weight.
- a reinforcing member may be fibers or yarns considered individually or in combination; in particular implemented by weaving, knitting, braiding; and / or nonwovens; and / or particles; a three-dimensional structure, for example honeycomb or alveolar; especially chosen from the family of materials: para-aramid, meta-aramid, silica-based fibers, glass fibers, polyethylene terephthalate, high-density polyethylene, poly (p-phenylene-2,6-benzobisoxazole) PBO, carbon , silicon carbide, alumina hydrate, stainless steel, gravel, sand, glass beads, steel balls, silica.
- FIG. 1 is a schematic representation of the reaction between a polyolefin (a1) according to the invention, in this specific example of a polyethylene, comprising at the end of the chain a reactive function X with a functionalization compound (b) comprising a double carbon-carbon bond and reactive function Y for the formation of an anti-shrink agent;
- Figure 2 is a schematic representation of a polyethylene having a mono-alcohol function at the end of unesterified chain;
- FIGS. 3A to 3C show schematically the reaction of a mole of polyethylene comprising a chain-end monohydric alcohol functional group with one mole of mono or polycarboxylic acid or its corresponding acid anhydride;
- FIGS. 3D and 3E show schematically the reaction of two moles of polyethylene having a chain-end monohydric alcohol function with one mole of mono or polycarboxylic acid or its corresponding acid anhydride.
- FIG. 1 schematically represents the reaction between a polyolefin (a1) according to the invention comprising a reactive function X with a functionalization compound (b) according to the invention comprising a carbon-carbon double bond and a Y function, which can to be defined taking into account the carbon-carbon double bond, for the formation of a functionalized anti-shrinkage agent (Al) according to the invention.
- the volume expansion measurements described in Table 1 below were carried out by dilatometry following the transition from the crystalline state to the amorphous state of said polyolefins (a-1 to 14).
- the polymers tested are polyethylenes comprising at the chain end a monoalcohol function (CAS number 71750-71-5).
- the expansion measurements are made by measuring the differences in density between the crystalline and amorphous phases.
- the crystallinity levels were calculated by the measurement of the differential scanning calorimetry (DSC) heat transfer enthalpy (Differential Scanning Calorimetry). The ratio of the enthalpy of melting obtained for each component relative to the theoretical melting enthalpy of a 100% crystalline polyethylene makes it possible to determine the degree of crystallinity (%).
- thermoplastic and semi-crystalline (all-al4) tested polyethylenes have expansion rates that can approach about 10%.
- rate of expansion is increasing with the degree of crystallinity of the polymers tested.
- FIGS. 3A to 3C show schematically the esterification reactions of the mono-alcohol functional groups at the chain end of the polyolefins garlic and at 12, the mixtures being equimolar between the polyolefins and the carboxylic acids.
- FIG. 3A shows the esterification of the monoalcohol function of the garlic polyolefin with maleic anhydride as functionalization compound (b) for the formation of the anti-shrinkage agent Al 11 according to the invention.
- FIG. 3B shows the esterification of the monoalcohol function of the garlic polyolefin with itaconic anhydride as functionalization compound (b) for the formation of the anti-shrinkage agent Al 12 according to the invention.
- FIG. 3C shows the esterification of the monoalcohol function of the polyolefin al2 with acrylic acid as functionalization compound (b) for the formation of the anti-shrinkage agent A123 according to the invention.
- This functionalization was carried out in bulk in the presence of a different acid and additional carboxylic acid, for example sulfuric acid between 0.05 and 2% by weight, as a catalyst and placing the reaction mixture under vacuum to extract the water produced by the condensation reaction.
- a different acid and additional carboxylic acid for example sulfuric acid between 0.05 and 2% by weight
- FIG. 3D shows the esterification of the monoalcohol function of the garlic polyolefin with methacrylic anhydride as the functionalization compound (b) for the formation of the anti-shrinkage agent Al 14 according to the invention.
- Functionalization of the garlic polyolefin was carried out in bulk with methacrylic anhydride.
- the first step of this functionalization is the opening of methacrylic anhydride and the methacrylic acid generation.
- This functionalization was also carried out massively in the presence of sulfuric acid, between 0.05 and 2% as a catalyst and by placing the reaction mixture under vacuum in order to extract the water produced by the condensation reaction.
- the polyolefins Ia and a 12 (referenced in Table 1) were esterified individually in admixture with carboxylic acids or their corresponding anhydrides for 1 h 30 with stirring at a temperature of 110 ° C.
- the number of moles of polyolefins garlic or 12 depends on the number of carboxyl function (-COOH) or (COO-CO) supported by the acid.
- -COOH carboxyl function
- COO-CO carboxyl function
- Table 2 below lists the degrees of crystallinity and melting temperatures obtained for the anti-shrinkage agents Al11 to A144, measured as described above with reference to Table 1.
- the degree of crystallinity (%) of the polyolefins garlic and 12 esterified and thus forming anti-shrinkage agents decreases due to esterification, but that this decrease depends on the grafted ester function. Indeed, the degree of crystallinity is maintained with respect to the anti-shrinkage agent Al11. Melting temperatures increased significantly for Alll and Al 12 anti-shrinkage agents. the opposite, the melting temperature decreased very strongly with respect to the anti-shrinkage agent A114. Finally, the degree of crystallinity and the melting temperature decreased slightly with regard to the anti-shrinkage agents A123 and A141 to A144. It is also noted that the influence of the functionalization on the melting temperature and the crystallinity rate is less significant when the number-average molar mass of the polyethylene increases.
- Figure 3E shows the same synthesis as that illustrated in Figure 3A for the first step. Nevertheless, the number of moles of polyethylene garlic being greater than the number of moles of maleic anhydride, the remaining polyethylene having a mono-alcohol function at the chain end reacts with the terminal acid function of the functionalized polyethylene so as to form an anti-shrinkage agent Al Comprising a reactive carbon-carbon double bond in radical polymerization disposed between two polyolefin chains.
- the shrinkage rates were measured on a polyester organic matrix not comprising a reinforcement.
- the measurement of the withdrawal is thus carried out by means of a rheometer (for example that under the reference Anton Paar MCR302).
- the sample of which it is desired to measure the shrinkage namely in a liquid resinous composition according to the invention, is arranged between two upper and lower trays distant by a determined distance (h), a determined constant force Fn being applied to the plate superior.
- h determined distance
- Fn constant force
- the rate of shrinkage (%) was measured for the polyolefins garlic to al4 and the anti-shrinkage agents Al 11, Al 12, A123 and Al 14 according to the invention (by the method described in paragraph II) implemented in a liquid resinous composition comprising 60 parts (g) of unsaturated polyester (Norsodyne M01510, CCP Composites), 20 parts of styrene as copolymerizable monomer, 20 parts (g) of a component selected from: a1 to Al4 and Al11, A112, A123 and A114, 150 parts (g) of calcium carbonate (Millicarb OG).
- This liquid resinous composition (I) to which 1.5% by weight of an initiator, for example benzoyl peroxide (PBO), is added is subjected to a temperature of 100 ° C. for at least 5 minutes.
- PBO benzoyl peroxide
- the half-life time of the PBO at 80 ° C. being one hour, the latter decomposes into two radicals which make it possible to initiate the crosslinking reaction of the resinous composition.
- the crosslinking is considered as total and the shrinkage can be determined by density measurements.
- the removal rates (%) obtained are listed in Table 3 below.
- the liquid resinous composition further comprises 1.5% by weight relative to the total weight of said composition of an organic peroxide (PBO - Perkadox CH-50).
- PBO - Perkadox CH-50 organic peroxide
- Specimens 15 cm long and 1 cm wide were molded into said composition in a mold closed by a counter mold, at an operating temperature Tw of about 100 ° C for 25 minutes.
- Three-point bending measurements were made on said test pieces using the Testometric M500-30 AT apparatus. These measurements were made according to the ISO 14125 standard, ie at the speed of 2m / min and with a range of 64mm.
- the compensation of the shrinkage in a polyester organic matrix during the crosslinking is possible by using a semi-crystalline and hot-melt polyolefin polymer which, during the polymerization, loses its crystallinity due to its total or partial melting allowing thus to generate an expansion that will compensate the withdrawal.
- the percentage of shrinkage (%) can be decreased while maintaining or even improving the mechanical performance of the organic polyester matrix by virtue of the presence of a function, for example an ester, which is capable of reacting with the unsaturated polyester during the reaction of thus preventing polymerization of the polyolefin polymer during cooling of the molded organic matrix and thus generates micro-voids detrimental to the mechanical performance of the organic matrix and thus the composite part to be molded.
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Abstract
Description
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FR1557149A FR3039549B1 (fr) | 2015-07-27 | 2015-07-27 | Procede de fabrication d'un agent anti-retrait pour le moulage d'un polyester insature en presence d'un diluant reactif, agent anti-retrait susceptible d'etre obtenu par ledit procede de fabrication |
PCT/FR2016/051802 WO2017017336A1 (fr) | 2015-07-27 | 2016-07-13 | Procede de fabrication d'un agent anti-retrait pour le moulage d'un polyester insature en presence d'un diluant reactif, agent anti-retrait susceptible d'etre obtenu par ledit procede de fabrication |
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CN115322479B (zh) * | 2022-08-11 | 2023-12-12 | 上海金发科技发展有限公司 | 一种低后收缩聚丙烯材料及其制备方法 |
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FR2426065A1 (fr) * | 1978-05-19 | 1979-12-14 | Owens Corning Fiberglass Corp | Polyester thermodurcissable tenace, a base principalement de dipropylene glycol, de polyol primaire et d'acide isophtalique |
GB8730153D0 (en) * | 1987-12-24 | 1988-02-03 | Univ Manchester | Polymer compositions |
DE4234324A1 (de) * | 1992-10-12 | 1994-04-14 | Basf Ag | Härtbare Formmasse |
EP0837049B1 (fr) * | 1996-10-17 | 2002-07-31 | Rohm And Haas Company | Procédé de préparation de monomères |
JP4056423B2 (ja) * | 2002-08-30 | 2008-03-05 | 三井化学株式会社 | ポリオレフィンマクロモノマーおよびその製造法 |
US7559639B2 (en) * | 2005-11-30 | 2009-07-14 | Xerox Corporation | Radiation curable ink containing a curable wax |
JP5221460B2 (ja) * | 2009-06-12 | 2013-06-26 | 東洋アドレ株式会社 | 相溶化剤及びそれを用いた樹脂組成物 |
US8309621B2 (en) * | 2009-12-18 | 2012-11-13 | Xerox Corporation | Curable phase change inks |
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