CN105646759B - 磷酸官能化不透明聚合物 - Google Patents
磷酸官能化不透明聚合物 Download PDFInfo
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- CN105646759B CN105646759B CN201510815194.5A CN201510815194A CN105646759B CN 105646759 B CN105646759 B CN 105646759B CN 201510815194 A CN201510815194 A CN 201510815194A CN 105646759 B CN105646759 B CN 105646759B
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 25
- 229920005787 opaque polymer Polymers 0.000 title abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 117
- 229920000642 polymer Polymers 0.000 claims description 64
- 239000000839 emulsion Substances 0.000 claims description 50
- 239000011258 core-shell material Substances 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 239000004014 plasticizer Substances 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- WIVTXBIFTLNVCZ-UHFFFAOYSA-N CC(=C)C(=O)OCCP(=O)=O Chemical group CC(=C)C(=O)OCCP(=O)=O WIVTXBIFTLNVCZ-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
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- 230000003111 delayed effect Effects 0.000 claims description 2
- 239000011246 composite particle Substances 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
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- 239000008199 coating composition Substances 0.000 abstract description 5
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- 239000008367 deionised water Substances 0.000 description 13
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 11
- 239000003973 paint Substances 0.000 description 10
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 hydroxyalkyl methacrylates Chemical class 0.000 description 4
- 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 3
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- 239000000654 additive Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000009918 complex formation Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000001007 puffing effect Effects 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000010350 erythorbic acid Nutrition 0.000 description 2
- 229940026239 isoascorbic acid Drugs 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- OXXWBUSPJWDOKF-UHFFFAOYSA-N CC(=C)C(=O)OCCCP(=O)=O Chemical compound CC(=C)C(=O)OCCCP(=O)=O OXXWBUSPJWDOKF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000002009 alkene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZZIBVROFKFXSAX-UHFFFAOYSA-N benzene-1,4-diol;methoxyethane Chemical compound CCOC.OC1=CC=C(O)C=C1 ZZIBVROFKFXSAX-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- POZFOZAEVMVUIZ-UHFFFAOYSA-N ethyl dihydrogen phosphate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOP(O)(O)=O POZFOZAEVMVUIZ-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001249 flow field-flow fractionation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
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- 235000021388 linseed oil Nutrition 0.000 description 1
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- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/12—Copolymers of styrene with unsaturated nitriles
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- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- 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
- C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
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- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- 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
- C08F8/44—Preparation of metal salts or ammonium salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/18—Plasticising macromolecular compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
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- 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
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- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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Abstract
本发明涉及用磷酸基官能化的不透明聚合物、TiO2粒子与所述不透明聚合物的复合物以及其制备方法。所述复合物适用于涂料配制品并且已显示在经涂布衬底中展示优于含有非官能化不透明聚合物和TiO2的组合物的改进的遮盖益处。
Description
背景技术
本发明涉及一种磷酸官能化不透明聚合物，其适用作着色涂料配制品中的添加剂。
不透明聚合物作为如油漆的着色涂料配制品中的添加剂众所周知并且用于改进经涂布衬底的遮盖力。不透明聚合物用于在不牺牲遮盖力的情况下降低配制品中相对昂贵的TiO2的负载，或维持TiO2的相同水平以改进遮盖力。不透明聚合物可以例如如U.S.6,020,435中所描述制备。
发现具有改进遮盖能力的添加剂将是着色涂料组合物领域中的进步。
发明内容
本发明通过提供一种制备磷酸官能化核-壳聚合物粒子的水性分散液的方法解决所属领域中的需要，所述方法包含以下步骤：a)在乳液聚合条件下使i)第一单体乳液与ii)平均粒径是80nm到180nm的酸官能化聚合物粒子的水性分散液接触以形成核-壳聚合物粒子的水性分散液；随后b)用可聚合塑化剂塑化核-壳聚合物粒子的壳部分；随后c)使核-壳聚合物粒子与水性碱接触以在不实质上聚合塑化剂的情况下使核膨胀；随后d)聚合塑化剂；
其中所述第一单体乳液包含a)以所述第一单体乳液中的单体的重量计，0.1重量％到5重量％的磷酸单体；和b)50重量％到99.9重量％的选自由以下组成的群组的第一非离子烯系不饱和单体：苯乙烯、甲基丙烯酸甲酯、丙烯腈和丙烯酸叔丁酯以及其组合；以及c)0.1重量％到15重量％羧酸官能化单体；
其中所述酸官能化聚合物粒子包含以所述聚合物粒子的重量计，20重量％到50重量％的羧酸单体的结构单元；和50重量％到80重量％的第二非离子烯系不饱和单体的结构单元；
其中所述塑化剂包含以所述聚合物粒子的重量计，7％到30％的第三非离子烯系不饱和单体；
其中所述磷酸官能化核-壳聚合物粒子的平均粒径在250nm到1.6μm范围内。
磷酸官能化核-壳聚合物粒子适用于与TiO2粒子形成复合物，所述复合物在油漆配制品中改进遮盖效率。
具体实施方式
在第一方面中，本发明是一种制备磷酸官能化核-壳聚合物粒子的水性分散液的方法，其包含以下步骤：a)在乳液聚合条件下使i)第一单体乳液与ii)平均粒径是80nm到180nm的酸官能化聚合物粒子的水性分散液接触以形成核-壳聚合物粒子的水性分散液；随后b)用可聚合塑化剂塑化核-壳聚合物粒子的壳部分；随后c)使核-壳聚合物粒子与水性碱接触以在不实质上聚合塑化剂的情况下使核膨胀；随后d)聚合塑化剂；
其中所述第一单体乳液包含a)以所述第一单体乳液中的单体的重量计，0.1重量％到5重量％的磷酸单体；和b)50重量％到99.9重量％的选自由以下组成的群组的第一非离子烯系不饱和单体：苯乙烯、甲基丙烯酸甲酯、丙烯腈和丙烯酸叔丁酯以及其组合；以及c)0.1重量％到15重量％羧酸官能化单体；
其中所述酸官能化聚合物粒子包含以所述聚合物粒子的重量计，20重量％到50重量％的羧酸单体的结构单元；和50重量％到80重量％的第二非离子烯系不饱和单体的结构单元；
其中所述塑化剂包含以所述聚合物粒子的重量计，7％到30％的第三非离子烯系不饱和单体；
其中所述磷酸官能化核-壳聚合物粒子的平均粒径在250nm到1.6μm范围内。
第一单体乳液包含以第一单体乳液中的单体的重量计，0.1重量％，优选地0.2重量％，更优选地0.5重量％到5重量％，更优选地到3重量％，并且最优选地到2重量％的磷酸单体。第一单体乳液进一步包含以第一单体乳液中的单体的重量计，50重量％，更优选地70重量％，并且最优选地85重量％到99.9重量％，并且更优选地到95重量％的第一非离子烯系不饱和单体。第一非离子烯系不饱和单体的折射率(Rf)优选地是至少1.4。
适合的磷酸单体的实例包括醇的膦酸酯和磷酸二氢酯，其中所述醇含有可聚合乙烯基或烯烃基或经所述基团取代。优选的磷酸二氢酯是甲基丙烯酸羟烷基酯的磷酸酯，包括甲基丙烯酸磷酸乙酯和甲基丙烯酸磷酸丙酯，其中甲基丙烯酸磷酸乙酯是尤其优选的。“甲基丙烯酸磷酸乙酯”(PEM)在本文中用于指以下结构：
其中R是H或
其中虚线表示与氧原子的连接点。
第一非离子烯系不饱和单体包括苯乙烯、甲基丙烯酸甲酯、丙烯腈或丙烯酸叔丁酯以及其组合。苯乙烯或苯乙烯与丙烯腈的组合是优选的单体。当苯乙烯和丙烯腈都使用时，苯乙烯与丙烯腈的优选的w/w比是98∶2到85∶15。
第一单体乳液进一步包含以第一单体乳液中的单体的重量计，0.1重量％，优选地0.2重量％，并且更优选地0.5重量％到15重量％，更优选地到10重量％，并且最优选地到5重量％的羧酸官能化单体。适合的羧酸官能化单体的实例包括丙烯酸、甲基丙烯酸、顺丁烯二酸、反丁烯二酸以及伊康酸，其中丙烯酸或甲基丙烯酸是优选的。
第一单体乳液可以包括其它单体。举例来说，第一单体乳液可以包括以第一单体乳液中的单体的重量计，呈0.1重量％，更优选地0.2重量％，到优选地20重量％，更优选地到10重量％，更优选地到5重量％，并且最优选地到2重量％的浓度的聚烯系不饱和单体。优选的聚烯系不饱和单体是二烯系不饱和单体和三烯系不饱和单体，如甲基丙烯酸烯丙酯(ALMA)、二乙烯基苯(DVB)、乙二醇二丙烯酸酯(EGDA)、乙二醇二甲基丙烯酸酯(EGDMA)、三羟甲基丙烷三丙烯酸酯(TMPTA)以及三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)。
酸官能化聚合物粒子包含a)以聚合物粒子的重量计，优选地25重量％，并且更优选地32重量％，到50重量％，优选地到40重量％，并且更优选地到36重量％的羧酸单体，优选地丙烯酸或甲基丙烯酸的结构单元；和b)以酸官能化聚合物粒子的重量计，优选地60重量％，并且更优选地64重量％，到优选地75重量％，并且更优选地到68重量％的第二非离子烯系不饱和单体的结构单元。优选的第二非离子烯系不饱和单体的实例包括甲基丙烯酸甲酯和苯乙烯，其中甲基丙烯酸甲酯是更优选的。酸官能化聚合物粒子的平均直径优选地是100nm，更优选地125nm到优选地160nm，更优选地到150nm，并且最优选地到140nm，如通过BI90普拉斯粒径分析器(BI90 Plus Particle Size Analyzer)测定。
第一单体乳液和酸官能化聚合物粒子的水性分散液在乳液聚合条件下一起接触以形成核-壳聚合物粒子的水性分散液。优选地，第一单体乳液的磷酸单体部分以分阶段方式添加到含有聚合物粒子的水性分散液的容器中以使得所有磷酸单体历经比单体乳液的其它单体短的时间段添加到反应容器中。更优选地，磷酸单体历经少于总单体乳液添加时间的60％的时间添加。最优选地，磷酸单体添加经延迟直到40％到75％的不存在磷酸单体的单体乳液添加到反应容器中。已出人意料地发现磷酸单体的添加的分阶段对复合物形成程度具有显著影响，其又有利地影响在最终涂布产品中观察到的遮盖力。
允许聚合进行到第一单体乳液中的单体的所需转化程度，优选地至少90％，更优选地至少95％，并且最优选地至少98％单体转化；在实现所需转化程度后，优选地抑制反应以停止或实质上停止未反应残余单体的聚合。抑制优选地使用抑制剂或氧化还原对进行。适合的抑制剂的实例包括4-羟基-2，2，6，6-四甲基哌啶-1-氧基(4-羟基-TEMPO)、2，2，6，6-四甲基哌啶-1-氧基(TEMPO)、单甲基乙醚氢醌(MEHQ)以及4-叔丁基儿茶酚。适合的氧化还原对的实例包括氧化剂，如叔丁基氢过氧化物(t-BHP)、叔戊基氢过氧化物(t-AHP)、过硫酸钠(NaPS)、过硫酸铵(APS)以及过氧化氢与还原剂，如异抗坏血酸(IAA)、亚硫酸氢钠以及硫酸钠的组合。通过允许反应进行到完成或实质上完成来停止或实质上停止聚合也是可能的，尽管不一定优选。
随后使可聚合塑化剂与磷酸官能化核-壳聚合物粒子接触以塑化壳，由此提供随后添加的水性碱穿过壳(伴随聚合物粒子的伴随膨胀)并且用中和到至少6，更优选地至少7，到10，更优选地到9的pH的水填充核的方式。适合的碱的实例包括碱金属氢氧化物、碱土金属氢氧化物、碱金属碳酸盐、碱土金属碳酸盐、胺以及NH4OH，其中NaOH、KOH以及NH4OH是尤其优选的碱。
可聚合塑化剂可以是任何烯系不饱和单体，但优选地是Tg高于50℃的单体(即，单体的均聚物的Tg如通过福克斯方程式(Fox equation)计算是高于50℃)或用交联剂共聚合的低Tg单体。优选的可聚合塑化剂的实例包括苯乙烯或甲基丙烯酸甲酯，或丙烯酸丁酯与二乙烯基苯或甲基丙烯酸烯丙酯的组合。
可聚合塑化剂以按核-壳聚合物粒子的重量计，优选地10重量％，并且更优选地12重量％，到优选地25重量％，并且更优选地到20重量％的浓度使用。应了解可聚合塑化剂可以包括来自第一单体乳液的未反应单体；尽管不优选，但有可能可聚合塑化剂完全由未反应单体产生。然而，优选的是使额外可聚合塑化剂与核-壳聚合物粒子的水性分散液接触。
在聚合物粒子已膨胀到其所需水平后，随后聚合可聚合塑化剂。优选的是在这一聚合步骤之后剩余少于1％，更优选地少于0.1％，并且最优选地少于0.01％的残余可聚合塑化剂。
磷酸官能化聚合物粒子有利地与颜料粒子(如TiO2粒子，尤其用硅烷或氧化铝表面处理的TiO2粒子的含水浆料)掺合以形成适用于在涂料组合物(如油漆配制品、纸涂料、喷墨涂料、印刷墨、防晒剂、指甲油以及木材涂料)中提供不透明度的复合物。
配制品还可以包括如以下的多种其它材料中的任一种：填充剂、粘合剂、流变改性剂、分散剂、表面活性剂、消泡剂、防腐剂、助流剂、均化剂以及中和剂。已发现与不形成复合物的不透明聚合物与颜料粒子的水性掺合物相比，复合物赋予配制品额外的遮盖益处。
在第二方面中，本发明是一种包含吸附到TiO2粒子的磷酸官能化核-壳聚合物粒子的水性分散液的复合物，其中核包含pH是至少6并且不大于10的水；其中核的平均直径是200nm到1.4μm，并且核-壳粒子的平均直径是225nm到1.6μm；其中壳包含a)50％到99.9％的一种或多种选自由以下组成的群组的单体的聚合物或共聚物：苯乙烯、甲基丙烯酸甲酯、丙烯腈以及丙烯酸叔丁酯；和b)0.1重量％到5重量％的磷酸单体的结构单元。
磷酸官能化核-壳聚合物粒子的优选最终核直径在250nm，并且更优选地275nm，到优选地500nm，更优选地到400nm，并且最优选地到350nm范围内，如通过实例章节中描述的空隙率测量测定。最终核-壳聚合物粒子的直径优选地在250nm，更优选地275nm，并且最优选地300nm，到优选地550nm，更优选地到425nm，并且最优选地到375nm范围内，如使用BI90普拉斯粒径分析器测定。最终核-壳聚合物粒子的空隙率(即，最终核的体积比最终核-壳聚合物粒子的总体积)优选地在30％，更优选地35％，并且最优选地40％，到优选地70％，更优选地到60％，并且最优选地到46％范围内。
实例
缩写
| NaPS | 过硫酸钠 |
| MMA | 甲基丙烯酸甲酯 |
| MAA | 甲基丙烯酸 |
| AA | 丙烯酸 |
| SDS | 十二烷基硫酸钠(23％水溶液) |
| STY | 苯乙烯 |
| AN | 丙烯腈 |
| EDTA | 乙二胺四乙酸四钠盐 |
| IAA | 异抗坏血酸 |
| BA | 丙烯酸丁酯 |
| DVB | 二乙烯基苯 |
| 4-羟基TEMPO | 4-羟基-2，2，6，6-四甲基哌啶-1-氧基 |
| t-BHP | 叔丁基氢过氧化物 |
| PEM | 甲基丙烯酸磷酸乙酯(60％活性) |
| ALMA | 甲基丙烯酸烯丙酯 |
| PS | 粒径 |
比较实例1-制备无磷酸官能度的不透明聚合物
在N2下向配备有浆式搅拌器、温度计、氮气入口以及回流冷凝器的5升四颈圆底烧瓶中添加去离子水(700g)。将内容物加热到89℃，接着添加溶解于去离子水(40g)中的NaPS(3.40g)随后紧接着添加实质上如US 6,020,435，实例1至16中所描述制备的66 MMA/34MAA种子材料(200.00g，32％固体，PS＝140nm，通过BI90普拉斯粒径分析器)。
将通过混合去离子水(320g)、SDS(15.9g)、STY(803.0g)、AN(90.2g)以及亚麻籽油脂肪酸(3.5g)制备的第一单体乳液(ME I)在78℃的温度下以6.0g/min的速率添加到锅中。在开始ME I添加之后的两分钟，向锅中添加与去离子水(50g)混合的AA(9.0g)的溶液。从开始ME I添加30min之后，馈送速率增加到12g/min，并且将溶解于去离子水(40g)中的过硫酸钠(0.85g)的混合物以1.0g/min的速率共馈送到锅中。随后使反应混合物的温度增加到84℃。从开始ME I添加45min之后，馈送速率增加到24g/min并且使温度增加到92℃。从开始MEI添加60min之后，馈送速率增加到30g/min。在完成ME I和共馈料添加后，使溶解于去离子水(20g)中的硫酸亚铁(0.02g)的溶液与溶解于两克去离子水中的EDTA(0.02g)的溶液混合。将这一混合物连同溶解于去离子水(20g)中的IAA(0.71g)的单独溶液一起添加到锅中。随后将批料保持在90℃下持续15min；将通过混合去离子水(40g)、SDS(3.4g)、BA(107.0g)、DVB(37.72g)以及4-羟基TEMPO(2.5g)制备的第二单体乳液(ME II)以45g/min的速率连同热去离子水(900g)一起添加到锅中。随后历经5min向锅中添加氢氧化铵(40.0g，28％水溶液)于去离子水(40g)中的溶液。批料随后在85℃下保持五分钟，在这一时间之后将与去离子水(40g)混合的t-BHP(1.5g)的溶液和与去离子水(40g)混合的IAA(0.85g)的溶液以0.8g/min的速率共馈送到锅中。在完成t-BHP和IAA共馈送之后，将批料冷却到室温并且过滤以去除形成的任何凝结物。最终乳胶的固体含量是30.5％。
实例1-5-制备甲基丙烯酸磷酸乙酯官能化不透明聚合物
通过比较实例1的程序制备实例，不同之处在于对于实例1-3，在75％ME1添加到锅中之后将PEM添加到ME1槽中；对于实例4-5，在33％ME1添加到锅中之后将PEM添加到ME1槽中。
空隙率测定
不透明聚合物的空隙率使用三个单独膨化杯重量测量测定。对于第一测量，通过将TEG(90.00g)和水(10.00g)放置在4盎司罐中制备三乙二醇(TEG)-水空白。搅拌TEG和水以形成充分分散混合物，将其倒入经称皮重的膨化杯中。获得这一混合物的重量(空白，为了随后计算称为BL)。通过将不透明聚合物乳液倒入经称皮重的膨化杯中并且获得不透明聚合物乳液的重量(为了随后计算称为OP)来获得第二测量值。对于第三测量，通过在搅拌下将TEG(90.00g)放置到4盎司罐中制备TEG与不透明聚合物乳液的混合物。将不透明聚合物乳液添加到被计算为等于含有10.00g水的乳液的量的罐中。在将不透明聚合物乳液的等分试样添加到TEG的2min内，将混合物倒入经称皮重的膨化杯中并且获得重量(OP/TEG混合物的重量，为了随后计算称为“OP-A”)。
不透明聚合物的空隙率是根据以下方程式。除通过膨化杯测量获得的值以外，还必须已知不透明聚合物乳液的固体含量(“固体”)。计算结果是不透明聚合物的空隙率(VF％)。
方程式术语
| BL | TEG/水空白的重量(克) |
| OP | 不透明聚合物乳液的重量(克) |
| OP<sub>a</sub> | 不透明聚合物乳液/TEG混合物的重量(克) |
| 固体 | 当干燥时保持固体的不透明聚合物乳液的百分比，表示为0与1之间的小数 |
| WBV | 不透明聚合物乳液的湿膨化值 |
| DBV | 不透明聚合物的干膨化值 |
| SBV | 固体不透明聚合物的膨化值 |
| TEGS | 与TEG和固体含量相关的中间计算值 |
| PS | 粒径 |
| VF％ | 不透明聚合物的空隙率，以百分比形式表示 |
空隙率的计算
其中，
测定不透明聚合物空隙直径
不透明聚合物的空隙直径可以使用不透明聚合物粒子的粒径和不透明聚合物粒子的空隙率计算。如下计算空隙直径：
空隙直径＝(VF％×(PS/2)3)1/3
表1阶段比率指核比内壳(ME I)比外壳(ME II)的比率。
表1-不透明聚合物的组成
| 实例编号 | 1 | 2 | 3 | 4 | 5 | 比较实例1 |
| PEM％<sup>a</sup> | 0.5 | 1.0 | 1.5 | 1.5 | 1.5 | 0 |
| 阶段比率 | 1∶14∶2.14 | 1∶14∶2.14 | 1∶14∶2.14 | 1∶14∶2.14 | 1∶14∶2.14 | 1∶14∶2.14 |
| 核MMA∶MAA | 66∶34 | 66∶34 | 66∶34 | 66∶34 | 66∶34 | 66∶34 |
| 核PS(nm) | 140 | 140 | 140 | 83 | 108 | 140 |
| ME I | ||||||
| STY | 88.42 | 87.85 | 87.3 | 91.45 | 91.45 | 89 |
| AN | 10 | 10 | 10 | 5 | 5 | 10 |
| AA | 1.0 | 1.73 | 1.0 | 0 | 0 | 1.0 |
| MAA | 0 | 0 | 0 | 1.5 | 1.5 | 0 |
| PEM<sup>a</sup> | 0.58 | 1.15 | 1.73 | 1.8 | 1.8 | 0 |
| ALMA | 0 | 0 | 0 | 0.25 | 0.25 | 0 |
| MEII | ||||||
| BA | 78 | 78 | 78 | 0 | 0 | 78 |
| STY | 0 | 0 | 0 | 100 | 100 | 0 |
| DVB | 22 | 22 | 22 | 0 | 0 | 22 |
| 粒径 | 458 | 375 | 360 | 270 | 330 | 423 |
| 空隙率 | 40.0 | 37.9 | 37.2 | 38.1 | 42 | 39.4 |
a针对PEM活性(报告量的60％)未调节。
将不透明聚合物配制成根据表2的油漆。(亚乐顺(ACRYSOL)和罗普莱克斯(RHOPLEX)是陶氏化学公司(The Dow Chemical Company)或其附属公司的商标。)
表2-用不透明聚合物配制的油漆
库贝尔卡-芒克(Kubelka-Munk)S/密耳测试方法
对于每种油漆，使用1.5密耳伯德(Bird)刮涂棒在黑色释放卡(Black ReleaseChart)(莱纳塔形式(Leneta Form)RC-BC)上制备四个刮涂物，并且允许所述卡干燥过夜。使用模板，在每一卡上切出3.25”×4”矩形。使用爱色丽色彩i7分光光度计(X-RiteColori7 Spectrophotometer)在划线区域中的每一个中测量Y-反射率五次，并且记录平均Y-反射率。对于每种油漆，在黑色释放卡上使用3”，25密耳块刮涂棒制备厚膜刮涂物，并且使所述卡干燥过夜。在刮涂物的五个不同区域中测量Y-反射率，并且记录平均Y-反射率。通过以下方程式1给出库贝尔卡-芒克遮盖力值S：
方程式1
其中X是平均膜厚度，R是厚膜的平均反射率，并且RB是在薄膜的黑色上方的平均反射率。X可以由漆膜的重量(Wpf)、干膜的密度(D)以及膜面积(A)计算。3.25”×4”模板的膜面积是13in2。
油漆实例和比较实例的遮盖力(S/密耳)数据概述在表3中。
表3-油漆样品的干遮盖力
a针对PEM活性(60％活性)未调节
数据显示PEM官能化样品都展示比含有非PEM官能化不透明聚合物的样品高的干遮盖力。PEM官能化不透明聚合物与TiO2之间的复合物形成的证据使用非对称流场流分离分图(Asymmetric Flow Field Flow Fractionation fractogram)发现，所述图显示与未官能化不透明聚合物相比的粒径增加。VSR 1050粘合剂、非PEM官能化不透明聚合物以及TiO2粒子的混合物显示在120nm(粘合剂)和约400nm(不透明聚合物与TiO2的未结合混合物)下的粒子的双峰分布；含有粘合剂、PEM官能化不透明聚合物以及TiO2的混合物得到在120nm、300nm(未结合TiO2)和在约700nm下的峰下的粒子的三峰分布，其显示不透明聚合物-TiO2复合物形成的证据。
Claims (13)
1.一种制备磷酸官能化核-壳聚合物粒子的水性分散液的方法，其包含以下步骤：a)在乳液聚合条件下使i)第一单体乳液与ii)平均粒径是80nm到180nm的酸官能化聚合物粒子的水性分散液接触以形成核-壳聚合物粒子的水性分散液，该平均粒径通过BI90普拉斯粒径分析器测定；随后b)用可聚合塑化剂塑化所述核-壳聚合物粒子的所述壳部分；随后c)使所述核-壳聚合物粒子与水性碱接触以在不实质上聚合所述塑化剂的情况下使所述核膨胀；随后d)聚合所述塑化剂；
其中所述第一单体乳液包含a)以所述第一单体乳液中的单体的重量计，0.1重量％到5重量％的磷酸单体；和b)50重量％到99.9重量％的选自由以下组成的群组的第一非离子烯系不饱和单体：苯乙烯、甲基丙烯酸甲酯、丙烯腈和丙烯酸叔丁酯以及其组合；以及c)0.1重量％到15重量％羧酸官能化单体；限制条件是，所述第一单体乳液中的所有组分的含量之和为100重量％；
其中所述酸官能化聚合物粒子包含以所述酸官能化聚合物粒子的重量计，20重量％到50重量％的羧酸单体的结构单元；和50重量％到80重量％的第二非离子烯系不饱和单体的结构单元；
其中所述塑化剂包含以所述酸官能化聚合物粒子的重量计，7重量％到30重量％的第三非离子烯系不饱和单体；
其中所述磷酸官能化核-壳聚合物粒子的平均粒径在步骤d)之后在250nm到1.6μm范围内，该平均粒径通过BI90普拉斯粒径分析器测定。
2.根据权利要求1所述的方法，其中所述第一单体乳液中的所述磷酸单体的浓度是0.2重量％到3重量％亚磷酸单体；其中所述第一单体乳液中的所述第一非离子烯系不饱和单体的浓度是70重量％到95重量％，并且其中所述第一单体乳液中的所述羧酸官能化单体的浓度是0.2重量％到0.5重量％，浓度都以所述第一单体乳液中的单体的重量计；并且其中所述塑化剂包含以所述酸官能化聚合物粒子的重量计10重量％到25重量％第三非离子烯系不饱和单体。
3.根据权利要求2所述的方法，以所述酸官能化聚合物粒子的重量计，其中所述酸官能化聚合物粒子中的所述羧酸单体的所述结构单元的浓度是25重量％到40重量％，并且其中所述第二非离子烯系不饱和单体的所述结构单元的浓度是60重量％到75重量％；并且其中酸官能化聚合物粒子的平均粒径是125nm到150nm，该平均粒径通过BI90普拉斯粒径分析器测定。
4.根据权利要求3所述的方法，其中所述第一单体乳液进一步包含0.1重量％到10重量％的选自由以下组成的群组的二烯系或三烯系不饱和单体的结构单元：甲基丙烯酸烯丙酯、二乙烯基苯、乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯以及三羟甲基丙烷三甲基丙烯酸酯。
5.根据权利要求3所述的方法，其中所述磷酸单体是甲基丙烯酸磷酸乙酯，其中所述酸官能化聚合物粒子中的所述羧酸单体的结构单元的浓度是32重量％到36重量％，并且所述第二非离子烯系不饱和单体的结构单元的浓度是64重量％到68重量％，其中所述羧酸单体是丙烯酸或甲基丙烯酸，并且其中所述第二非离子烯系不饱和单体是甲基丙烯酸甲酯。
6.根据权利要求5所述的方法，其中所述第一单体乳液包含以所述第一单体乳液中的单体的重量计，0.5重量％到2重量％甲基丙烯酸磷酸乙酯；和0.5重量％到5重量％所述丙烯酸或甲基丙烯酸。
7.根据权利要求1所述的方法，其中在步骤a)中，所述第一单体乳液在乳液聚合条件下历经第一时间段添加到所述酸官能化聚合物粒子的所述水性分散液中，并且所述第一单体乳液的所述磷酸单体部分历经少于所述第一时间段的60％的第二时间段添加到所述酸官能化聚合物粒子的所述水性分散液中。
8.根据权利要求7所述的方法，其中所述磷酸单体添加经延迟直到40重量％到75重量％所述第一单体乳液添加到所述酸官能化聚合物粒子的所述水性分散液中。
9.根据权利要求8所述的方法，其中允许所述第一单体乳液与酸官能化聚合物粒子的所述水性分散液的聚合进行到单体到所述核-壳聚合物粒子的至少98重量％转化，在这一时间之后使抑制剂与所述核-壳聚合物粒子的所述水性分散液接触以停止或实质上停止聚合。
10.根据权利要求9所述的方法，其中所述可聚合塑化剂以按所述磷酸官能化核-壳聚合物粒子的重量计，12重量％到20重量％苯乙烯或甲基丙烯酸甲酯或丙烯酸丁酯与二乙烯基苯或甲基丙烯酸烯丙酯的组合的浓度添加，其中所述水性碱是NaOH、KOH或NH4OH。
11.根据权利要求10所述的方法，其中在所述可聚合塑化剂聚合之后少于0.01重量％的所述可聚合塑化剂剩余。
12.根据权利要求1所述的方法，其中在步骤d)之后，所述磷酸官能化核-壳聚合物粒子与TiO2掺合以形成复合粒子的水性分散液。
13.一种复合物，其包含吸附到TiO2粒子的、通过权利要求1～12中任一项所述的方法制备的磷酸官能化核-壳聚合物粒子的水性分散液，其中所述核包含pH是至少6并且不大于10的水；其中所述核的平均直径是200nm到1.4μm；并且所述核-壳粒子的平均直径是225nm到1.6μm；其中所述壳包含a)50重量％到99.9重量％的一种或多种选自由以下组成的群组的单体的聚合物或共聚物：苯乙烯、甲基丙烯酸甲酯、丙烯腈以及丙烯酸叔丁酯；和b)0.1重量％到5重量％的磷酸单体的结构单元。
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| CN108641039B (zh) * | 2018-04-11 | 2021-02-26 | 华南师范大学 | 一种包覆型核壳结构复合颗粒及其制备方法和应用 |
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| CN1517412A (zh) * | 2003-01-24 | 2004-08-04 | 罗姆和哈斯公司 | 有机-无机复合颗粒及其制备方法 |
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