CN115605433A - 碳酸铈（iii）分散体的制备 - Google Patents
碳酸铈（iii）分散体的制备 Download PDFInfo
- Publication number
- CN115605433A CN115605433A CN202180022258.XA CN202180022258A CN115605433A CN 115605433 A CN115605433 A CN 115605433A CN 202180022258 A CN202180022258 A CN 202180022258A CN 115605433 A CN115605433 A CN 115605433A
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- Prior art keywords
- composition
- cerium
- iii
- polymer
- carbonate
- Prior art date
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- KHSBAWXKALEJFR-UHFFFAOYSA-H cerium(3+);tricarbonate;hydrate Chemical compound O.[Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O KHSBAWXKALEJFR-UHFFFAOYSA-H 0.000 title claims abstract description 47
- 239000006185 dispersion Substances 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title description 11
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000000049 pigment Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims description 49
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 11
- 239000003086 colorant Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 amine carboxylic acid Chemical class 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000010434 nepheline Substances 0.000 claims description 3
- 229910052664 nepheline Inorganic materials 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical class OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims description 2
- 229940038472 dicalcium phosphate Drugs 0.000 claims description 2
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- CYKDLUMZOVATFT-UHFFFAOYSA-N ethenyl acetate;prop-2-enoic acid Chemical class OC(=O)C=C.CC(=O)OC=C CYKDLUMZOVATFT-UHFFFAOYSA-N 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 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
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 10
- 230000014759 maintenance of location Effects 0.000 abstract description 10
- 238000009472 formulation Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000008199 coating composition Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- 239000004926 polymethyl methacrylate Substances 0.000 description 12
- 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 11
- 239000001099 ammonium carbonate Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 9
- 235000012501 ammonium carbonate Nutrition 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 241000801593 Pida Species 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- ZBIKORITPGTTGI-UHFFFAOYSA-N [acetyloxy(phenyl)-$l^{3}-iodanyl] acetate Chemical compound CC(=O)OI(OC(C)=O)C1=CC=CC=C1 ZBIKORITPGTTGI-UHFFFAOYSA-N 0.000 description 4
- 229920005822 acrylic binder Polymers 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- MUUZQJVCOSXKMS-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate;tetrahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MUUZQJVCOSXKMS-UHFFFAOYSA-P 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- 239000004606 Fillers/Extenders Substances 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- IDDVVGWTUJSOIV-UHFFFAOYSA-O azanium cerium(3+) tetranitrate tetrahydrate Chemical compound [NH4+].O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IDDVVGWTUJSOIV-UHFFFAOYSA-O 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- BXLLINKJZLDGOX-UHFFFAOYSA-N dimethoxyphosphorylmethanamine Chemical compound COP(=O)(CN)OC BXLLINKJZLDGOX-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000006233 lamp black Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- IAFBRPFISOTXSO-UHFFFAOYSA-N 2-[[2-chloro-4-[3-chloro-4-[[1-(2,4-dimethylanilino)-1,3-dioxobutan-2-yl]diazenyl]phenyl]phenyl]diazenyl]-n-(2,4-dimethylphenyl)-3-oxobutanamide Chemical compound C=1C=C(C)C=C(C)C=1NC(=O)C(C(=O)C)N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(C)=O)C(=O)NC1=CC=C(C)C=C1C IAFBRPFISOTXSO-UHFFFAOYSA-N 0.000 description 1
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 1
- SYFQYGMJENQVQT-UHFFFAOYSA-N 6-amino-2-[bis(carboxymethyl)amino]hexanoic acid Chemical compound NCCCCC(C(O)=O)N(CC(O)=O)CC(O)=O SYFQYGMJENQVQT-UHFFFAOYSA-N 0.000 description 1
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- RPBJCMGPMCAUSR-UHFFFAOYSA-O azanium;cerium(3+);tetranitrate Chemical compound [NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O RPBJCMGPMCAUSR-UHFFFAOYSA-O 0.000 description 1
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- PYUYQYBDJFMFTH-WMMMYUQOSA-N naphthol red Chemical compound CCOC1=CC=CC=C1NC(=O)C(C1=O)=CC2=CC=CC=C2\C1=N\NC1=CC=C(C(N)=O)C=C1 PYUYQYBDJFMFTH-WMMMYUQOSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 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
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
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Abstract
本发明涉及一种组合物，该组合物包含聚合物和碳酸铈(III)。该组合物用于包括颜料、染料或色调剂或其组合的涂料配制品中，以促进由这些配制品形成的涂料中的颜色保持和减弱不期望的颜色形成。
Description
相关申请的引证
本申请要求于2020年3月20日提交的美国临时申请号62/992,424的优先权。
背景技术
在外部漆领域中，期望在延长的时间段内保持新鲜外观的漆涂覆的基底。这种“新鲜涂漆的(freshly painted)”外观可以通过三种相互关联的特性来测量：耐沾污性(Dirt-pickup resistance)(DPUR)、光泽保持性(gloss retention)、以及色调保持性(tintretention)。其中，色调保持性尤为突出，因为较暗和较深的颜色在外部应用中变得更为流行。
色调保持性的损失，也称为褪色，被认为由介导的光催化聚合物和由 TiO2引起的着色剂降解引起，TiO2在大多数漆配制品中用作不透明颜料。 TiO2颗粒吸收UV光，并且在水存在下生成高反应性羟基，其反应性地降解聚合物主链和着色剂，从而引起光泽降低、褪色和不期望的颜色形成。
通过在聚合物或着色剂降解发生之前使用UV吸收剂通过阻挡UV光来防止自由基形成和抗氧化剂来猝灭自由基，已很大程度上实现了减轻外部涂层降解的尝试。不幸的是，UV吸收剂需要足够长的路径长度以发生吸收并且因此仅在透明顶部涂层中有效。抗氧化剂(如受阻胺、受阻酚、碳中心自由基(基团，radical)、亚磷酸酯和硫化物)倾向于从涂覆的基底浸出，因此仅提供短期保护。因此，在外部涂层领域中发现更有效的方式以实现颜色保留并减少在涂覆的表面中不期望的颜色形成将是有利的。
发明内容
本发明通过提供一种包含聚合物和碳酸铈(III)颗粒的组合物解决了本领域中的需要。
具体实施方式
在第一方面中，本发明是一种包含聚合物和碳酸铈(III)颗粒的组合物。本发明的组合物可用于减少涂料中的褪色并减少不需要的颜色体的形成。
在这一方面中，聚合物优选与液体形成溶液或分散体。在本发明的这一方面的一个实施方式中，组合物是聚合物颗粒(胶乳，latex)和碳酸铈 (III)颗粒的水性分散体。碳酸铈(III)颗粒的粒径不受限制，但是对于某些应用(如半光泽涂层配制品)，优选的是铈(III)颗粒是纳米级颗粒。
如在本文所使用的，“纳米级碳酸铈(III)颗粒”是指具有如通过动态光散射测量的不大于500nm的z-平均粒径的碳酸铈(III)颗粒。术语“纳米分散体”是指纳米级碳酸铈(III)颗粒的水性分散体。在另一方面中，纳米级碳酸铈(III)颗粒具有不大于300nm的z-平均粒径；在另一方面中，不大于200nm；在另一方面中，不小于50nm。
碳酸铈(III)的纳米级分散体有利地如下制备：水溶性铈(III)铵盐、水溶性碳酸盐、以及封端配体有利地在足以产生碳酸铈(III)颗粒的纳米分散体的条件下在水中在8(优选9)至12(优选11)的范围内的pH下混合在一起。水溶性铈(III)铵盐与水溶性碳酸盐的摩尔：摩尔比优选在 2：1、更优选1：1至优选1：20、更优选1：10的范围内；水溶性铈(III) 铵盐与封端配体的摩尔：摩尔比优选在50：1、更优选30：1至1：1的范围内。反应通常在环境温度或环境温度附近进行，并且反应通常在一小时内完成。
如在本文所使用的，“水溶性铈(III)铵盐”是指按所使用的比例在水中至少10％可溶的铈(III)铵盐。优选的水溶性铈(III)铵盐是硝酸铈 (III)铵。类似地，术语“水溶性碳酸盐”是指按所使用的比例在水中至少10％可溶的碱金属或铵的碳酸盐或碳酸氢盐。水溶性碳酸盐的实例包括碳酸钠、碳酸钾、碳酸铵、碳酸氢钠和碳酸氢钾，其中碳酸铵是优选的。
如在本文所使用的，“封端配体”是胺羧酸或其盐、胺膦酸或其盐、或者用羧酸基团官能化的聚合物或其盐。“胺羧酸”是指包含至少一个胺基团和至少一个羧酸基团的化合物。优选地，胺羧酸是氨基乙酸或其盐；优选地，氨基乙酸包括至少两个羧酸基团；更优选地，氨基乙酸是二乙酸胺、三乙酸胺、或四乙酸胺，其实例包括乙二胺四乙酸(EDTA)、乙二胺二乙酸(EDDA)、以及氮川三乙酸(nitrolotriacetic acid，氨三乙酸)(NTA)。
用羧酸基团官能化的聚合物可以是例如由含羧酸(如丙烯酸)单体的均聚反应产生的均聚物，或由含羧酸单体与一种或多种另外的单体(其不需要羧酸官能化)的共聚反应产生的共聚物。用羧酸基团官能化的均聚物的实例是聚丙烯酸(PAA)。
“胺膦酸”是指包含至少一个胺基团和至少一个膦酸基团的化合物。封端配体可以包括一个或多个膦酸以及一个或多个羧酸基团、以及其盐。胺膦酸的实例包括氨基三甲基膦酸(ATMP)、6-氨基-2-[双(羧甲基)氨基] 己酸和N-(膦酰甲基)亚氨基二乙酸(PIDA)。
在另一方面中，本发明是一种组合物，该组合物包含具有在5nm至 500nm范围内的z-平均粒径的碳酸铈(III)颗粒的水性分散体。分散体优选还包含封端配体，其被认为促进纳米分散颗粒的形成，同时稳定颗粒以防聚集。
基于水和碳酸铈(III)的重量，碳酸铈(III)在水中的浓度优选在0.2 重量％、更优选0.5重量％、最优选1重量％至25重量％、更优选21重量％的范围内。更典型地，调节反应物的浓度以形成1至5重量％固体的最终分散体；更高固体含量的组合物可以通过离心、随后去除上清液或真空去除水来制备。
基于聚合物的重量，聚合物与碳酸铈(III)的重量比优选在0.2重量％、更优选0.5重量％、并且最优选1重量％至10重量％、更优选8重量％、并且最优选5重量％的范围内。包含胶乳(latex)和碳酸铈(III)颗粒的组合物在涂料组合物、尤其是包含颜料或着色剂或两者的涂料组合物的领域中是有用的。颜料包括不透明颜料和增量剂(extender)。不透明颜料包括TiO2、BaSO4和有机中空球聚合物颗粒(HSP)。TiO2可以是锐钛矿或金红石，并且是被钝化或未钝化的。TiO2的商业实例为Ti-Pure-R706 TiO2和DeGussa P25 TiO2光催化剂。组合物可以包括锐钛矿和金红石的组合、钝化和未钝化的TiO2。
合适的增量剂包括碳酸盐、二氧化硅、硅酸盐、铝硅酸盐、磷酸盐、以及非中空有机微球。增量剂的更具体实例包括滑石、粘土、云母、绢云母(sericite)、CaCO3、霞石(nepheline)、长石、硅灰石、高岭石、磷酸二钙、以及硅藻土。
着色剂可以是有机或无机的、可分散的(色调剂，tint)或可溶的(染料)。合适的着色剂的实例包括亚甲基蓝、酞菁蓝、酞菁绿、单芳基黄 (monoarylide yellow)、二芳基黄(diarylide yellow)、苯并咪唑酮黄、杂环黄、DNA橙、吡咯橙、喹吖啶酮品红、喹吖啶酮紫、二噁嗪紫、喹吖啶酮红、萘酚红、吡咯红、金属化偶氮红、非金属化偶氮红、炭黑、油烟(lampblack)、黑色氧化铁、黄色氧化铁、棕色氧化铁、以及红色氧化铁。
在另一方面，本发明是一种组合物，该组合物包含在分散的碳酸铈(III) 颗粒的存在下溶解在溶剂(如氯仿)中的聚合物或共聚物(如聚(甲基丙烯酸甲酯)(PMMA))。本发明的这一方面的组合物可用于例如汽车前灯的外壳。
在另一方面中，本发明是一种包含碳酸铈(III)颗粒和纯聚合物的组合物。这种组合物可以通过混合碳酸铈(III)颗粒与挤出的聚合物熔体来制备。
组合物可以包含其他组分(如流变改性剂、表面活性剂和分散剂)。
合适的聚合物的实例包括聚丙烯酸酯、聚(苯乙烯-丙烯酸酯)、聚苯乙烯、聚乙酸乙烯酯、聚氨酯、聚(乙酸乙烯酯-丙烯酸酯)、硅酮、环氧树脂、聚烯烃、纤维素、以及聚硅酸盐。优选的胶乳的实例包括以下的结构单元： a)甲基丙烯酸甲酯或苯乙烯；b)丙烯酸酯单体，其是丙烯酸正丁酯、丙烯酸乙酯或丙烯酸2-乙基己基酯；c)羧酸单体，其是甲基丙烯酸或丙烯酸。还可能令人期望的是用磷酸单体(如甲基丙烯酸磷酸乙酯)将胶乳官能化。
如本文所使用的，命名单体的术语“结构单元”是指在聚合之后单体的残余部分。例如，甲基丙烯酸甲酯的结构单元如下所示：
甲基丙烯酸甲酯的结构单元
其中虚线表示结构单元与聚合物骨架的附接点。
碳酸铈(III)纳米级分散体在如乳胶漆配制品的应用中是尤其有用的，在这些应用中颜色和光泽保留是令人期望的。
实施例1-4-制备碳酸铈(III)颗粒的水性纳米分散体
在以下实施例中，通过动态光散射测定z-平均粒径。
实施例1-制备通过EDTA稳定的纳米级碳酸铈(III)颗粒的水性分散体
将硝酸铈(III)铵四水合物的水溶液(2g在100mL去离子水中)添加到250mL塑料瓶中。将EDTA(50mg)和碳酸铵(1g)分别溶解在水 (50mL)中，然后在搅拌(600rpm)10min的情况下，在25s内添加到硝酸铈(III)铵四水合物的溶液中。观察到混合物的pH值为8.0±0.3。
将产物混合物分到四个40mL离心管中，随后以20,000rpm进行离心6min。收集每个管中的白色产物并用25mL水洗涤(包括5min涡旋混合)，以确保去除可溶性硝酸盐和过量碳酸铵。洗涤和离心后的最终产物作为具有20wt％固体含量的湿糊剂而获得。
为了研究EDTA的负载对碳酸铈(III)特性的影响，使用100mg和 500mg的EDTA将该实施例重复两次。发现碳酸铈颗粒的z-平均粒径是 125nm(50mg EDTA)、118nm(100mgEDTA)、以及114nm(500mg EDTA)。
实施例2-制备通过NTA稳定的纳米级碳酸铈(III)颗粒的水性分散体
除了使用NTA(65mg)代替EDTA作为封端配体之外，基本上遵循实施例1中所描述的程序。洗涤和离心后的最终产物作为具有20wt％固体含量的湿糊剂而获得。
用32.5mg的NTA重复该实施例。发现碳酸铈颗粒的z-平均粒径是 157nm(32.5mgNTA)和115nm(65mg NTA)。
实施例3-制备通过PIDA稳定的纳米级碳酸铈(III)颗粒的水性分散体
将硝酸铈(III)铵四水合物(2g在100mL去离子水中)的水溶液添加到250mL塑料瓶中。将PIDA(72mg)和碳酸铵(1g)分别溶解在水 (50mL)中，然后在搅拌(600rpm)10min的情况下，在25s内添加到硝酸铈(III)铵四水合物的溶液中。观察到混合物的pH值为8.0±0.3。
将产物混合物分到四个40mL离心管中，随后以20,000rpm进行离心 6min。收集每个管中的白色产物并用25mL水洗涤(包括5min涡旋混合)，以确保去除可溶性硝酸盐和过量碳酸铵。洗涤和离心后的最终产物作为具有20wt％固体含量的湿糊剂而获得。发现碳酸铈颗粒的z-平均粒径是105 nm。
实施例4-制备通过PAA稳定的纳米级碳酸铈(III)颗粒的水性分散体
将硝酸铈(III)铵四水合物(2g在100mL去离子水中)的水溶液添加到250mL塑料瓶中。将PAA(500mg的50％水溶液，MW＝2000g/mol) 和碳酸铵(1g)分别溶解在水(50mL)中，然后在搅拌(600rpm)10min 的情况下，在25s内添加到硝酸铈(III)铵四水合物的溶液中。观察到混合物的pH值为8.0±0.3。
将产物混合物分到四个40mL离心管中，随后以20,000rpm进行离心 6min。收集每个管中的白色产物并用25mL水洗涤(包括5min涡旋混合)，以确保去除可溶性硝酸盐和过量碳酸铵。洗涤和离心后的最终产物作为具有20wt％固体含量的湿糊剂而获得。
使用1.1g和2.2g的50％水溶液PAA重复实施例两次。发现通过动态光散射(DLS)测定的碳酸铈颗粒的z-平均粒径是105nm(0.5g PAA)、 105nm(1.1g PAA)、以及20nm(2.2gNTA)。
实施例5-7-用染料和色调剂制备涂层配制品
在以下制备中，丙烯酸粘合剂具有以下特征：(49BA/50MMA/1MAA)， z-平均粒径＝98nm，固体含量为40.2wt.％。
用染料制备漆配制品：
如下制备两种单独的分散体：
A.将Ti-Pure-R706 TiO2(3.5g)、任选的基于Ti-Pure-R706 TiO2重量的10％DeGussa P25 TiO2光催化剂、TAMOLTM 1124分散剂(Dow Chemical Company或其附属公司的商标，相对于颜料重量0.3wt.％)、1M NH4OH(10 μL)和3.5x10-4M刚果红染料或亚甲基蓝染料(0.7mL)的水溶液在1700 rpm在ZrO2珠(10mm)的存在下混合，以形成TiO2浆料。从浆料中去除ZrO2珠，随后随时间将另外量的染料溶液(1.27mL)添加到浆料中。然后将混合物混合(3500rpm持续3min)以获得4.65g的75wt.％颜料浆料。
B.将2wt.％至5wt.％碳酸铈(III)(相对于在步骤A中的Ti-Pure-R706 的重量)的固体(如以上描述的在不具有封端配体或具有封端配体的情况下制备的20％固体的湿糊剂，如实施例2中所描述)与水(0.86mL至0.44 mL，取决于固体)组合。用1M NH4OH将所得溶液的pH调节至pH 9。剪切混合物(3500rpm持续4min)，随后超声处理(10min)。
在搅拌下将来自步骤A的浆料与丙烯酸粘合剂(12.79g)进行混合。将来自步骤B的分散体与来自步骤A的浆料混合并且剪切混合物(3500 rpm持续1min)。随后，将ACRYSOLTM2020E增稠剂(陶氏化学公司或其附属公司的商标，0.6g)添加到混合物中并且混合(3500rpm持续3min) 以获得在约16％颜料体积浓度(PVC)下的最终漆配制品。
用色调剂制备漆配制品：
将Ti-Pure-R706 TiO2(4.6g)、TAMOLTM 1124分散剂(相对于颜料重量0.3wt.％)、1M NH4OH(10μL)、DeGussa P25 TiO2光催化剂(0.36g)、Colortrend有机红808着色剂(0.44g)和水(1.53g)在2100rpm下在 ZrO2珠的存在下混合。从浆料中去除ZrO2珠并再次混合(3500rpm，3min) 浆料以获得7g的75wt.％颜料浆料。将浆料与步骤B中描述的分散体混合(除了仅根据实施例2制备碳酸铈(III))以形成具有约16％的PVC的最终漆配制品。
涂层的UV诱导的光降解
漆配制品使用3密耳棒涂膜器施加在聚丙烯酸基底上。将施加的涂层在环境条件下干燥72h。然后将干燥涂层在254-nm UV光(140-150Lux) 下照射4h。
将一部分涂层(200mg)从聚丙烯酸基底刮下，与1mL乙醇组合，并且超声处理15min。然后将混合物涡旋5min，并且通过UV-vis光谱分析含有残留染料的上清液，以确定染料降解程度。
实施例5-通过UV-Vis的染料降解，含P25
如上所描述的，当含有Ti-R706-TiO2、DeGussa P25、丙烯酸粘合剂、刚果红染料和碳酸铈(III)，不含封端配体的样品暴露于UV光时，染料降解程度为8％。相比之下，不含碳酸铈(III)的降解程度是40％。
实施例6-通过UV-Vis的染料降解，不含P25
如上所描述的，当含有Ti-R706-TiO2、丙烯酸粘合剂、亚甲基蓝染料和碳酸铈(III)，不含封端配体的样品暴露于UV光时，染料降解程度为 0％。相比之下，不含碳酸铈(III)的降解程度是15％。
实施例7-通过UV-Vis的色调剂降解，含P25
如上所描述的，当使含有Ti-R706-TiO2、DeGussa P25、丙烯酸粘合剂、有机红色色调剂和碳酸铈(III)，具有封端配体(如实施例2中所描述) 的样品暴露于UV光时，发现颜色保留是完全保留的。相比之下，没有碳酸铈(III)的样品显示出显著的颜色损失。
聚甲基丙烯酸甲酯的UV诱导的光降解：
将a)溶解在CHCl3中的PMMA和b)碳酸铈(III)颗粒(如在实施例1或3中制备的；基于PMMA的重量2或5wt.％)的混合物倒入表面皿(watch glass)中并且允许在环境条件下干燥16h。在干燥16h后，然后将PMMA膜在254-nm UV光(140-150Lux)下照射4h。
实施例8-用EDTA封端的碳酸铈(III)进行的PMMA的UV光降解
对于含有用EDTA封端的碳酸铈(III)(基于PMMA的重量为2重量％) 的照射的PMMA膜，没有观察到黄化。相比之下，不含碳酸铈(III)的浇铸膜展现出显著的黄化。
实施例9-用PIDA封端的碳酸铈(III)进行的PMMA的UV光降解
对于含有用PIDA封端的碳酸铈(III)(基于PMMA的重量为5重量％) 的照射的PMMA膜，没有观察到黄化。相比之下，不含碳酸铈(III)的浇铸膜展现出显著的黄化。
这些研究证明，碳酸铈(III)实质性地改善了在由涂料配制品制备的涂层中的褪色并且显著地减弱了不期望的颜色形成。
Claims (12)
1.一种组合物，包括聚合物和碳酸铈(III)颗粒。
2.根据权利要求1所述的组合物，其中，所述聚合物与液体形成溶液或分散体。
3.根据权利要求2所述的组合物，所述组合物是聚合物颗粒和所述碳酸铈(III)颗粒的水性分散体。
4.根据权利要求3所述的组合物，其中，所述聚合物颗粒是聚丙烯酸酯、聚(苯乙烯-丙烯酸酯)、聚苯乙烯、聚乙酸乙烯酯、聚氨酯、聚(乙酸乙烯酯-丙烯酸酯)、硅酮、环氧树脂、聚烯烃、纤维素以及聚硅酸酯。
5.根据权利要求4所述的组合物，所述组合物还包含颜料、着色剂、或者颜料和着色剂两者。
6.根据权利要求5所述的组合物，其中，所述颜料选自由以下各项组成的组：TiO2、BaSO4、有机中空球形聚合物颗粒、滑石、粘土、云母、绢云母、CaCO3、霞石、长石、硅灰石、高岭石、磷酸二钙、硅藻土以及非中空有机微球。
7.根据权利要求6所述的组合物，其中，所述碳酸铈(III)颗粒是纳米级颗粒，并且其中，所述组合物还包含封端配体，所述封端配体是胺羧酸或其盐、胺膦酸或其盐、或者用羧酸基团官能化的聚合物或其盐。
8.根据权利要求7所述的组合物，其中，所述颜料包含TiO2，其中，所述TiO2是锐钛矿、金红石或它们的组合；并且其中，所述TiO2是钝化的、未钝化的或它们的组合。
9.根据权利要求8所述的组合物，其中，所述聚合物颗粒包括以下的结构单元：a)甲基丙烯酸甲酯、苯乙烯或它们的组合；b)丙烯酸酯单体，所述丙烯酸酯单体是丙烯酸正丁酯、丙烯酸乙酯、丙烯酸2-乙基己基酯或它们的组合；以及c)羧酸单体，所述羧酸单体是甲基丙烯酸、丙烯酸或它们的组合。
10.根据权利要求8所述的组合物，其中，所述聚合物颗粒包括甲基丙烯酸甲酯、丙烯酸正丁酯和甲基丙烯酸的结构单元。
11.根据权利要求10所述的组合物，其中，所述聚合物颗粒还包括甲基丙烯酸磷酸乙酯的结构单元。
12.根据权利要求2所述的组合物，其中，所述聚合物在有机溶剂中形成溶液，并且其中，所述聚合物是甲基丙烯酸甲酯的聚合物或共聚物。
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| CN108864802A (zh) * | 2018-05-27 | 2018-11-23 | 复旦大学 | 一种光扩散功能涂层材料及其制备方法 |
| KR20220002992A (ko) * | 2019-04-23 | 2022-01-07 | 더 리전츠 오브 더 유니버시티 오브 캘리포니아 | 탄산세륨(iii) 제형 |
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