CN111234086A - High-solid-content low-viscosity redispersible vinyl acetate-acrylic emulsion powder and preparation method thereof - Google Patents
High-solid-content low-viscosity redispersible vinyl acetate-acrylic emulsion powder and preparation method thereof Download PDFInfo
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- CN111234086A CN111234086A CN202010051251.8A CN202010051251A CN111234086A CN 111234086 A CN111234086 A CN 111234086A CN 202010051251 A CN202010051251 A CN 202010051251A CN 111234086 A CN111234086 A CN 111234086A
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- Prior art keywords
- vinyl acetate
- acrylic emulsion
- initiator
- formula amount
- protective colloid
- Prior art date
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 103
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 103
- 239000000839 emulsion Substances 0.000 title claims abstract description 81
- 239000000843 powder Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 76
- 239000000084 colloidal system Substances 0.000 claims abstract description 70
- 230000001681 protective effect Effects 0.000 claims abstract description 70
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000008234 soft water Substances 0.000 claims abstract description 42
- 239000012874 anionic emulsifier Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 35
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 239000004816 latex Substances 0.000 claims abstract description 28
- 229920000126 latex Polymers 0.000 claims abstract description 28
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 77
- 229910021389 graphene Inorganic materials 0.000 claims description 76
- 239000007864 aqueous solution Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 46
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- MFISPHKHJHQREG-UHFFFAOYSA-N trichloro(oct-7-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CCCCCCC=C MFISPHKHJHQREG-UHFFFAOYSA-N 0.000 claims description 18
- 229920001971 elastomer Polymers 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002472 Starch Polymers 0.000 claims description 13
- 239000001913 cellulose Substances 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000008107 starch Substances 0.000 claims description 13
- 235000019698 starch Nutrition 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 229920001038 ethylene copolymer Polymers 0.000 claims description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 7
- 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 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- BCSSWMSPHLKCMJ-UHFFFAOYSA-N 2-(hydroxymethyl)-n-methylprop-2-enamide Chemical compound CNC(=O)C(=C)CO BCSSWMSPHLKCMJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- -1 alkyl phenol sulfate Chemical compound 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229940044652 phenolsulfonate Drugs 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 238000010276 construction Methods 0.000 abstract description 4
- 238000004383 yellowing Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N 1-dodecanol group Chemical group C(CCCCCCCCCCC)O LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 239000005543 nano-size silicon particle Substances 0.000 description 6
- 230000010355 oscillation Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 5
- 229960000892 attapulgite Drugs 0.000 description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 229910052625 palygorskite Inorganic materials 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- QWGLNWHWBCINBS-UHFFFAOYSA-N 3-nonylphenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1 QWGLNWHWBCINBS-UHFFFAOYSA-N 0.000 description 4
- 229940029565 3-nonylphenol Drugs 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 4
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 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
- C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- 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
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—Compositions of 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a high-solid-content low-viscosity redispersible vinyl acetate emulsion powder and a preparation method thereof, wherein the emulsion powder product is prepared from a main monomer, a crosslinking monomer, an anionic emulsifier, a nonionic emulsifier, an initiator, a protective colloid, a pH regulator and soft water as raw materials, and has the advantages of low surface tension, excellent water resistance, good yellowing resistance, good acid and alkali resistance, high solid content and low viscosity in construction and cost. The invention combines the vinyl acetate-acrylic emulsion with the latex powder Vac/E commonly used at present to prepare a novel dispersible latex powder product, which has high solid content, low viscosity, great advantages in construction and cost, improved weather resistance and water resistance, and effectively improved impact resistance.
Description
Technical Field
The invention relates to redispersible vinyl acetate emulsion powder, and in particular relates to redispersible vinyl acetate emulsion powder with high solid content and low viscosity and a preparation method thereof. Belongs to the technical field of redispersible latex powder.
Background
According to statistics of relevant experts, in 2003, the global yield of the redispersible latex powder is 19 ten thousand tons, the redispersible latex powder is mainly used in Europe and North America, and the consumption of the Chinese market is less than 5000 tons. In 2007, the market consumption of the Chinese redispersible latex powder reaches 4-5 ten thousand tons. In 2010, the demand of domestic redispersible latex powder reaches 10 ten thousand tons. By 2018, according to incomplete statistics, the demand of the redispersible latex powder in China reaches 60 ten thousand tons.
The redispersible latex powder is prepared by carrying out spray drying on high molecular polymer emulsion, and aggregating together from the initial 2 mu m to form spherical particles of 80-120 mu m. Since the surface of the particles is coated with an inorganic, hard-structured powder, we have obtained a dry polymer powder. They are easily poured and bagged and stored in warehouses. When the powder is mixed with water, cement or gypsum-based mortar, it can be redispersed, and the elementary particles (2 μm) therein can be reformed into a state equivalent to the original latex, so it is called redispersible latex powder.
At present, the main redispersible rubber powder at home and abroad is vinyl acetate and ethylene copolymerized rubber powder (Vac/E). However, in view of the properties of the Vac/E emulsion, although it can play a role in improving leveling property, flexibility, adhesion, thixotropy and workability in mortar, the Vac/E emulsion has great defects in weather resistance, chemical resistance and water resistance, and the range of glass transition temperature of the Vac/E emulsion is too small, which limits the application range.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the redispersible latex powder with high solid content and low viscosity and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the vinyl acetate-acrylic emulsion is prepared from the following raw materials in parts by weight: 40-75 parts of vinyl acetate, 20-40 parts of 2-ethylhexyl acrylate, 2-15 parts of a crosslinking monomer, 0.1-1 part of an anionic emulsifier, 0.5-7.5 parts of a nonionic emulsifier, 0.5-1.5 parts of an initiator, 5-10 parts of a protective colloid, 0.2-0.4 part of a pH regulator and 80-140 parts of soft water; wherein the crosslinking monomer is selected from any one or more of vinyl unsaturated carboxylic acid, vinyl unsaturated amide, hydroxyethyl methacrylate, ethyl laurate and vinyl versatate.
Preferably, the vinyl unsaturated carboxylic acid is selected from any one or more of itaconic acid, acrylic acid, methacrylic acid or maleic anhydride; the vinyl unsaturated amide is selected from any one or more of acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide or methyl methylolacrylamide.
Preferably, the anionic emulsifier is selected from any one or more of alkylphenol sulfate, alkylphenol succinate or alkylphenol sulfonate; the nonionic emulsifier is selected from alkylphenol polyoxyethylene ether or fatty alcohol polyoxyethylene ether with the EO number of 7-10.
Preferably, the initiator is persulfate, and is selected from any one or more of ammonium persulfate, sodium persulfate and ammonium persulfate.
Preferably, the protective colloid is selected from any one or more of polyvinyl alcohol, cellulose or starch.
Preferably, the pH regulator is strong ammonia water with the mass concentration of 25-28%.
The preparation method of the vinyl acetate-acrylic emulsion comprises the following specific steps:
(1) adding 0.35-0.55 times of formula amount of soft water, 0.5-0.65 times of formula amount of anionic emulsifier, 0.5-0.65 times of formula amount of nonionic emulsifier, formula amount of protective colloid and pH regulator into a polymerization kettle, heating to 90 ℃, cooling to 80 ℃ after the protective colloid is completely dissolved, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 5-6 hours, keeping the temperature for reaction for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
Preferably, in the step (2), the preparation method of the aqueous initiator solution is as follows: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
Preferably, in the step (2), before the vinyl acetate and the 2-ethylhexyl acrylate are fed, a modification treatment is performed, and the specific method is as follows: firstly, uniformly stirring vinyl acetate and 2-ethylhexyl acrylate, then adding the organic modified doped graphene, and uniformly stirring; the dosage of the organic modified doped graphene is 0.005-0.008 times of the weight of vinyl acetate, and the organic modified doped graphene is obtained by carrying out silicon and phosphorus codoping and reduction on graphene oxide to obtain doped graphene and then carrying out modification treatment on the doped graphene oxide by using 7-octenyl trichlorosilane.
Further preferably, the preparation method of the doped graphene is as follows: adding nano silicon powder and pyrophosphoric acid into graphene oxide dispersion liquid, heating for 8-9 hours at 480-500 ℃ under the helium atmosphere and ultrasonic oscillation conditions, reducing, and performing post-treatment to obtain doped graphene; wherein the molar ratio of the nano silicon powder to the pyrophosphoric acid to the graphene oxide contained in the graphene oxide dispersion liquid is 0.01-0.02: 0.04-0.05: 1, adding graphene oxide into water with the weight being 8-10 times that of the graphene oxide, and carrying out ultrasonic oscillation for 30-40 minutes to obtain the graphene oxide dispersion liquid.
More preferably, the graphene oxide is prepared by adopting an improved Hummers method; the specific method for reduction is as follows: adding hydrazine hydrate, stirring and heating for 2-3 hours at the temperature of 60-80 ℃, and cooling to room temperature (25 ℃); the specific method of post-treatment is as follows: centrifuging, washing to neutrality, and vacuum drying; wherein the temperature of vacuum drying is 60 ℃, and the drying time is 24 hours.
Further preferably, the specific method for modifying the 7-octenyltrichlorosilane comprises the following steps: adding doped graphene into a mixture with a volume ratio of 1: 9, soaking the mixture of 7-octenyltrichlorosilane and toluene for 12 hours, and performing suction filtration to obtain the product; the mol ratio of the doped graphene to the 7-octenyl trichlorosilane is 1: 1.2 to 1.5.
The redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity is prepared by the vinyl acetate-acrylic emulsion.
The preparation method of the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity comprises the following steps of mixing vinyl acetate/ethylene copolymer rubber powder (Vac/E) and the vinyl acetate-acrylic emulsion according to a mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
Preferably, the dosage of the anti-caking agent and the dosage of the protective colloid aqueous solution are respectively 0.02-0.03 time and 20-30 times of the weight of the vinyl acetate/ethylene copolymerized rubber powder.
Preferably, the anti-caking agent is selected from any one or more of diatomite, aluminum silicate, talcum powder, attapulgite or kaolin.
Preferably, the protective colloid aqueous solution is obtained by adding the protective colloid into soft water with the weight of 50-80 times and uniformly dispersing by ultrasonic waves.
Further preferably, the protective colloid is selected from any one or more of polyvinyl alcohol, cellulose or starch.
The invention has the beneficial effects that:
the vinyl acetate-acrylic latex is prepared from the main monomer, the crosslinking monomer, the anionic emulsifier, the nonionic emulsifier, the initiator, the protective colloid, the pH regulator and soft water, and has the advantages of low surface tension, excellent water resistance, good yellowing resistance, good acid and alkali resistance, high solid content and low viscosity in construction and cost. The invention combines the vinyl acetate-acrylic emulsion with the latex powder Vac/E commonly used at present to prepare a novel dispersible latex powder product, which has high solid content, low viscosity, great advantages in construction and cost, improved weather resistance and water resistance, and effectively improved impact resistance.
In the preparation process of the vinyl acetate-acrylic emulsion, part of soft water, part of anionic emulsifier, part of nonionic emulsifier, protective colloid and pH regulator in the formula amount are mixed in a polymerization kettle and then are kept warm for standby; then adding the anionic emulsifier and the cationic emulsifier in the rest formula amount and vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and part of the initiator aqueous solution in the formula amount into an emulsifying kettle, and fully mixing to prepare a mixed solution; and finally, adding the rest initiator aqueous solution into the polymerization kettle, slightly stirring, dropwise adding the mixed solution, and preserving heat for reaction after dropwise adding to obtain a product. The dripping time is very critical, the dripping time is too short, a large amount of heat can be emitted after rapid reaction, the local temperature is too high, the system temperature is difficult to control, part of monomers directly escape, and part of monomers are lost; the dropping time is too long, partial reaction is sufficient in the dropping micro range, but the reaction is easy to crosslink into a net shape, and the product performance is influenced.
Before the vinyl acetate and the 2-ethylhexyl acrylate are fed, organic modified doped graphene is introduced for modification treatment, so that on one hand, the solid content is further improved, and on the other hand, the unique mechanical property, electronic effect and thermal property of the graphene are beneficial to further improving various properties of the emulsion. The atomic diameters of silicon and phosphorus are different from those of carbon. Silicon tends to form a regular tetrahedral structure, and a certain interval is formed between graphene molecules to prevent agglomeration of the graphene; phosphorus also tends to form regular tetrahedral structure, which is embedded with the silicon three-dimensional structure, and contributes to the improvement of the stability of doping. However, graphene is poor in solubility and difficult to uniformly disperse in the system, the applicant utilizes 7-octenyltrichlorosilane to organically modify the graphene, and double bonds in the graphene are also polymerized with main monomers, crosslinking monomers and the like in the subsequent polymerization reaction process, so that the compatibility problem is fundamentally solved, and the product performance is ensured.
Detailed Description
The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.
Example 1:
the vinyl acetate-acrylic emulsion is prepared from the following raw materials in parts by weight: 40 parts of vinyl acetate, 40 parts of acrylic acid-2-ethylhexyl ester, 2 parts of a crosslinking monomer, 1 part of an anionic emulsifier, 0.5 part of a nonionic emulsifier, 1.5 parts of an initiator, 5 parts of a protective colloid, 0.4 part of a pH regulator and 80 parts of soft water; wherein the crosslinking monomer is an ethylenically unsaturated carboxylic acid.
The vinyl unsaturated carboxylic acid is acrylic acid; the vinyl unsaturated amide is dimethylacrylamide.
The anionic emulsifier is sodium dodecyl sulfate; the nonionic emulsifier is lauryl alcohol polyoxyethylene ether with the EO number of 10.
The initiator is ammonium persulfate. The protective colloid is starch. The pH regulator is strong ammonia water with the mass concentration of 25%.
The preparation method of the vinyl acetate-acrylic emulsion comprises the following specific steps:
(1) adding 0.55 times of soft water, 0.5 times of anionic emulsifier, 0.65 times of nonionic emulsifier, protective colloid and pH regulator into a polymerization kettle, heating to 90 ℃, cooling to 80 ℃ when the protective colloid is completely dissolved, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 5 hours, keeping the temperature for reaction for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
In the step (2), the preparation method of the initiator aqueous solution comprises the following steps: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
The redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity is prepared by the vinyl acetate-acrylic emulsion.
The preparation method of the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity comprises the following steps of mixing vinyl acetate/ethylene copolymer rubber powder (Vac/E) and the vinyl acetate-acrylic emulsion according to a mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
The dosage of the anticaking agent and the dosage of the protective colloid aqueous solution are respectively 0.03 time and 20 times of the weight of the vinyl acetate/ethylene copolymerized rubber powder. The anti-caking agent is talcum powder. The protective colloid aqueous solution is obtained by adding protective colloid into soft water with the weight of 80 times and uniformly dispersing by ultrasonic waves. The protective colloid is starch.
Example 2:
the vinyl acetate-acrylic emulsion is prepared from the following raw materials in parts by weight: 75 parts of vinyl acetate, 20 parts of 2-ethylhexyl acrylate, 15 parts of a crosslinking monomer, 0.1 part of an anionic emulsifier, 7.5 parts of a nonionic emulsifier, 0.5 part of an initiator, 10 parts of a protective colloid, 0.2 part of a pH regulator and 140 parts of soft water; wherein the cross-linking monomer is prepared from the following components in a mass ratio of 1: 3 hydroxyethyl methacrylate and ethyl laurate.
The mass ratio of the vinyl unsaturated carboxylic acid is 1: 2 itaconic acid, methacrylic acid; the mass ratio of the vinyl unsaturated amide is 1: 3 acrylamide, methylolacrylamide.
The anionic emulsifier is prepared from the following components in a mass ratio of 1: 2 sodium dodecyl sulfate, sodium dodecyl benzene sulfonate; the mass ratio of the nonionic emulsifier is 1: nonylphenol polyoxyethylene ether with 7EO number of 3 and lauryl alcohol polyoxyethylene ether.
The initiator is prepared from the following components in a mass ratio of 1: 2 sodium persulfate and ammonium persulfate. The protective colloid is prepared from the following components in percentage by mass 1: 3 polyvinyl alcohol and cellulose. The pH regulator is strong ammonia water with the mass concentration of 28%.
The preparation method of the vinyl acetate-acrylic emulsion comprises the following specific steps:
(1) adding 0.35 times of soft water, 0.65 times of anionic emulsifier, 0.5 times of nonionic emulsifier, protective colloid and pH regulator into a polymerization kettle, heating to 90 deg.C, cooling to 80 deg.C, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 6 hours, keeping the temperature for reaction for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
In the step (2), the preparation method of the initiator aqueous solution comprises the following steps: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
The redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity is prepared by the vinyl acetate-acrylic emulsion.
The preparation method of the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity comprises the following steps of mixing vinyl acetate/ethylene copolymer rubber powder (Vac/E) and the vinyl acetate-acrylic emulsion according to a mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
The dosage of the anticaking agent and the protective colloid aqueous solution is respectively 0.02 time and 30 times of the weight of the vinyl acetate/ethylene copolymerized rubber powder. The anti-caking agent is prepared from the following components in a mass ratio of 1: 2 diatomaceous earth, kaolin. The protective colloid aqueous solution is obtained by adding protective colloid into soft water with the weight of 50 times and uniformly dispersing by ultrasonic waves. The protective colloid is prepared from the following components in percentage by mass 1: 3 polyvinyl alcohol and cellulose.
Example 3:
the vinyl acetate-acrylic emulsion is prepared from the following raw materials in parts by weight: 55 parts of vinyl acetate, 30 parts of 2-ethylhexyl acrylate, 10 parts of a crosslinking monomer, 0.7 part of an anionic emulsifier, 3.5 parts of a nonionic emulsifier, 1 part of an initiator, 8 parts of a protective colloid, 0.3 part of a pH regulator and 100 parts of soft water; wherein the cross-linking monomer is prepared from the following components in a mass ratio of 1: 1.2: 3: 3: 4 vinyl unsaturated carboxylic acid, vinyl unsaturated amide, hydroxyethyl methacrylate, ethyl laurate, and vinyl versatate.
The mass ratio of the vinyl unsaturated carboxylic acid is 1: 2.5: 3.5: 3.8 itaconic acid, acrylic acid, methacrylic acid, maleic anhydride; the mass ratio of the vinyl unsaturated amide is 1: 1.4: 1.9: 2.8: 3.8 acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide, methylolmethacrylamide.
The anionic emulsifier is prepared from the following components in a mass ratio of 1: 3.5 sodium dodecyl sulfate, sodium dodecyl benzene sulfonate; the mass ratio of the nonionic emulsifier is 1: 1.3 nonylphenol polyoxyethylene ether with 8EO number or lauryl alcohol polyoxyethylene ether.
The initiator is prepared from the following components in a mass ratio of 1: 1.4: 2.5 of ammonium persulfate, sodium persulfate and ammonium persulfate. The protective colloid is prepared from the following components in percentage by mass 1: 1.3: 0.7 polyvinyl alcohol, cellulose, starch. The pH regulator is strong ammonia water with mass concentration of 26%.
The preparation method of the vinyl acetate-acrylic emulsion comprises the following specific steps:
(1) adding 0.45 time of soft water, 0.6 time of anionic emulsifier, 0.6 time of nonionic emulsifier, protective colloid and pH regulator into a polymerization kettle, heating to 90 ℃, cooling to 80 ℃ when the protective colloid is completely dissolved, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 5.5 hours, keeping the temperature for reacting for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
In the step (2), the preparation method of the initiator aqueous solution comprises the following steps: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
The redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity is prepared by the vinyl acetate-acrylic emulsion.
The preparation method of the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity comprises the following steps of mixing vinyl acetate/ethylene copolymer rubber powder (Vac/E) and the vinyl acetate-acrylic emulsion according to a mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
The dosage of the anticaking agent and the protective colloid water solution is respectively 0.025 times and 25 times of the weight of the vinyl acetate/ethylene copolymerized rubber powder. The anti-caking agent is prepared from the following components in a mass ratio of 1: 1.9: 2.5: 3.5: 3.8 of diatomite, aluminum silicate, talcum powder, attapulgite and kaolin. The protective colloid aqueous solution is obtained by adding protective colloid into 60 times of soft water by weight and uniformly dispersing by ultrasonic. The protective colloid is prepared from the following components in percentage by mass 1: 1.4: 0.7 polyvinyl alcohol, cellulose, starch.
Example 4:
the vinyl acetate-acrylic emulsion is prepared from the following raw materials in parts by weight: 55 parts of vinyl acetate, 30 parts of 2-ethylhexyl acrylate, 10 parts of a crosslinking monomer, 0.7 part of an anionic emulsifier, 3.5 parts of a nonionic emulsifier, 1 part of an initiator, 8 parts of a protective colloid, 0.3 part of a pH regulator and 100 parts of soft water; wherein the cross-linking monomer is prepared from the following components in a mass ratio of 1: 1.2: 3: 3: 4 vinyl unsaturated carboxylic acid, vinyl unsaturated amide, hydroxyethyl methacrylate, ethyl laurate, and vinyl versatate.
The mass ratio of the vinyl unsaturated carboxylic acid is 1: 2.5: 3.5: 3.8 itaconic acid, acrylic acid, methacrylic acid, maleic anhydride; the mass ratio of the vinyl unsaturated amide is 1: 1.4: 1.9: 2.8: 3.8 acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide, methylolmethacrylamide.
The anionic emulsifier is prepared from the following components in a mass ratio of 1: 3.5 sodium dodecyl sulfate, sodium dodecyl benzene sulfonate; the mass ratio of the nonionic emulsifier is 1: 1.3 nonylphenol polyoxyethylene ether with 8EO number or lauryl alcohol polyoxyethylene ether.
The initiator is prepared from the following components in a mass ratio of 1: 1.4: 2.5 of ammonium persulfate, sodium persulfate and ammonium persulfate. The protective colloid is prepared from the following components in percentage by mass 1: 1.3: 0.7 polyvinyl alcohol, cellulose, starch. The pH regulator is strong ammonia water with mass concentration of 26%.
The preparation method of the vinyl acetate-acrylic emulsion comprises the following specific steps:
(1) adding 0.45 time of soft water, 0.6 time of anionic emulsifier, 0.6 time of nonionic emulsifier, protective colloid and pH regulator into a polymerization kettle, heating to 90 ℃, cooling to 80 ℃ when the protective colloid is completely dissolved, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 5.5 hours, keeping the temperature for reacting for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
In the step (2), the preparation method of the initiator aqueous solution comprises the following steps: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
In the step (2), before the vinyl acetate and the 2-ethylhexyl acrylate are fed, modification treatment is carried out, and the specific method comprises the following steps: firstly, uniformly stirring vinyl acetate and 2-ethylhexyl acrylate, then adding the organic modified doped graphene, and uniformly stirring; the dosage of the organic modified doped graphene is 0.005 time of the weight of vinyl acetate, and the organic modified doped graphene is obtained by modifying graphene with 7-octenyl trichlorosilane.
The specific method for modifying the 7-octenyl trichlorosilane comprises the following steps: adding graphene into a mixture with a volume ratio of 1: 9, soaking the mixture of 7-octenyltrichlorosilane and toluene for 12 hours, and performing suction filtration to obtain the product; the molar ratio of the graphene to the 7-octenyltrichlorosilane is 1: 1.5.
the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity is prepared by the vinyl acetate-acrylic emulsion.
The preparation method of the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity comprises the following steps of mixing vinyl acetate/ethylene copolymer rubber powder (Vac/E) and the vinyl acetate-acrylic emulsion according to a mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
The dosage of the anticaking agent and the protective colloid water solution is respectively 0.025 times and 25 times of the weight of the vinyl acetate/ethylene copolymerized rubber powder. The anti-caking agent is prepared from the following components in a mass ratio of 1: 1.9: 2.5: 3.5: 3.8 of diatomite, aluminum silicate, talcum powder, attapulgite and kaolin. The protective colloid aqueous solution is obtained by adding protective colloid into 60 times of soft water by weight and uniformly dispersing by ultrasonic. The protective colloid is prepared from the following components in percentage by mass 1: 1.4: 0.7 polyvinyl alcohol, cellulose, starch.
Example 5:
the vinyl acetate-acrylic emulsion is prepared from the following raw materials in parts by weight: 55 parts of vinyl acetate, 30 parts of 2-ethylhexyl acrylate, 10 parts of a crosslinking monomer, 0.7 part of an anionic emulsifier, 3.5 parts of a nonionic emulsifier, 1 part of an initiator, 8 parts of a protective colloid, 0.3 part of a pH regulator and 100 parts of soft water; wherein the cross-linking monomer is prepared from the following components in a mass ratio of 1: 1.2: 3: 3: 4 vinyl unsaturated carboxylic acid, vinyl unsaturated amide, hydroxyethyl methacrylate, ethyl laurate, and vinyl versatate.
The mass ratio of the vinyl unsaturated carboxylic acid is 1: 2.5: 3.5: 3.8 itaconic acid, acrylic acid, methacrylic acid, maleic anhydride; the mass ratio of the vinyl unsaturated amide is 1: 1.4: 1.9: 2.8: 3.8 acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide, methylolmethacrylamide.
The anionic emulsifier is prepared from the following components in a mass ratio of 1: 3.5 sodium dodecyl sulfate, sodium dodecyl benzene sulfonate; the mass ratio of the nonionic emulsifier is 1: 1.3 nonylphenol polyoxyethylene ether with 8EO number or lauryl alcohol polyoxyethylene ether.
The initiator is prepared from the following components in a mass ratio of 1: 1.4: 2.5 of ammonium persulfate, sodium persulfate and ammonium persulfate. The protective colloid is prepared from the following components in percentage by mass 1: 1.3: 0.7 polyvinyl alcohol, cellulose, starch. The pH regulator is strong ammonia water with mass concentration of 26%.
The preparation method of the vinyl acetate-acrylic emulsion comprises the following specific steps:
(1) adding 0.45 time of soft water, 0.6 time of anionic emulsifier, 0.6 time of nonionic emulsifier, protective colloid and pH regulator into a polymerization kettle, heating to 90 ℃, cooling to 80 ℃ when the protective colloid is completely dissolved, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 5.5 hours, keeping the temperature for reacting for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
In the step (2), the preparation method of the initiator aqueous solution comprises the following steps: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
In the step (2), before the vinyl acetate and the 2-ethylhexyl acrylate are fed, modification treatment is carried out, and the specific method comprises the following steps: firstly, uniformly stirring vinyl acetate and 2-ethylhexyl acrylate, then adding the organic modified doped graphene, and uniformly stirring; the dosage of the organic modified doped graphene is 0.005 time of the weight of vinyl acetate, and the organic modified doped graphene is obtained by doping and reducing oxidized graphene with silicon to obtain doped graphene and then modifying the doped graphene with 7-octenyl trichlorosilane.
The preparation method of the doped graphene comprises the following steps: adding nano silicon powder into the graphene oxide dispersion liquid, heating for 8 hours at 500 ℃ under the helium atmosphere and ultrasonic oscillation conditions, reducing, and performing post-treatment to obtain the doped graphene; wherein the molar ratio of the nano silicon powder to the graphene oxide contained in the graphene oxide dispersion liquid is 0.06: 1, adding graphene oxide into water with the weight being 10 times that of the graphene oxide, and carrying out ultrasonic oscillation for 30 minutes to obtain the graphene oxide dispersion liquid.
The graphene oxide is prepared by adopting an improved Hummers method; the specific method for reduction is as follows: adding hydrazine hydrate, stirring and heating for 2 hours at 80 ℃, and cooling to room temperature (25 ℃); the specific method of post-treatment is as follows: centrifuging, washing to neutrality, and vacuum drying; wherein the temperature of vacuum drying is 60 ℃, and the drying time is 24 hours.
The specific method for modifying the 7-octenyl trichlorosilane comprises the following steps: adding doped graphene into a mixture with a volume ratio of 1: 9, soaking the mixture of 7-octenyltrichlorosilane and toluene for 12 hours, and performing suction filtration to obtain the product; the mol ratio of the doped graphene to the 7-octenyl trichlorosilane is 1: 1.5.
the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity is prepared by the vinyl acetate-acrylic emulsion.
The preparation method of the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity comprises the following steps of mixing vinyl acetate/ethylene copolymer rubber powder (Vac/E) and the vinyl acetate-acrylic emulsion according to a mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
The dosage of the anticaking agent and the protective colloid water solution is respectively 0.025 times and 25 times of the weight of the vinyl acetate/ethylene copolymerized rubber powder. The anti-caking agent is prepared from the following components in a mass ratio of 1: 1.9: 2.5: 3.5: 3.8 of diatomite, aluminum silicate, talcum powder, attapulgite and kaolin. The protective colloid aqueous solution is obtained by adding protective colloid into 60 times of soft water by weight and uniformly dispersing by ultrasonic. The protective colloid is prepared from the following components in percentage by mass 1: 1.4: 0.7 polyvinyl alcohol, cellulose, starch.
Example 6:
the vinyl acetate-acrylic emulsion is prepared from the following raw materials in parts by weight: 55 parts of vinyl acetate, 30 parts of 2-ethylhexyl acrylate, 10 parts of a crosslinking monomer, 0.7 part of an anionic emulsifier, 3.5 parts of a nonionic emulsifier, 1 part of an initiator, 8 parts of a protective colloid, 0.3 part of a pH regulator and 100 parts of soft water; wherein the cross-linking monomer is prepared from the following components in a mass ratio of 1: 1.2: 3: 3: 4 vinyl unsaturated carboxylic acid, vinyl unsaturated amide, hydroxyethyl methacrylate, ethyl laurate, and vinyl versatate.
The mass ratio of the vinyl unsaturated carboxylic acid is 1: 2.5: 3.5: 3.8 itaconic acid, acrylic acid, methacrylic acid, maleic anhydride; the mass ratio of the vinyl unsaturated amide is 1: 1.4: 1.9: 2.8: 3.8 acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide, methylolmethacrylamide.
The anionic emulsifier is prepared from the following components in a mass ratio of 1: 3.5 sodium dodecyl sulfate, sodium dodecyl benzene sulfonate; the mass ratio of the nonionic emulsifier is 1: 1.3 nonylphenol polyoxyethylene ether with 8EO number or lauryl alcohol polyoxyethylene ether.
The initiator is prepared from the following components in a mass ratio of 1: 1.4: 2.5 of ammonium persulfate, sodium persulfate and ammonium persulfate. The protective colloid is prepared from the following components in percentage by mass 1: 1.3: 0.7 polyvinyl alcohol, cellulose, starch. The pH regulator is strong ammonia water with mass concentration of 26%.
The preparation method of the vinyl acetate-acrylic emulsion comprises the following specific steps:
(1) adding 0.45 time of soft water, 0.6 time of anionic emulsifier, 0.6 time of nonionic emulsifier, protective colloid and pH regulator into a polymerization kettle, heating to 90 ℃, cooling to 80 ℃ when the protective colloid is completely dissolved, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 5.5 hours, keeping the temperature for reacting for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
In the step (2), the preparation method of the initiator aqueous solution comprises the following steps: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
In the step (2), before the vinyl acetate and the 2-ethylhexyl acrylate are fed, modification treatment is carried out, and the specific method comprises the following steps: firstly, uniformly stirring vinyl acetate and 2-ethylhexyl acrylate, then adding the organic modified doped graphene, and uniformly stirring; the dosage of the organic modified doped graphene is 0.005 time of the weight of vinyl acetate, and the organic modified doped graphene is obtained by carrying out silicon and phosphorus codoping and reduction on oxidized graphene to obtain doped graphene and then carrying out modification treatment on the doped graphene by using 7-octenyl trichlorosilane.
The preparation method of the doped graphene comprises the following steps: adding nano silicon powder and pyrophosphoric acid into graphene oxide dispersion liquid, heating for 8 hours at 500 ℃ under the conditions of helium atmosphere and ultrasonic oscillation, reducing, and performing post-treatment to obtain doped graphene; wherein the molar ratio of the nano silicon powder to the pyrophosphoric acid to the graphene oxide contained in the graphene oxide dispersion liquid is 0.02: 0.04: 1, adding graphene oxide into water with the weight being 10 times that of the graphene oxide, and carrying out ultrasonic oscillation for 30 minutes to obtain the graphene oxide dispersion liquid.
The graphene oxide is prepared by adopting an improved Hummers method; the specific method for reduction is as follows: adding hydrazine hydrate, stirring and heating for 2 hours at 80 ℃, and cooling to room temperature (25 ℃); the specific method of post-treatment is as follows: centrifuging, washing to neutrality, and vacuum drying; wherein the temperature of vacuum drying is 60 ℃, and the drying time is 24 hours.
The specific method for modifying the 7-octenyl trichlorosilane comprises the following steps: adding doped graphene into a mixture with a volume ratio of 1: 9, soaking the mixture of 7-octenyltrichlorosilane and toluene for 12 hours, and performing suction filtration to obtain the product; the mol ratio of the doped graphene to the 7-octenyl trichlorosilane is 1: 1.5.
the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity is prepared by the vinyl acetate-acrylic emulsion.
The preparation method of the redispersible vinyl acetate-acrylic emulsion powder with high solid content and low viscosity comprises the following steps of mixing vinyl acetate/ethylene copolymer rubber powder (Vac/E) and the vinyl acetate-acrylic emulsion according to a mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
The dosage of the anticaking agent and the protective colloid water solution is respectively 0.025 times and 25 times of the weight of the vinyl acetate/ethylene copolymerized rubber powder. The anti-caking agent is prepared from the following components in a mass ratio of 1: 1.9: 2.5: 3.5: 3.8 of diatomite, aluminum silicate, talcum powder, attapulgite and kaolin. The protective colloid aqueous solution is obtained by adding protective colloid into 60 times of soft water by weight and uniformly dispersing by ultrasonic. The protective colloid is prepared from the following components in percentage by mass 1: 1.4: 0.7 polyvinyl alcohol, cellulose, starch.
Comparative example 1
In the preparation of the vinyl acetate-acrylic emulsion, the dropping time of the step (3) was 4.5 hours.
The rest is the same as example 1.
Comparative example 2
In the preparation of the vinyl acetate-acrylic emulsion, the dropping time of the step (3) was 6.5 hours.
The rest is the same as example 1.
Test examples
Referring to GB/T11175-2002, various performance indexes of the vinyl acetate-acrylic emulsion obtained in examples 1-6 and comparative examples 1 and 2 are examined, and the results are shown in Table 1.
TABLE 1 Performance index Studies of vinyl acetate/acrylic emulsions
| Solid content (%) | Viscosity (mpa.s) | |
| Example 1 | 55.6 | 1800 |
| Example 2 | 56.1 | 1650 |
| Example 3 | 56.7 | 1500 |
| Example 4 | 58.5 | 1350 |
| Example 5 | 62.3 | 1160 |
| Example 6 | 66.9 | 805 |
| Comparative example 1 | 41.1 | 1860 |
| Comparative example 2 | 55.3 | 2450 |
As can be seen from table 1, the vinyl acetate emulsions of examples 1 to 6 have characteristics of high solid content and low viscosity, wherein examples 4, 5 and 6 have higher solid content and lower viscosity due to the introduction of graphene in the preparation process of the vinyl acetate emulsions, and compared with example 6, the performance of example 4 is slightly inferior to that of example 6 because graphene is directly introduced and graphene of example 5 is doped with silicon only. The dropping time of comparative example 1 is short, the solid content is obviously reduced, and the dropping time of comparative example 2 is long, and the viscosity is obviously too high.
The performance test of the latex powder products obtained in the examples 1-6 and the comparative example 2 is carried out by referring to GB/T29594-2013, and the results are shown in Table 2. Preparing a sample in the detection of the impact strength reference tensile strength, and detecting by using a KCJ-50 type impact strength tester; the water resistance was measured by measurement of the hydrophobic angle (KSV CAM 200 contact angle gauge, Helsinki, finland); the yellowing resistance can be referred to GB/T1865-2009.
TABLE 2 Performance examination of redispersible latex powders
As shown in Table 2, the latex powder products of examples 1 to 6 have small average particle size, good redispersibility, large tensile strength, elongation at break and impact strength, excellent mechanical properties, large hydrophobic angle, good water resistance, good mechanical stability and chemical stability, good weather resistance and good yellowing resistance. In examples 4, 5 and 6, graphene is introduced in the preparation process of the vinyl acetate-acrylic emulsion, and the performances are more excellent, compared with example 6, the graphene is directly introduced in example 4, and the graphene in example 5 is only doped with silicon, so that the performances are slightly poorer than those in example 6. The dropping time of comparative examples 1 and 2 was short or long, and the respective properties were remarkably deteriorated. The dripping time is very critical, the dripping time is too short, a large amount of heat can be released after rapid reaction, the local temperature is too high, the system temperature is difficult to control, part of monomers directly escape, and part of monomers are lost; the dropping time is too long, partial reaction is sufficient in the dropping micro range, but the reaction is easy to crosslink into a net shape, and the product performance is influenced.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Claims (10)
1. The vinyl acetate-acrylic emulsion is characterized by being prepared from the following raw materials in parts by weight: 40-75 parts of vinyl acetate, 20-40 parts of 2-ethylhexyl acrylate, 2-15 parts of a crosslinking monomer, 0.1-1 part of an anionic emulsifier, 0.5-7.5 parts of a nonionic emulsifier, 0.5-1.5 parts of an initiator, 5-10 parts of a protective colloid, 0.2-0.4 part of a pH regulator and 80-140 parts of soft water; wherein the crosslinking monomer is selected from any one or more of vinyl unsaturated carboxylic acid, vinyl unsaturated amide, hydroxyethyl methacrylate, ethyl laurate and vinyl versatate.
2. The vinyl acetate-acrylic emulsion according to claim 1, wherein said vinyl unsaturated carboxylic acid is selected from any one or more of itaconic acid, acrylic acid, methacrylic acid or maleic anhydride; the vinyl unsaturated amide is selected from any one or more of acrylamide, methacrylamide, dimethylacrylamide, methylolacrylamide or methyl methylolacrylamide.
3. The vinyl acetate-acrylic emulsion according to claim 1 wherein said anionic emulsifier is selected from any one or more of alkyl phenol sulfate, alkyl phenol succinate and alkyl phenol sulfonate; the nonionic emulsifier is selected from alkylphenol polyoxyethylene ether or fatty alcohol polyoxyethylene ether with the EO number of 7-10.
4. The vinyl acetate-acrylic emulsion according to claim 1 wherein said initiator is a persulfate salt selected from any one or more of ammonium persulfate, sodium persulfate and ammonium persulfate.
5. The vinyl acetate emulsion according to claim 1, wherein said protective colloid is selected from one or more of polyvinyl alcohol, cellulose and starch.
6. The method for preparing vinyl acetate-acrylic emulsion according to any one of claims 1 to 5, which comprises the following steps:
(1) adding 0.35-0.55 times of formula amount of soft water, 0.5-0.65 times of formula amount of anionic emulsifier, 0.5-0.65 times of formula amount of nonionic emulsifier, formula amount of protective colloid and pH regulator into a polymerization kettle, heating to 90 ℃, cooling to 80 ℃ after the protective colloid is completely dissolved, and keeping the temperature for later use;
(2) then preparing an initiator aqueous solution from the initiator with the formula amount according to the rest formula amount by using soft water with the formula amount, then adding the anionic emulsifier and the cationic emulsifier with the formula amount according to the rest formula amount, vinyl acetate, 2-ethylhexyl acrylate, a crosslinking monomer and 66% of the initiator aqueous solution with the formula amount into an emulsifying kettle, and fully mixing to obtain a mixed solution;
(3) and (3) finally, adding the rest initiator aqueous solution into the polymerization kettle obtained in the step (1), stirring for 5 minutes, then dropwise adding the mixed solution obtained in the step (2), wherein the dropwise adding time is 5-6 hours, keeping the temperature for reaction for 1.5 hours after the dropwise adding is finished, naturally cooling to 30 ℃, and discharging to obtain the vinyl acetate-acrylic emulsion.
7. The method according to claim 6, wherein in the step (2), the aqueous solution of the initiator is prepared as follows: adding the initiator into soft water, and stirring until the initiator is completely dissolved.
8. The preparation method according to claim 6, wherein in the step (2), the vinyl acetate and the 2-ethylhexyl acrylate are modified before being fed, and the method comprises the following specific steps: firstly, uniformly stirring vinyl acetate and 2-ethylhexyl acrylate, then adding the organic modified doped graphene, and uniformly stirring; the dosage of the organic modified doped graphene is 0.005-0.008 times of the weight of vinyl acetate, and the organic modified doped graphene is obtained by carrying out silicon and phosphorus codoping and reduction on graphene oxide to obtain doped graphene and then carrying out modification treatment on the doped graphene oxide by using 7-octenyl trichlorosilane.
9. A high-solid low-viscosity redispersible vinyl acetate-acrylic emulsion powder prepared by using the vinyl acetate-acrylic emulsion of any one of claims 1 to 5.
10. The method for preparing the redispersible latex powder of vinyl acetate-acrylic emulsion with high solid content and low viscosity as claimed in claim 9, wherein the vinyl acetate/ethylene copolymer rubber powder and the latex powder of vinyl acetate-acrylic emulsion are mixed according to the mass ratio of 7: 3, uniformly stirring, adding an anti-caking agent and a protective colloid aqueous solution, uniformly stirring, and spray-drying to obtain the redispersible acrylic latex powder with high solid content and low viscosity.
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