CN110872366B - 用于制备多级聚合物颗粒的水分散体的方法 - Google Patents
用于制备多级聚合物颗粒的水分散体的方法 Download PDFInfo
- Publication number
- CN110872366B CN110872366B CN201910719806.9A CN201910719806A CN110872366B CN 110872366 B CN110872366 B CN 110872366B CN 201910719806 A CN201910719806 A CN 201910719806A CN 110872366 B CN110872366 B CN 110872366B
- Authority
- CN
- China
- Prior art keywords
- monomer
- weight
- polymer particles
- core
- weight percent
- 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.)
- Active
Links
- 239000002245 particle Substances 0.000 title claims abstract description 113
- 229920000642 polymer Polymers 0.000 title claims abstract description 104
- 239000006185 dispersion Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 162
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 80
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 27
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 10
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims abstract description 8
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims abstract description 7
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940119545 isobornyl methacrylate Drugs 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 40
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical group CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims description 2
- -1 defoamers Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 229920005787 opaque polymer Polymers 0.000 abstract description 9
- 239000008199 coating composition Substances 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000004816 latex Substances 0.000 description 13
- 229920000126 latex Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 5
- 235000010350 erythorbic acid Nutrition 0.000 description 5
- 229940026239 isoascorbic acid Drugs 0.000 description 5
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-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
- 239000000049 pigment Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 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 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 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
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 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
- 231100000017 mucous membrane irritation Toxicity 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C09D5/022—Emulsions, e.g. oil in water
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F20/70—Nitriles; Amides; Imides
-
- 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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- 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
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
本发明涉及制备多级聚合物颗粒的水分散体的方法,其包括在乳液聚合条件下并且以分级方式,使羧酸官能化核聚合物颗粒的水分散体与第一单体和第二单体接触。所述核包括高Tg疏水单体的结构单元和/或所述第一单体包括高Tg疏水单体,并且所述第二单体包括至少80%的苯乙烯。所述高Tg疏水单体是甲基丙烯酸环己酯、甲基丙烯酸异冰片酯、甲基丙烯酸4‑叔丁酯、叔丁基苯乙烯或甲基丙烯酸正丁酯或其组合。所述多级聚合物颗粒可用作不透明聚合物,其用于着色涂层调配物中以降低TiO2的负载量。所述颗粒呈现出优异的抗塌陷强度和异常低的干体积密度,并且不需要丙烯腈来实现这种所期望的性能组合。
Description
背景技术
本发明涉及用于制备多级聚合物颗粒的水分散体的方法,所述多级聚合物颗粒的水分散体可用于改善着色涂层调配物中的遮盖效率。
二氧化钛(TiO2)是因为其极高的折射率而选择用于涂料调配物的不透明化颜料;然而,TiO2的高成本已经促使研究人员研究在保持高不透明化(遮盖)效率的同时减少其负载量的方法。一个这种方法是已知作为不透明聚合物的高散射聚合物颜料的开发和商业化,已经发现其在较低颜料体积浓度(PVC)TiO2下保持遮盖效率。US6,020,435公开了含有酸官能化核的核-壳聚合物颗粒的水分散体的制备,其在使核中和后转化为不透明聚合物,并且随后用分散体涂布基材,从而允许水蒸发,以形成具有空心颗粒的膜。
不透明聚合物的效率提高主要来自两个因素:低干体积密度和抗塌陷强度:不幸的是,实现较低干体积密度以实现遮盖效率的进一步提高的努力降低了抗塌陷强度。这种相关性并不令人惊讶,因为低干体积密度与较大的核相关,因此在期望的粒度处与较大的核壳重量与重量比相关;结果是更容易塌陷的较薄壳。已经发现丙烯腈结合到中间或后中间聚合阶段——核阶段之后的一个阶段或多个阶段——导致形成具有较低干体积密度和可接受的抗塌陷强度下的不透明聚合物;然而,丙烯腈具有急性毒性,并且已经观察到使暴露的工人发生粘膜刺激、头痛、头晕和恶心。因此,制备不具有丙烯腈官能化的抗塌陷的低干体积密度聚合物颗粒是有利的。
发明内容
本发明通过提供一种用于制备多级聚合物颗粒的水分散体的方法应对本领域的需要,所述方法包括以下步骤:
a)在乳液聚合条件下,使核聚合物颗粒的水分散体与第一单体接触,以形成核/第一级聚合物颗粒的水分散体;以及
b)在乳液聚合条件下,使所述核/第一级聚合物颗粒的水分散体与第二单体接触,以形成所述水分散体多级聚合物颗粒;以及
c)用碱中和所述多级聚合物颗粒的水分散体;其中
所述核聚合物颗粒包括25重量%到60重量%的羧酸单体或其盐的结构单元、40重量%到75重量%的非离子烯键式不饱和单体的结构单元、以及至多总计15重量%的苯乙烯和高Tg疏水单体的结构单元;其中
所述高Tg疏水单体是选自由以下组成的组的一种或多种单体:甲基丙烯酸环己酯、甲基丙烯酸异冰片酯、甲基丙烯酸4-叔丁酯、叔丁基苯乙烯和甲基丙烯酸正丁酯;
所述第一单体包括5重量%到15重量%的羧酸单体或其盐;2)45重量%到55重量%的苯乙烯;3)37重量%到47重量%的甲基丙烯酸甲酯或所述高Tg疏水单体或其组合;并且
所述第二单体包括80重量%到99.9重量%的苯乙烯和0.1重量%到0.5重量%的多烯键式不饱和单体;其中,
所述核聚合物颗粒与所述第一单体和第二单体的总量的重量与重量比处于1:9到1:20的范围中;并且所述第一单体与所述第二单体的重量与重量比处于1:3到1:8的范围中;
条件是按所述核/第一级聚合物颗粒的重量计,所述核/第一级聚合物颗粒包括2重量%到15重量%的所述高Tg疏水单体的结构单元。
本发明的方法通过提供一种用于制备不透明聚合物的方法来满足需要,所述不透明聚合物具有优异的抗塌陷强度和异常低的干体积密度,而不具有丙烯腈。
具体实施方式
本发明是一种用于制备多级聚合物颗粒的水分散体的方法,其包括以下步骤:
a)在乳液聚合条件下,使核聚合物颗粒的水分散体与第一单体接触,以形成核/第一级聚合物颗粒的水分散体;以及
b)在乳液聚合条件下,使所述核/第一级聚合物颗粒的水分散体与第二单体接触,以形成所述水分散体多级聚合物颗粒;以及
c)用碱中和所述多级聚合物颗粒的水分散体;其中
所述核聚合物颗粒包括25重量%到60重量%的羧酸单体或其盐的结构单元、40重量%到75重量%的非离子烯键式不饱和单体的结构单元、以及至多总计15重量%的苯乙烯和高Tg疏水单体的结构单元;其中
所述高Tg疏水单体是选自由以下组成的组的一种或多种单体:甲基丙烯酸环己酯、甲基丙烯酸异冰片酯、甲基丙烯酸4-叔丁酯、叔丁基苯乙烯和甲基丙烯酸正丁酯;
所述第一单体包括5重量%到15重量%的羧酸单体或其盐;2)45重量%到55重量%的苯乙烯;3)37重量%到47重量%的甲基丙烯酸甲酯或所述高Tg疏水单体或其组合;并且
所述第二单体包括80重量%到99.9重量%的苯乙烯和0.1重量%到0.5重量%的多烯键式不饱和单体;其中,
所述核聚合物颗粒与所述第一单体和第二单体的总量的重量与重量比处于1:9到1:20的范围中;并且所述第一单体与所述第二单体的重量与重量比处于1:3到1:8的范围中;
条件是按所述核/第一级聚合物颗粒的重量计,所述核/第一级聚合物颗粒包括2重量%到15重量%的所述高Tg疏水单体的结构单元。
通过本发明的方法制备的多级聚合物颗粒具有核-壳形态。核可以通过单级或多级方法生产,优选地在如正十二烷基硫醇或巯基乙醇等链转移剂的存在下生产。核也可以从种子过程制备。制备核的优选方法在US6,020,435中描述。
如本文所使用的,术语“结构单元”是指在聚合之后引述单体的剩余部分。例如,甲基丙烯酸甲酯的结构单元如下示出:
甲基丙烯酸甲酯的结构单元
优选地,按第一单体的重量计,核聚合物颗粒包括30重量%、更优选地35重量%、以及最优选地38重量%到优选地50重量%、更优选地到45重量%、以及最优选地到42重量%的羧酸单体或其盐的结构单元。
核聚合物颗粒还优选地包括50重量%、更优选地55重量%、以及最优选地58重量%到优选地70重量%、更优选地到65重量%、以及最优选地到62重量%的非离子烯键式不饱和单体的结构单元。
核聚合物颗粒优选地包括5重量%到10重量%的苯乙烯和/或高Tg疏水单体的结构单元,所述疏水单体选自由以下组成的组:甲基丙烯酸环己酯、甲基丙烯酸异冰片酯、甲基丙烯酸4-叔丁酯、叔丁基苯乙烯以及甲基丙烯酸正丁酯。术语“高Tg单体”是指形成在25℃下不成膜的均聚物的单体。在一个优选实施例中,按核聚合物颗粒的重量计,核聚合物颗粒包括5重量%、更优选地6重量%到10重量%的高Tg疏水单体的结构单元。在另一个实施例中,按核的重量计,核包括小于10重量%、更优选地小于5重量%、以及最优选地小于1重量%的苯乙烯的结构单元。
羧酸官能化单体的实例包含甲基丙烯酸、丙烯酸以及衣康酸,优选丙烯酸和甲基丙烯酸。非离子烯键式不饱和单体的实例包含C1-C10丙烯酸烷基酯和甲基丙烯酸酯,如甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯以及2-丙烯酸乙基己酯;以及苯乙烯。甲基丙烯酸甲酯和甲基丙烯酸丁酯是用于制备第一相的优选非离子烯键式不饱和单体。
使用BI-90Plus Brookhaven粒子分析器通过光散射测量,核聚合物颗粒的平均粒度优选地处于80nm到150nm的范围内。
第一单体优选地包括6重量%、更优选地7重量%到12重量%、更优选地到9重量%的羧酸单体的结构单元,优选地甲基丙烯酸或丙烯酸。第二单体优选地包括83重量%到91重量%的苯乙烯;第二单体进一步优选地包括8重量%到12重量%的甲基丙烯酸甲酯;优选地0.5重量%到4重量%的羧酸单体;并且优选地0.1重量%到0.4重量%的多烯键式不饱和单体,如二乙烯基苯或甲基丙烯酸烯丙酯。在另一个实施例中,按第一单体的重量计,第一单体包括5重量%到15重量%的高Tg疏水单体的结构单元。在另一个实施例中,按第一单体的重量计,第一单体包括小于10重量%、更优选地小于5重量%、以及最优选地小于1重量%的苯乙烯的结构单元。
核聚合物颗粒与第一单体和第二单体的总量的重量与重量比优选地处于1:11、更优选地1:12到1:18、以及更优选地到1:16的范围中;并且第一单体与第二单体的重量与重量比优选地处于1:4、更优选地1:5到优选地1:7的范围中。
多级聚合物颗粒优选地分三级由第一相聚合物颗粒的水分散体制备。在优选方法中,将第一单体以包括甲基丙烯酸、甲基丙烯酸甲酯和苯乙烯的第一单体乳液(ME 1)形式加入到含有固体含量处于20重量%、更优选地25重量%到40重量%、更优选地到35重量%的范围中的核聚合物颗粒的水分散体的釜中,并且在乳液聚合条件下共聚,以形成核/第一级(也被称为核/粘结层)聚合物颗粒的分散体。在一个实施例中,核聚合物颗粒包括5重量%、更优选地6重量%到15重量%、以及更优选地到10重量%的疏水高Tg单体的结构单元。ME 1优选地包括,按ME 1单体的重量计,6重量%、更优选地7重量%到12重量%、以及更优选地到9重量%的甲基丙烯酸或丙烯酸;按ME 1单体的重量计,优选地48重量%到52重量%的苯乙烯;以及按ME 1单体的重量计,优选地20重量%到40重量%的甲基丙烯酸甲酯。在一个实施例中,ME 1包括0重量%的疏水高Tg单体;在另一个实施例中,按ME 1单体的重量计,ME 1包括2重量%、以及更优选地4重量%到12重量%、以及更优选地到10重量%的疏水高Tg单体。核聚合物颗粒或粘结层或两者包括高Tg疏水单体的结构单元。ME 1与核的重量与重量比优选地处于0.5:1、更优选地1:1到4:1、以及更优选地到3:1的范围中。
第二单体优选地在如下两级(指定为ME 2A和ME 2B)中与核/第一级聚合物颗粒的分散体接触:在完成向釜中加入ME 1后,在乳液聚合条件下将包括78重量%到86.5重量%的苯乙烯、12重量%到18.5重量%的甲基丙烯酸甲酯、1重量%到4重量%的甲基丙烯酸或丙烯酸以及0.1重量%到0.6重量%的二乙烯基苯的甲基丙烯酸烯丙酯的第二单体乳液(ME2A)加入到釜中。ME 2A还优选地包含0.2重量%到0.8重量%的亚麻籽油脂肪酸。ME 2A与ME1的重量与重量比优选地处于3.5:1、更优选地4:1、以及最优选地4.5:1到6:1、更优选地到5.5:1、以及最优选地到5:1的范围中。
在~15分钟的合适保持时间后,将含有苯乙烯和4-羟基TEMPO的第三单体乳液(ME2B)进给到反应器中,然后加入热的去离子水和中和量的碱,如NH4OH,或碱金属氢氧化物,如浓NaOH。用叔丁基氢过氧化氢(t-BHP)和异抗坏血酸(IAA)有利地追捕分散体,并且过滤内容物以除去任何凝结物。ME 2B与ME 2A的重量与重量比优选地处于0.1:1、更优选地0.15:1到0.5:1、更优选地到0.3:1、以及最优选地到0.25:1的范围中。
因此,在本发明的优选方面,第二单体在乳液聚合条件下分两级加入:在第一级中,按第二单体A的重量计,包括78重量%到86.5重量%的苯乙烯、12重量%到18.5重量%的甲基丙烯酸甲酯、1重量%到4重量%的甲基丙烯酸或丙烯酸、以及0.1重量%到0.6重量%的多烯键式不饱和单体的第二单体A与核/第一级聚合物颗粒的水分散体在乳液聚合条件下接触,以形成多级聚合物颗粒的中间分散体;然后,按第二单体B的重量计,包括优选地至少98重量%、优选地100重量%的苯乙烯的第二单体B与多级聚合物颗粒的中间分散体接触,以形成最终的多级聚合物颗粒的水分散体。第二单体A与第二单体B的重量与重量比处于3:1、更优选地3.5:1、更优选地4:1、以及最优选地4.5:1到6:1、更优选地到5.5:1、以及最优选地到5:1的范围中。
优选地,使用BI-90Plus Brookhaven粒子分析器通过光散射测量的中和的多级聚合物颗粒的平均粒度处于150nm、更优选地200nm、最优选地350nm;到600nm、更优选地到500nm、最优选地到450nm的范围中。多级聚合物颗粒的水分散体的固体含量优选地处于10重量%到35重量%的范围中。
多级聚合物颗粒的水分散体可用作不透明化聚合物添加剂,其允许减少涂料调配物中TiO2的负载量。当含有这些不透明化聚合物添加剂的调配物作为涂层涂覆到基材上并且使其干燥时,形成了干体积密度处于0.50g/cc到0.55g/cc范围中的抗塌陷不透明聚合物。迄今为止,只有在第二相中包含丙烯腈才能实现具有如此低水平的干体积密度的抗塌陷不透明聚合物;然而,令人惊讶地发现,不再需要丙烯腈以及甲基丙烯腈、丙烯酰胺和甲基丙烯酰胺来实现迄今为止仅通过包含这些难以处理的单体就可实现的性能。因此,按第二相的重量计,多级聚合物颗粒的第二相优选地包括小于10重量%、更优选地小于1重量%、更优选地小于0.1重量%、以及最优选地0的丙烯腈、甲基丙烯腈、丙烯酰胺和甲基丙烯酰胺的结构单元。
本发明的多级聚合物颗粒的水分散体可用作涂料调配物中的补充不透明化颜料。另一方面,本发明是一种着色水基涂层组合物,其包括多级聚合物颗粒的分散体、流变改性剂、粘合剂,TiO2和选自由以下组成的组的至少一种添加剂:表面活性剂、消泡剂、灭微生物剂、分散剂、聚结剂和中和剂。
S/Mil测量
Kubelka-Munk散射系数(S/Mil)
散射系数(S/Mil)是多级聚合物颗粒的水分散体的不透明度的量度。将分散体样品与RHOPLEXTMAC-264乳液聚合物(AC-264,陶氏化学公司(The Dow Chemical Company)或其附属公司的商标)以15%水分散体/85%AC-264的重量与重量比,在固体基质上共混。将7密耳共混物的湿膜拉在一片黑色乙烯基上方,用艾姆斯计(Ames Gauge)测量四个小的限定区域中所述乙烯基的厚度。将膜在低相对湿度(<40%R.H.)下干燥2小时。通过Gardner仪器反射计在四个限定区域上方测量干膜的反射率。还使用艾姆斯计在同一限定区域上方确定干膜的厚度。计算限定区域中的每一个限定区域的散射系数:
R=反射率
T=以密耳为单位的膜厚度
然后对四个S/Mil测量值取平均值,以获得膜的S/Mil。
塌陷性
塌陷性指示分散的多级聚合物颗粒抵抗作用在内部微孔的壁上的干燥力的能力。当湿度高时,这些力最大,其导致颗粒缓慢干燥。使用与用于确定上述S/Mil的基本上相同的程序确定塌陷性,除了第二水分减少是在85%R.H.下干燥过夜,然后在<40%R.H.下干燥1小时。
实例
如US6,020,435中所述,进行核的水分散体的制备。表1展示了用于制备核的水分散体的单体和相对量,以及通过Brookhaven BI 90粒度分析器测量的核颗粒的固体含量和平均粒度。MMA是指甲基丙烯酸甲酯;MAA是指甲基丙烯酸;CHMA是指甲基丙烯酸环己酯;t-BuSty是指叔丁基苯乙烯;Sty是指苯乙烯;t-BuMA是指甲基丙烯酸叔丁酯;t-BuMA是指甲基丙烯酸叔丁酯。
此外,术语粘结涂层用于描述由ME 1中的单体形成的聚合物。
表1——核的单体分布、粒度和固体含量
中间物实例编号 | 单体分布 | 粒度 | 固体% |
1 | 66MMA/34MAA | 140nm | 32.1% |
2 | 62MMA/34MAA/4CHMA | 140nm | 32.1% |
3 | 58MMA/34MAA/8CHMA | 138nm | 32.1% |
4 | 56MMA/34MAA/10t-BuSty | 141nm | 32.4% |
5 | 56MMA/10Sty/34MAA | 135nm | 31.9% |
6 | 56MMA/10t-BuMA/34MAA | 140nm | 31.6% |
7 | 55MMA/10BMA/35MAA | 140nm | 31.7% |
8 | 56MMA/8IBOMA/34MAA | 140nm | 31.7% |
对比实例1——在核或ME 1中不用疏水高Tg单体的聚合物颗粒的水分散体的制备
将去离子水(800g)加入配备有桨式搅拌器、温度计、氮气入口和回流冷凝器的5L4颈圆底烧瓶(釜)中;在N2下将釜加热到89℃,此时加入过硫酸钠(3.2g)溶解的去离子水(30g),然后立即加入中间物实例1的核(186.9g)。将通过混合去离子水(60.0g)、十二烷基硫酸钠(SDS,4.0g,23%活性)、苯乙烯(60.0g)、MMA(50.4g)以及MAA(9.6g)制备的单体乳液(ME 1)以3.0g/min的速率在77-79℃的温度下加入到釜中。在完成加入ME 1后,将通过混合去离子水(187.0g)、SDS(8.0g,23%活性)、苯乙烯(491.4g)、MMA(72.0g)、MAA(10.8g)、亚麻子油脂肪酸(LOFA3.6g)以及甲基丙烯酸烯丙酯(ALMA1.80g)制备的第二单体乳液(ME 2)以10g/m的速率进给到反应器15分钟,在此期间允许温度升高到84℃。15分钟后,ME 2的进料速率增加到20g/min,并且将溶解在去离子水(62.0g)中的过硫酸钠(0.75g)的单独混合物以1.5g/min的速率共进给到反应器。在ME 2进料过程期间,允许反应混合物的温度增加到92-93℃。在ME 2的加入和共进给完成后,将0.1%FeSO4.7H2O(20.0g)/1%VERSENETM螯合剂(2.0g,陶氏化学公司或其附属公司的商标)的混合物加入到釜中;将温度在~92℃下保持15分钟,在所述时间后,将通过混合去离子水(46g)、SDS(1.7g)、苯乙烯(144.0g)以及4-羟基-2,2,6,6-四甲基哌啶-1-氧基(4-羟基TEMPO,3.0g)制备的第三单体乳液(ME 3)以40g/min的速率进给到釜。在ME 3的加入完成后,将热的去离子水(300g)加入到釜中,然后在10分钟内加入50%氢氧化钠(26.6g)和热水(450g)的混合物。然后,反应混合物在80-85℃的温度下保持5分钟,在所述时间后,将t-BHP(1.2g)和去离子水(25g)的混合物加入到釜中。然后在25分钟内将异抗坏血酸(IAA,0.65g)和去离子水(50g)的混合物进给到釜。在IAA共进给完成后,将釜冷却到室温,并且过滤内容物以除去形成的任何凝结物。最终乳胶的固体含量为28.5%、pH为8.6,并且粒度为427nm。计算出此聚合物的干密度为0.517g/mL。低RHS/Mil为1.34,高RH S/Mil为0.97,并且塌陷%为28%。
实例1——在ME 1中用CHMA制备聚合物颗粒的水分散体
除了使用中间物实例1的核(188.1g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(44.4g)、MAA(9.6g)和CHMA(6.0g)。最终乳胶的固体含量为28.5%、pH为8.9,并且粒度为384nm。计算出此聚合物的干密度为0.533g/cc。低RH S/Mil为1.31,高RH S/Mil为1.23,并且塌陷%为6%。
实例2——在ME 1中用CHMA制备聚合物颗粒的水分散体
除了使用中间物实例1的核(188.7g)之外,随后进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(26.4g)、MAA(9.6g)和CHMA(24.0g)。最终乳胶的固体含量为28.8%、pH为8.9,并且粒度为415nm。计算出此聚合物的干密度为0.541g/cc。低RH S/Mil为1.28,高RH S/Mil为1.22,并且塌陷%为5%。
实例3——在核中用CHMA制备聚合物颗粒的水分散体
除了使用中间物实例3的核(186.9g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(26.4g)、MAA(9.6g)和CHMA(12.0g)。最终乳胶的固体含量为28.2%、pH为8.9,并且粒度为412nm。计算出此聚合物的干密度为0.541g/cc。低RH S/Mil为1.32,高RH S/Mil为1.32,并且塌陷%为0%。
实例4——在核中用叔丁基苯乙烯制备聚合物颗粒的水分散体
除了如中间物实例4中所述制备核(185.2g)之外,随后进行对比实例1的程序。最终乳胶的固体含量为28.4%、pH为8.75,并且粒度为409nm。计算出此聚合物的干密度为0.541g/cc。低RH S/Mil为1.40,高RH S/Mil为1.28,并且塌陷%为8.5%。
实例5——在核和粘结涂层中用叔丁基苯乙烯制备聚合物颗粒的水分散体
除了使用中间物实例4的核(185.2g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(44.4g)、MAA(9.6g)、t-BuSty(6.4g)。最终乳胶的固体含量为28.4%、pH为8.85,并且粒度为403nm。计算出此聚合物的干密度为0.543g/cc。低RH S/Mil为1.40,高RH S/Mil为1.33,并且塌陷%为5%。
对比实例2——在核中用苯乙烯制备聚合物颗粒的水分散体
除了如中间物实例5中所述制备核(188.1g)之外,随后进行对比实例1的程序。最终乳胶的固体含量为28.5%、pH为8.7,并且粒度为403nm。计算出此聚合物的干密度为0.539g/cc。低RH S/Mil为1.40,高RH S/Mil为1.19,并且塌陷%为15.0%。
实例6——在核中用苯乙烯并且在粘结涂层中用CHMA制备聚合物颗粒的水分散体
除了使用中间物实例5的核(186.3g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(38.4g)、MAA(9.6g)以及CHMA(12.0g)。最终乳胶的固体含量为28.4%、pH为8.5,并且粒度为405nm。计算出此聚合物的干密度为0.536g/cc。低RH S/Mil为1.38,高RH S/Mil为1.33,并且塌陷%为3.5%。
实例7——在核和粘结涂层中用甲基丙烯酸叔丁酯制备聚合物颗粒的水分散体
除了使用中间物实例6的核(189.9g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(38.4g)、MAA(9.6g)以及t-BuMA(12.0g)。最终乳胶的固体含量为28.6%、pH为8.5,并且粒度为437nm。计算出此聚合物的干密度为0.543g/cc。低RH S/Mil为1.35,高RH S/Mil为1.25,并且塌陷%为7.5%。
实例8——在核中用甲基丙烯酸叔丁酯并且在粘结涂层中用甲基丙烯酸环己酯制备聚合物颗粒的水分散体
除了使用中间物实例6的核(189.9g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(44.4g)、MAA(9.6g)以及CHMA(6.0g)。最终乳胶的固体含量为28.6%、pH为8.4,并且粒度为424nm。计算出此聚合物的干密度为0.531g/cc。低RH S/Mil为1.40,高RH S/Mil为1.31,并且塌陷%为6.5%。
实例9——在核和粘结涂层中用甲基丙烯酸叔丁酯制备聚合物颗粒的水分散体
除了使用中间物实例7的核(189.3g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(38.4g)、MAA(9.6g)以及t-BMA(12.0g)。最终乳胶的固体含量为28.8%、pH为8.5,并且粒度为427nm。计算出此聚合物的干密度为0.569g/cc。低RH S/Mil为1.29,高RH S/Mil为1.22,并且塌陷%为5.5%。
实例10——在核中用甲基丙烯酸异冰片酯制备聚合物颗粒的水分散体
除了如中间物实例8中所述制备核(186.3g)之外,进行对比实例1的程序。最终乳胶的固体含量为28.5%、pH为8.8,并且粒度为424nm。计算出此聚合物的干密度为0.540g/cc。低RH S/Mil为1.31,高RH S/Mil为1.21,并且塌陷%为7.5%。
实例11——在粘结涂层中用甲基丙烯酸异冰片酯制备聚合物颗粒的水分散体
除了使用中间物实例1的核(188.7g)之外,进行对比实例1的程序;并且ME 1单体为苯乙烯(60.0g)、MMA(38.4g)、MAA(9.6g)以及IBOMA(12.0g)。最终乳胶的固体含量为28.6%、pH为8.9,并且粒度为413nm。计算出此聚合物的干密度为0.539g/cc。低RH S/Mil为1.27,高RH S/Mil为1.23,并且塌陷%为3.0%。
数据表明,可以以小于10%的抗塌陷强度制备干体积密度小于0.55g/cc的多级聚合物颗粒的分散体,其在不透明聚合物领域中被认为是可接受的。
Claims (9)
1. 一种用于制备多级聚合物颗粒的水分散体的方法,其包括以下步骤:
a)在乳液聚合条件下,使核聚合物颗粒的水分散体与第一单体接触,以形成核/第一级聚合物颗粒的水分散体;以及
b)在乳液聚合条件下,使所述核/第一级聚合物颗粒的水分散体与第二单体接触,以形成所述水分散体多级聚合物颗粒;以及
c)用碱中和所述多级聚合物颗粒的水分散体;其中
所述核聚合物颗粒包括25重量%到60重量%的羧酸单体或其盐的结构单元、40重量%到75重量%的非离子烯键式不饱和单体的结构单元、以及至多总计15重量%的苯乙烯和高Tg疏水单体的结构单元;其中
所述高Tg疏水单体是选自由以下组成的组的一种或多种单体:甲基丙烯酸环己酯、甲基丙烯酸异冰片酯、甲基丙烯酸4-叔丁酯、叔丁基苯乙烯和甲基丙烯酸正丁酯;
所述第一单体包括5重量%到15重量%的羧酸单体或其盐;2)45重量%到55重量%的苯乙烯;3)37重量%到47重量%的甲基丙烯酸甲酯或所述高Tg疏水单体或其组合;并且
所述第二单体包括80重量%到99.9重量%的苯乙烯和0.1重量%到0.5重量%的多烯键式不饱和单体;其中,
所述核聚合物颗粒与所述第一单体和第二单体的总量的重量与重量比处于1:9到1:20的范围中;并且所述第一单体与所述第二单体的重量与重量比处于1:3到1:8的范围中;
条件是按所述核/第一级聚合物颗粒的重量计,所述核/第一级聚合物颗粒包括2重量%到15重量%的所述高Tg疏水单体的结构单元。
2. 根据权利要求1所述的方法,其中所述核聚合物颗粒与所述第一单体和第二单体的总量的重量与重量比处于1:11到1:18的范围中;并且其中所述第一单体与所述第二单体的重量与重量比处于1:4到1:7的范围中。
3. 根据权利要求2所述的方法,其中
a)按所述核聚合物颗粒的重量计,所述核聚合物颗粒包含25重量%到50重量%的羧酸单体或其盐、40重量%到70重量%的非离子烯键式不饱和单体;以及5重量%到10重量%的所述高Tg疏水单体;其中
b)按所述第一单体的重量计,所述第一单体包括6重量%到12重量%的羧酸单体或其盐;并且其中
c)按所述第二单体的重量计,所述第二单体包括83重量%到91重量%的苯乙烯;8重量%到12重量%的甲基丙烯酸甲酯;0.5重量%到4重量%的甲基丙烯酸或丙烯酸;以及0.1重量%到0.4重量%的多烯键式不饱和单体。
4. 根据权利要求2所述的方法,其中
a)按所述核聚合物颗粒的重量计,所述核聚合物颗粒包含30重量%到50重量%的羧酸单体或其盐、以及50重量%到70重量%的非离子烯键式不饱和单体;其中
b)按所述第一单体的重量计,所述第一单体包括6重量%到12重量%的羧酸单体或其盐、以及5重量%到15重量%的所述高Tg疏水单体;并且其中
c)按所述第二单体的重量计,所述第二单体包括83重量%到91重量%的苯乙烯;8重量%到12重量%的甲基丙烯酸甲酯;0.5重量%到4重量%的甲基丙烯酸或丙烯酸;以及0.1重量%到0.4重量%的多烯键式不饱和单体。
5. 根据权利要求2所述的方法,其中
a)按所述核聚合物颗粒的重量计,所述核聚合物颗粒包括25重量%到50重量%的羧酸单体或其盐、以及40重量%到70重量%的非离子烯键式不饱和单体、以及5重量%到10重量%的所述高Tg疏水单体;其中
b)按所述第一单体的重量计,所述第一单体包括6重量%到12重量%的羧酸单体或其盐、以及5重量%到15重量%的所述高Tg疏水单体;其中
c)按所述第二单体的重量计,所述第二单体包括83重量%到91重量%的苯乙烯;8重量%到12重量%的甲基丙烯酸甲酯;0.5重量%到4重量%的甲基丙烯酸或丙烯酸;以及0.1重量%到0.4重量%的多烯键式不饱和单体。
6. 根据权利要求5所述的方法,其中在乳液聚合条件下,所述第二单体在第一级和第二级中与核/第一级聚合物颗粒的所述分散体接触,其中
a)按所述第一级第二单体的重量计,所述第一级第二单体包括78重量%到86.5重量%的苯乙烯、12重量%到18.5重量%的甲基丙烯酸甲酯、1重量%到4重量%的甲基丙烯酸或丙烯酸、以及0.1重量%到0.4重量%的二乙烯基苯的甲基丙烯酸烯丙酯,都与所述接触;并且
b)按所述第二级第二单体的重量计,所述第二级第二单体包括大于98重量%的苯乙烯;
其中第一级第二单体与第二级第二单体的重量与重量比处于3:1到6:1的范围中。
7.根据权利要求2所述的方法,其中按所述第一单体和第二单体的重量计,所述第一单体和第二单体包括小于1重量%的丙烯腈、甲基丙烯腈、丙烯酰胺和甲基丙烯酰胺的结构单元。
8.根据权利要求7所述的方法,其中按所述第一单体和第二单体的重量计,所述第一单体和第二单体包括小于0.1重量%的丙烯腈、甲基丙烯腈、丙烯酰胺和甲基丙烯酰胺。
9.根据权利要求1所述的方法,其进一步包括使所述多级聚合物颗粒的水分散体与流变改性剂、粘合剂、TiO2和选自由以下组成的组的至少一种添加剂接触:表面活性剂、消泡剂、灭微生物剂、分散剂、聚结剂和中和剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201862726631P | 2018-09-04 | 2018-09-04 | |
US62/726631 | 2018-09-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110872366A CN110872366A (zh) | 2020-03-10 |
CN110872366B true CN110872366B (zh) | 2023-10-20 |
Family
ID=67850976
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910719806.9A Active CN110872366B (zh) | 2018-09-04 | 2019-08-06 | 用于制备多级聚合物颗粒的水分散体的方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10919999B2 (zh) |
EP (1) | EP3620476B1 (zh) |
KR (1) | KR20200027421A (zh) |
CN (1) | CN110872366B (zh) |
AU (1) | AU2019219735A1 (zh) |
BR (1) | BR102019017218A2 (zh) |
CA (1) | CA3053813A1 (zh) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2019204505C1 (en) * | 2018-07-19 | 2023-10-26 | Rohm And Haas Company | Process for preparing an aqueous dispersion of multistage polymer particles |
WO2021225769A1 (en) | 2020-05-08 | 2021-11-11 | Rohm And Haas Company | Aqueous dispersion opacifying pigment particles |
CN112409530B (zh) * | 2020-11-18 | 2022-12-27 | 广东巴德富新材料有限公司 | 一种用于不透明聚合物的种子乳液及其制备方法 |
WO2022115137A1 (en) * | 2020-11-30 | 2022-06-02 | Emission Inc. | Fluorescent microspheres evenly coated with magnetic particles and methods of use |
CN117136203A (zh) * | 2021-04-01 | 2023-11-28 | 巴斯夫欧洲公司 | 空心聚合物颗粒的水性聚合物分散体 |
AU2022390021A1 (en) * | 2021-11-22 | 2024-06-20 | Rohm And Haas Company | Aqueous dispersion of opacifying pigment-binder hybrid polymer particles |
WO2023091641A1 (en) | 2021-11-22 | 2023-05-25 | Rohm And Haas Company | Method for preparing opacifying pigment-binder hybrid polymer particles |
WO2023192105A1 (en) | 2022-03-29 | 2023-10-05 | Rohm And Haas Company | Aqueous dispersion of biocide-free organic opacifying pigment particles |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101624429A (zh) * | 2008-07-08 | 2010-01-13 | 罗门哈斯公司 | 芯-壳聚合物颗粒 |
CN103596999A (zh) * | 2011-03-21 | 2014-02-19 | 土耳其有机化工公司 | 含核鞘壳聚合物颗粒的乳浊液的制备方法 |
WO2016095197A1 (en) * | 2014-12-19 | 2016-06-23 | Dow Global Technologies Llc | Aqueous polymer dispersion and preparation method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR940007353B1 (ko) * | 1991-12-13 | 1994-08-16 | 고려화학 주식회사 | 코아-쉘 유화 중합체의 제조방법 및 이를 함유하는 분산액 |
US6020435A (en) | 1997-11-05 | 2000-02-01 | Rohm And Haas Company | Process for preparing polymer core shell type emulsions and polymers formed therefrom |
US6673451B2 (en) * | 2000-10-12 | 2004-01-06 | Rohn And Haas Company | Process for forming an aqueous polymeric dispersion |
US8895658B2 (en) * | 2012-12-18 | 2014-11-25 | Columbia Insurance Company | Grafted pigment dispersing polymeric additive and paint employing the same with improved hiding |
-
2019
- 2019-08-06 CN CN201910719806.9A patent/CN110872366B/zh active Active
- 2019-08-19 BR BR102019017218-5A patent/BR102019017218A2/pt active Search and Examination
- 2019-08-20 AU AU2019219735A patent/AU2019219735A1/en active Pending
- 2019-08-21 KR KR1020190102175A patent/KR20200027421A/ko not_active Application Discontinuation
- 2019-08-30 US US16/556,607 patent/US10919999B2/en active Active
- 2019-09-03 EP EP19195252.2A patent/EP3620476B1/en active Active
- 2019-09-03 CA CA3053813A patent/CA3053813A1/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101624429A (zh) * | 2008-07-08 | 2010-01-13 | 罗门哈斯公司 | 芯-壳聚合物颗粒 |
CN103596999A (zh) * | 2011-03-21 | 2014-02-19 | 土耳其有机化工公司 | 含核鞘壳聚合物颗粒的乳浊液的制备方法 |
WO2016095197A1 (en) * | 2014-12-19 | 2016-06-23 | Dow Global Technologies Llc | Aqueous polymer dispersion and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
EP3620476A1 (en) | 2020-03-11 |
EP3620476B1 (en) | 2023-12-27 |
CN110872366A (zh) | 2020-03-10 |
US20200071439A1 (en) | 2020-03-05 |
US10919999B2 (en) | 2021-02-16 |
KR20200027421A (ko) | 2020-03-12 |
AU2019219735A1 (en) | 2020-03-19 |
BR102019017218A2 (pt) | 2020-03-17 |
CA3053813A1 (en) | 2020-03-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110872366B (zh) | 用于制备多级聚合物颗粒的水分散体的方法 | |
CN110872367B (zh) | 多级聚合物颗粒的水分散体 | |
CA2855046C (en) | Bimodal adsorbing latex | |
US9303161B2 (en) | Dispersion of adsorbing emulsion polymer particles | |
DE60303485T2 (de) | Wässrige Beschichtungszusammensetzung auf Acrylbasis | |
KR970009356B1 (ko) | 음이온종(種) 추출 시스템을 포함한 수성 도포 조성물 및 이에 사용되는 수성 부산물 | |
EP0073529A2 (en) | Preparation of sequential polymers and use thereof in coating compositions and as thickening agents | |
CN105646759A (zh) | 磷酸官能化不透明聚合物 | |
GB2194543A (en) | Sequentially-produced polymer particles, aqueous dispersions thereof, processes for preparing them, and uses thereof | |
AU2020369865A1 (en) | Aqueous composition of organic polymeric microspheres, binder particles, and ion exchange resin | |
US10519281B2 (en) | Aqueous dispersion of fluoroalkylated polymer particles with acorn morphology | |
BR102019019257A2 (pt) | Balanceador dinâmico com um acionamento de motor sem armação | |
JPH0655875B2 (ja) | アニオン性アクリルラテックス組成物の製造法 | |
KR101057532B1 (ko) | 자동차용 수용성 상도 도료의 제조방법 | |
CN118234767A (zh) | 用于制备乳浊颜料-粘结剂杂化聚合物颗粒的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |