EP1570009A1 - Particules dissymetriques de taille nanometrique ou mesoscopique, et leur procede de preparation. - Google Patents
Particules dissymetriques de taille nanometrique ou mesoscopique, et leur procede de preparation.Info
- Publication number
- EP1570009A1 EP1570009A1 EP03780239A EP03780239A EP1570009A1 EP 1570009 A1 EP1570009 A1 EP 1570009A1 EP 03780239 A EP03780239 A EP 03780239A EP 03780239 A EP03780239 A EP 03780239A EP 1570009 A1 EP1570009 A1 EP 1570009A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- group
- inorganic
- polymer
- chosen
- 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- Withdrawn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
- 239000002245 particle Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000010954 inorganic particle Substances 0.000 claims abstract description 30
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000003993 interaction Effects 0.000 claims abstract description 5
- -1 vinyl compound Chemical class 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 71
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910010272 inorganic material Inorganic materials 0.000 claims description 15
- 239000011147 inorganic material Substances 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012429 reaction media Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 10
- 239000011707 mineral Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011368 organic material Substances 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000005024 alkenyl aryl group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical group NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 125000001165 hydrophobic group Chemical group 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000013980 iron oxide Nutrition 0.000 claims description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical group 0.000 claims description 2
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 230000000306 recurrent effect Effects 0.000 abstract 1
- 238000000502 dialysis Methods 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- RXRHXOLQBOFMDI-UHFFFAOYSA-N methoxymethane;2-methylprop-2-enoic acid Chemical compound COC.CC(=C)C(O)=O RXRHXOLQBOFMDI-UHFFFAOYSA-N 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- DHKQRNSPTWYPEX-UHFFFAOYSA-N 11-(4-ethenylbenzoyl)oxyundecyl-dimethyl-octadecylazanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCOC(=O)C1=CC=C(C=C)C=C1 DHKQRNSPTWYPEX-UHFFFAOYSA-N 0.000 description 1
- YZSYUHBWZOBIDQ-UHFFFAOYSA-M 11-(4-ethenylbenzoyl)oxyundecyl-dimethyl-octadecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCOC(=O)C1=CC=C(C=C)C=C1 YZSYUHBWZOBIDQ-UHFFFAOYSA-M 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000008119 colloidal silica Substances 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
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052592 oxide mineral Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
-
- 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
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- 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
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- Nanometric or mesoscopic size asymmetrical particles and process for their preparation
- the present invention relates to asymmetrical particles of nanometric or mesoscopic size, comprising a part constituted by an inorganic material and a part constituted by an organic material, as well as a process for their preparation.
- asymmetric particles comprising two organic parts by reaction of latex particles (polystyrene) with styrene monomer in the presence of divinylbenzene as crosslinking agent, of 2-2'-azobis- (2-methylbutyronitrile) as initiator of polymerization and poly-N-vinyl pyrrolidone as a stabilizer.
- Such a method thus consists in growing a polymer by the radical route from a preconstituted latex particle and swollen with a mixture of monomers under conditions such that phase separation of the latex and of the polymer formed is favored.
- WO 01/85324 discloses the preparation of solid particles of amphiphilic nature.
- the process consists in partially modifying the surface of a mineral particle by organic chains of hydrophobic nature.
- the product obtained is an emulsifying composition comprising nanometric mineral particles having a core of mineral material and a hydrophobic organic coating on part of its surface, the hydrophobic coating being obtained in particular by covalent bonding from a compound comprising a long alkyl chain. and a silanol group.
- a process is also known for preparing silica particles on the surface of which small particles of polystyrene are fixed.
- Said method comprises a first step during which a suspension of silica particles is prepared, a second step during which adsorbed on said silica particles a macromonomer of hydrophilic PEG methacrylate, a third fifth step during which an emulsion polymerization of styrene is carried out in the presence of the modified silica particles.
- the concentrations of macromonomer used are 0.1 and 0.05 gL -1 for a concentration of silica particles of 10 gL "1.
- the particles obtained by this process consist of a silica core and small polymer nodules distributed regularly on the surface of the silica core (Cf.
- the aim of the present invention is to provide particles of nanometric or mesoscopic dimensions comprising an organic part and an inorganic part, by nanometric dimensions are understood to be dimensions between 1 nm and 100 nm, and by mesoscopic dimensions are understood to include dimensions between 100 nm and 1 ⁇ m.
- the particles according to the present invention are asymmetrical particles of dimensions, nanometric or mesoscopic, having an inorganic part constituted by a material A and an organic part constituted by a material B. They are characterized in that: the inorganic material A is an oxide mineral or a metal; organic material B is a polymer consisting of repeating units derived from a vinyl compound; the organic part has a substantially spherical shape; the two parts are linked by physicochemical or covalent interactions; - The dimension of each of the parts is between 5 nm and 1 ⁇ m, preferably between 50 nm and 250 nm.
- the inorganic material A can be a mineral oxide or a metal.
- the mineral oxide can be chosen, for example, from silica, iron oxides, aluminosilicates (such as, for example, clays and zeolites), titanium dioxide or alumina.
- the metal can be chosen, for example, from metals which are stable in an aqueous medium (for example gold, silver and palladium).
- the inorganic material carries an organic group. Such a group can be chosen, for example, from alkyl groups, amine, thiol or nitrile functions. Silica is particularly preferred as inorganic material A.
- R, R ′ or R ′′ represents an alkyl group or an aryl group, it may carry a functional group, chosen for example from halides and amino groups.
- the polymer constituting the organic material B can be crosslinked or uncrosslinked.
- a polystyrene or a copolymer of styrene and divinylbenzene are particularly preferred as organic material B.
- the inorganic part of the asymmetrical particles of the invention may have the shape of a sphere, ellipse, disc, wafer or rod, while the organic part always has a substantially spherical shape.
- the inorganic part has a spherical shape, and in this case, the asymmetrical particles have a dumbbell shape when the organic and inorganic parts have substantially the same size, or a snowman shape if the 'one of the parts has a dimension clearly more important than the other.
- the shape of the asymmetrical particles of the invention can be identified by various microscopy techniques, in particular by transmission electron microscopy.
- the process for obtaining particles is characterized in that it comprises the following stages: a) during a first stage, the surface of particles constituted by the inorganic material A is modified and whose dimension is between 5 nm and 1 ⁇ m using a coupling agent C which comprises a function F c which has an affinity for one or more precursors of polymer B; b) during a second step, the modified inorganic particles obtained at the end of step a) are brought into contact with the precursor (s) of polymer B, in the presence of a radical initiator and of a surfactant in solution in a solvent, in proportions which allow the formation of a polymer nodule per inorganic particle.
- step a it is advantageous to use an amount of coupling agent which corresponds to approximately 0.1 mole of coupling agent per m 2 of silica particle surface.
- Np denotes the number of polymerization seeds
- TA the surfactant
- I 1 the radical initiator
- the number of polymerization seeds can be estimated as a first approximation by the relation Np ⁇ [TA] ° ' 6 [I] ° ' 4 .
- the operator will carry out preliminary tests, within the reach of those skilled in the art, by varying the concentrations of TA and I , to determine the optimal concentrations.
- Another procedure consists in fixing the quantity of monomer, initiator and surfactant, as well as the reaction time and temperature, and in carrying out tests with different concentrations of silica particles having a given dimension, in order to determine the optimal amount of said particles.
- This second mode of implementation is particularly preferred.
- the implementation of steps a) and b) of the method makes it possible to obtain asymmetrical particles in the form of a colloidal solution in a solvent.
- the particles can be recovered in the form of powder by elimination of the solvent, when the organic part of the particle consists of a polymer whose glass transition temperature is higher than room temperature.
- the particles can be recovered by lyophilization.
- the initial inorganic particles of material A used in step a) of the process can have the shape of a sphere, ellipse, disc, plate or rod.
- the shape of the particles used is found in the inorganic part of the asymmetrical particles obtained after the treatment of step b). It is preferable to use inorganic particles having a narrow size distribution, to obtain hybrid particles of the same kind.
- the polymer nodules which form all have substantially the same dimension. With larger or smaller inorganic particles, they will form hybrid particles in the shape of snowmen. With inorganic particles of the same size, they will form dumbbell-shaped hybrid particles. Very small inorganic particles may not fix a nodule, and very large inorganic particles may fix two nodules.
- the initial inorganic particles are preferably used for step a) in the form of a colloidal suspension whose solid content is between 2 and 35%, preferably from 10 to 25% and whose pH is adjusted so as to allow interaction with coupling agent C.
- the inorganic particles A used in step a) of the process are chosen as a function of the material desired for the inorganic part of the asymmetrical particles which it is desired to prepare, it being understood that the material of the initial particle is identical to the material of the part inorganic of the asymmetric particle.
- a particularly interesting case is constituted by the use of silica particles having a diameter of about 100 nm.
- Such particles can be obtained by the sol-gel route, well known in particular under the name of the St ⁇ ber process.
- a basic hydroalcoholic solution is prepared by adding an aqueous ammonia solution to a given volume of alcohol, preferably ethanol.
- alcohol preferably ethanol.
- a tetraalkoxysilane type silica precursor preferably tetraethoxysilane
- Step a) can be implemented in different ways.
- the inorganic particles are brought into contact with, as coupling agent C, a macromolecule having a hydrophilic chain terminated by a polymerizable function F c , said macromolecule being designated below by macromonomer, and the reaction medium with stirring for a certain period.
- macromonomers mention may be made of poly (ethylene oxide), hydroxycelluloses, poly (vinylpyrrolidone), poly (acrylic acid) and poly (polyvinyl alcohol), said compounds carrying the function F c polymerizable by the route aforementioned radical.
- the polymerizable function Fc can be for example a vinyl group, a methacrylate group or an allyl group.
- a poly (ethylene glycol) monomethyl ether methacrylate can be advantageously used as a macromonomer.
- the quantity of macromonomer required it is for example possible to measure the adsorption isotherm of the macromonomer chosen on the inorganic particle. If adsorption is effectively observed, the skilled person can carry out preliminary tests by placing themselves at low concentrations, which are generally sufficient in order to avoid promoting nucleation of particles in the continuous phase during the stage. b), to determine the optimal conditions.
- step a) can be implemented by covalent grafting of a coupling agent C carrying a function F c copolymerizable with the precursor (s) of polymer B.
- a coupling agent can be chosen in particular from silanes carrying polymerizable groups such as vinyl, allyl, styryl, methacryloyl and acryloyl groups. Methacryloylalkyltrialcoxysilanes are particularly preferred.
- the process for modifying the inorganic particles consists in adsorbing the coupling agent on the surface of the particles, then in heating the reaction medium to the temperature required to ensure the covalent grafting of the compound by hydrolysis-condensation reaction. X groups with surface hydroxyl groups. The excess of the various reagents can be eliminated from the reaction medium at the end of the process by dialysis.
- the particles thus obtained are formed by a core of inorganic material carrying on its surface organic substituents which have a free polymerizable function. This process is particularly interesting when the mineral oxide is silica.
- the coupling agent fixed by covalent grafting can be chosen from organothi ⁇ ls RSH and amines RNH 2 in which R is a substituent carrying the functional group F c having an affinity for the polymer B or a precursor of said polymer.
- R is a substituent carrying the functional group F c having an affinity for the polymer B or a precursor of said polymer.
- the coupling agent can also be chosen from aminosilanes and thiosilanes which are grafted onto the metal particle respectively by the amine function or by the thio function, and which would allow the subsequent condensation of a silane carrying the function F c required by the nature of the polymer used in step b).
- the inorganic particles are suspended at a pH close to neutrality so that they are charged at the surface, in the presence of an amphiphilic compound constituted by a hydrophobic part which has a polymerizable group and by a polar head which carries a charge opposite to that of the surface.
- Amphiphilic compounds can strongly adsorb on the surface of the inorganic particle through electrostatic interactions.
- These amphiphilic molecules, which simultaneously have a surfactant (surfactant) character and which are monomers, are known to those skilled in the art under the name of surfmers.
- surfmers As examples of surfmers, mention may be made of compounds derived from styrene sulfonates (with a negatively charged hydrophilic polar head) and quaternary alkylammoniums (with a positively charged polar head), the two types of compounds carrying a hydrophobic group (such as a long alkyl chain for example) terminated by a polymerizable function.
- N N-dimethyl-N- [11- (p-vinylbenzoyloxy) undecyl] octadecylammonium bromide, the synthesis of which is described by Jung et al. in Langmuir 2000, 16, 4185-4195), is a typical case of polymerizable quaternary ammonium.
- step b There are also different modes of implementation of step b).
- step b) is carried out by bringing the particles of inorganic material into contact
- step b) is carried out by bringing the particles of material A obtained into contact at the end of step a) with an oligomer of polymer B in the presence of a polymerization initiator.
- the polymerization process in step b) can be stopped by cooling the reaction medium to room temperature, then by dialyzing the cooled reaction medium so as to remove the traces of monomer and initiator which did not react, as did the excess surfactant.
- the asymmetrical particles obtained at the end of step b) can be subjected to an additional treatment aimed at modifying the surface groups of the material A not modified during step b).
- the precursor of polymer B is a monomer
- it is preferably chosen from compounds having a vinyl group which plays the role of polymerizable function F B.
- Mention may be made in particular of the monomers which contain a vinyl group, in particular styrene, ⁇ -methylstyrene, vinyl-pyridine, vinyl acetate, or vinyl propionate.
- Mention may also be made of the monomers comprising an acrylic group, in particular vinyl esters of the methyl methacrylate, ethyl acrylate, butyl acrylate, ethylhexyl methacrylate, acrylonitrile, methacrylonitrile type.
- crosslinked organic material B a mixture of monomers comprising one or more of the above monomers is used, and a crosslinking monomer comprising a second group F B.
- crosslinking monomers mention may be made of ethylene glycol dimethacrylate.
- polymer B diethylene glycol dimethacrylate, vinyl methacrylate, divinylbenzene.
- the proportion of monomer capable of crosslinking relative to the monofunctional monomer is preferably from 1 to 10% by weight.
- the precursor of polymer B is an oligomer, it is preferably chosen from the polymers or copolymers obtained from a monomer as defined above. above, or from a mixture of monomers optionally comprising a crosslinking monomer.
- Water or a water-alcohol mixture (preferably ethanol) is preferably used as solvent, in water / alcohol proportions between 100/0 and 50/50.
- the surfactant makes it possible to carry out the reaction in emulsion or in miniemulsion. It can be chosen from anionic, cationic or nonionic surfactants.
- nonionic surfactants polyoxyethylenated alkylphenols can be used, for example.
- anionic surfactant an alkyl benzene sulfonate or an alkyl sulfonate can be used, for example.
- a steric stabilizer such as poly (N-vinylpyrrolidone) or hydroxypropylcellulose is added to the reaction medium.
- the shape of the asymmetrical particles obtained at the end of step b) depends on the one hand on the shape of the initial inorganic particles and on the other hand on the duration of step b).
- the asymmetrical particles obtained have a shape comprising two spherical parts.
- the inorganic part is more important than the organic part.
- the duration of step b) increases, the size of the two parts becomes equal and we first obtain a "dumbbell" shape, then a snowman shape in which the inorganic part is smaller than the organic part. .
- the asymmetrical particles obtained by the process of the invention can be modified by reaction of the active functions present on the organic part or on the mineral part.
- the particles of the invention can be used in many technical fields. An appropriate modification of their amphiphilic character according to their chemical characteristic, and the choice of a particular size make it possible to stabilize many emulsions "O / W". Thus, the particles could be useful especially in the paint industry.
- the initial inorganic particles were used, silica particles of about 100 nanometers in diameter, prepared by a sol-gel process, called "Stober process", in the following manner.
- a basic hydroalcoholic solution was prepared by adding 75 ml of an aqueous ammonia solution with an average mass percentage of 29% in ammonia to a 1 L of ethanol. After homogenization, 30 mL of tetraethoxysilane was added as a silica precursor, and the reaction medium was left for 12 hours, with moderate stirring and controlling the temperature.
- the excess reagents were removed by successive dialysis in dialysis bags immersed in distilled water so as to exchange the ethanol solvent for water.
- the dialysis bags are made up of a regenerated cellulose membrane. Dialysis is considered complete when the pH of the water outside the membrane approaches neutrality (between 7 and 8).
- the suspension obtained was concentrated by immersing the dialysis bag in a concentrated aqueous solution containing about 200 gL "1 of Poly Ethylene Glycol (35000 g.mol " 1 ). The concentration of silica in the suspension was then determined by measuring the mass of a dry extract.
- Examples 1 to 3 illustrate the modification of the surface of the initial inorganic particles, in accordance with the first step of the process of the invention.
- Examples 4 and 5 illustrate the preparation of asymmetrical particles from silica particles whose surface has been modified.
- the surface of the initial silica particles was modified in the following manner, from suspensions of the particles having the respective concentrations indicated in the table below.
- an aqueous solution of poly (ethylene glycol) monomethyl ether methacrylate (which is a macromolecule having a hydrophilic chain terminated by a polymerizable function) was added, in proportions such that the amount of macromonomer is close to 2 mg per m 2 of silica (it being recalled that the surface of a silica particle is taken equal to 4. ⁇ .r 2 , r being the mean radius of the particle).
- poly (ethylene glycol) monomethyl ether methacrylate which is a macromolecule having a hydrophilic chain terminated by a polymerizable function
- the agitation is reduced to 300 revolutions. min "1 ; after a period t, the reaction medium is brought to room temperature, then a dialysis is carried out under the conditions described above to remove the traces of monomer and of unreacted initiator as well as the excess surfactant.
- the dissymmetrical particles obtained were characterized by transmission electron microscopy.
- FIG. 1 represents a micrograph of the asymmetrical particles obtained from the silica particles having a diameter of 100 nm modified according to example 1, and treated with styrene respectively for a duration of 45 min (la) and 60 min (lb) .
- the asymmetrical particles After 45 min, the asymmetrical particles have a "dumbbell" shape with a part silica (in dark gray) and a polymer part (in lighter gray) each of spherical shape and of a size close to
- the asymmetrical particles have a "snowman" shape in which the polymer part has a size greater than that of the silica part which remains that of the original silica particles, namely
- FIG. 2 represents a micrograph of the asymmetrical particles obtained from the silica particles having a diameter of 50 nm modified according to Example 1 and treated with styrene respectively for a period of
- FIG. 3 represents a micrograph of the asymmetrical particles obtained from the silica particles having a diameter of 150 nm modified according to Example 1 and treated with styrene respectively for a period of
- FIG. 4 represents a micrograph of the asymmetrical particles obtained from the silica particles having a diameter of 80 nm modified according to Example 2 and treated with styrene respectively for a period of
- Example 4 The procedure of Example 4 was reproduced, using particles obtained according to Example 1, but replacing the styrene with a mixture of styrene and divinylbenzene. During a first test, a mixture consisting of 9.9 g of styrene and 0.1 g of divinylbenzene was used. In a second test, a mixture consisting of 9.8 g of styrene and 0.2 g of divinylbenzene was used
- the polymer nodules attached to the silica particles in both cases consist of a crosslinked polystyrene.
- FIG. 5 represents a micrograph of the asymmetric particles obtained during the first test from initial silica particles of 100 nm in diameter surface modified according to Example 1. They have a shape in "snowman" in which the polymer part (light gray) has a size larger than that of the silica part (dark gray) which remains that of the original silica particles.
- Example 5 The procedure of Example 5 was reproduced using initial silica particles of 80 nm in diameter surface modified according to Example 2, and a styrene / divinylbenzene mixture 95/5 by mass.
- FIG. 5 represents a micrograph of the asymmetrical particles obtained respectively after a treatment time of 60 min (6a) and 120 min (6b).
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Silicon Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
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FR0213800A FR2846572B1 (fr) | 2002-11-05 | 2002-11-05 | Particules dissymetriques de taille nanometrique ou mesoscopique, et leur procede de preparation |
FR0213800 | 2002-11-05 | ||
PCT/FR2003/003211 WO2004044061A1 (fr) | 2002-11-05 | 2003-10-28 | Particules dissymetriques de taille nanometrique ou mesoscopique, et leur procede de preparation. |
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EP03780239A Withdrawn EP1570009A1 (fr) | 2002-11-05 | 2003-10-28 | Particules dissymetriques de taille nanometrique ou mesoscopique, et leur procede de preparation. |
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US (1) | US8029897B2 (fr) |
EP (1) | EP1570009A1 (fr) |
JP (1) | JP2006505665A (fr) |
AU (1) | AU2003288335A1 (fr) |
FR (1) | FR2846572B1 (fr) |
WO (1) | WO2004044061A1 (fr) |
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FR2862236B1 (fr) * | 2003-11-13 | 2006-07-28 | Centre Nat Rech Scient | Particules inorganiques dissymetriques, procede pour leur preparation. |
FR2877262B1 (fr) | 2004-10-29 | 2007-04-27 | Centre Nat Rech Scient Cnrse | Fibres composites et fibres dissymetriques a partir de nanotubes de carbonne et de particules colloidales |
EP1726609A1 (fr) * | 2005-05-25 | 2006-11-29 | DSM IP Assets B.V. | couche hydrophobe |
JP2007038643A (ja) * | 2005-06-29 | 2007-02-15 | Oji Paper Co Ltd | 複合微粒子、分散液、分散液の製造方法、インクジェット記録体及びインクジェット記録体の製造方法 |
DE102006012467A1 (de) * | 2006-03-17 | 2007-09-20 | Merck Patent Gmbh | Redispergierbare Nanopartikel |
US7875654B2 (en) * | 2007-03-23 | 2011-01-25 | The Board Of Trustees Of The University Of Illinois | System for forming janus particles |
KR100862554B1 (ko) * | 2007-05-09 | 2008-10-09 | 엘지전자 주식회사 | 복수의 구조체를 포함하는 광학 필름, 이를 포함하는백라이트 유닛 및 액정 표시 소자 |
KR100963898B1 (ko) * | 2008-05-30 | 2010-06-17 | 연세대학교 산학협력단 | 고분자가 그래프팅된 무기물 복합체 및 그 제조방법 |
US8207547B2 (en) * | 2009-06-10 | 2012-06-26 | Brudgelux, Inc. | Thin-film LED with P and N contacts electrically isolated from the substrate |
FR2969508B1 (fr) * | 2010-12-22 | 2015-11-13 | Univ Bordeaux 1 | Particules dissymetriques (particules de janus) et leur procede de synthese par electrochimie bipolaire. |
CN102558916B (zh) * | 2011-12-16 | 2013-08-07 | 天津大学 | 一种基于电荷环境调控的纳米二氧化硅粒子表面改性方法及应用 |
FR3003573B1 (fr) | 2013-03-22 | 2017-10-27 | Michelin & Cie | Composition de caouthcouc comportant des particules hybrides |
CN104525067B (zh) * | 2014-12-11 | 2016-08-24 | 同济大学 | 一种具有石榴状结构的功能复合微球及其制备方法 |
JP6482384B2 (ja) * | 2015-05-28 | 2019-03-13 | 旭化成株式会社 | 複合粒子及びこれを含有する水性分散液 |
CN111185168B (zh) * | 2020-01-14 | 2023-02-03 | 上海华谊(集团)公司 | 一种纳米金催化剂、其制备和应用 |
CN115595129B (zh) * | 2022-10-10 | 2023-07-14 | 南方海洋科学与工程广东省实验室(湛江) | 负载金属氧化物的粘土流型调节剂制备方法、粘土流型调节剂及水基钻井液 |
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US5856379A (en) * | 1996-01-16 | 1999-01-05 | Fuji Photo Film Co., Ltd. | Aqueous dispersion of core/shell-type composite particles with colloidal silica as the cores and with organic polymer as the shells and production method thereof |
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JPH04139264A (ja) * | 1990-10-01 | 1992-05-13 | Diafoil Co Ltd | 有機架橋高分子被覆二酸化ケイ素粒子の製造方法 |
GB9127293D0 (en) * | 1991-12-23 | 1992-02-19 | Ici Plc | Coating pigment particles with polymers |
GB9211822D0 (en) * | 1992-06-04 | 1992-07-15 | Tioxide Group Services Ltd | Composite pigmentary material |
FR2721615A1 (fr) * | 1994-06-24 | 1995-12-29 | Rhone Poulenc Chimie | Procédé de préparation de particules d'oxyde métallique organophiles. |
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2003
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- 2003-10-28 WO PCT/FR2003/003211 patent/WO2004044061A1/fr active Application Filing
- 2003-10-28 JP JP2004551084A patent/JP2006505665A/ja active Pending
- 2003-10-28 AU AU2003288335A patent/AU2003288335A1/en not_active Abandoned
- 2003-10-28 EP EP03780239A patent/EP1570009A1/fr not_active Withdrawn
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US20060134420A1 (en) | 2006-06-22 |
AU2003288335A8 (en) | 2004-06-03 |
WO2004044061A1 (fr) | 2004-05-27 |
US8029897B2 (en) | 2011-10-04 |
FR2846572A1 (fr) | 2004-05-07 |
FR2846572B1 (fr) | 2004-12-31 |
JP2006505665A (ja) | 2006-02-16 |
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