CN114195930A - Modified potassium silicate styrene-acrylic emulsion and preparation method thereof, and preservative-free and solvent-free aqueous polymer material and preparation method thereof - Google Patents
Modified potassium silicate styrene-acrylic emulsion and preparation method thereof, and preservative-free and solvent-free aqueous polymer material and preparation method thereof Download PDFInfo
- Publication number
- CN114195930A CN114195930A CN202111646742.8A CN202111646742A CN114195930A CN 114195930 A CN114195930 A CN 114195930A CN 202111646742 A CN202111646742 A CN 202111646742A CN 114195930 A CN114195930 A CN 114195930A
- Authority
- CN
- China
- Prior art keywords
- styrene
- free
- mixed solution
- potassium silicate
- acrylic emulsion
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 49
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical class [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920001909 styrene-acrylic polymer Polymers 0.000 title claims abstract description 32
- 239000002861 polymer material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004945 emulsification Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 36
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 silicon modified potassium silicate Chemical class 0.000 claims abstract description 8
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000006254 rheological additive Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims 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 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 5
- 235000010446 mineral oil Nutrition 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000007798 antifreeze agent Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000142 Sodium polycarboxylate Polymers 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 2
- 241000276489 Merlangius merlangus Species 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 230000002528 anti-freeze Effects 0.000 claims 1
- 239000003755 preservative agent Substances 0.000 abstract description 10
- 230000002335 preservative effect Effects 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 239000003292 glue Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 239000003973 paint Substances 0.000 description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000004111 Potassium silicate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 229910052913 potassium silicate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- JAYAURNSBGONCJ-UHFFFAOYSA-N 1-(1-hydroxypropan-2-yloxy)heptan-2-ol Chemical compound CCCCCC(O)COC(C)CO JAYAURNSBGONCJ-UHFFFAOYSA-N 0.000 description 1
- XRNFIFFUKRDOFY-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]heptan-2-ol Chemical compound CCCCCC(O)COC(C)COC(C)CO XRNFIFFUKRDOFY-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010012442 Dermatitis contact Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 208000010247 contact dermatitis Diseases 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ITFGZZGYXVHOOU-UHFFFAOYSA-N n,n-dimethylmethanamine;methyl hydrogen sulfate Chemical compound C[NH+](C)C.COS([O-])(=O)=O ITFGZZGYXVHOOU-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- 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
- 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
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the field of aqueous high polymer materials, and particularly relates to a modified potassium silicate styrene-acrylic emulsion and a preparation method thereof, and a preservative-free and solvent-free aqueous high polymer material and a preparation method thereof. The modified potassium silicate styrene-acrylic emulsion comprises methyl methacrylate, butyl acrylate, styrene, sodium bicarbonate, potassium persulfate, an emulsifier, a silane coupling agent, quaternary ammonium salt containing unsaturated double bonds, organic silicon modified potassium silicate, protective glue and water. The preservative-free and solvent-free aqueous polymer material provided by the invention is not added with a preservative and an organic solvent, has extremely low VOC, SVOC and TVOC, is not detected out free formaldehyde, and has the characteristics of excellent saltpetering resistance, saltpetering alkalinity resistance, storage stability and the like.
Description
Technical Field
The invention belongs to the field of aqueous high polymer materials, and particularly relates to a modified potassium silicate styrene-acrylic emulsion and a preparation method thereof, and a preservative-free and solvent-free aqueous high polymer material and a preparation method thereof.
Background
The water paint uses water as dispersion medium and is rich in nutrients available to many microbes, such as cellulose, emulsion, etc. Under the condition of proper temperature and humidity, the water-based paint is easy to breed a large amount of microbes such as bacteria, fungi and mould fungi, the microbes not only pollute the paint, but also seriously affect the quality of the paint, and further cause abnormal viscosity, poor fluidity, serious layering, mildewing, peculiar smell generation and the like of the paint. According to the prior art, a preservative mildew preventive is often added to the water-based paint to prevent the generation of bacterial mildew so as to ensure the quality stability of the product, wherein isothiazolinone is more. Research shows that the preservative has potential contact allergy, can cause contact dermatitis of human bodies, and generates serious allergic reaction. In addition, isothiazolinone compounds can enter the body through human body contact, which directly or indirectly affects normal hormone metabolism, and metabolites and conversion products thereof often show certain biological activity and bioaccumulation.
The emulsion used in the existing water-based paint generally has a certain film-forming temperature, and when the ambient temperature is lower than the film-forming temperature of the emulsion, the emulsion is not easy to form a film, so a certain amount of film-forming auxiliary agent is usually added. The film-forming assistant is a high-boiling-point organic solvent, and can be slowly released into the air in the drying process of a paint film, so that adverse effects are brought to human health and environment.
The Chinese invention patent application with the publication number of CN1954039A discloses a preservative-free coating agent, a preparation method and application thereof. The patent mainly describes that the paint consists of 29 percent potassium silicate aqueous solution, vinyl ester copolymer (containing different amounts of vinyl acetate, VeoVa10 and ethylene copolymer dispersion), film forming auxiliary agent (at least one of petroleum solvent, Texanol, TxiB, butyl glycol, butyl diglycol, butyl dipropylene glycol and butyl tripropylene glycol), thickening agent, wetting agent and defoaming agent. The pH value of the vinyl ester copolymer used in the preservative-free coating agent is 4.4, no additional preservative is added during storage by directly adding potassium silicate into the formula, and the preservative-free coating agent has higher risk of saltpetering alkalinity. And in addition, a film forming auxiliary agent is required to be added to assist film forming during use, and a large amount of organic solvent is introduced during actual use, so that harm to human bodies and environment is caused.
With the continuous enhancement of health consciousness of people and the continuous improvement of the national requirement on environmental protection, the development of a water-based high polymer material which has the characteristics of no preservative, no solvent, extremely low TVOC and the like and can be widely applied to places such as children rooms, schools, hospitals and the like is urgently needed.
Disclosure of Invention
The invention aims to develop a preservative-free and solvent-free aqueous polymer material, solve the problems in the background art and meet the requirements of people on health and environmental protection. The prepared preservative-free and solvent-free aqueous polymer material is not added with preservative and organic solvent, has extremely low VOC, SVOC and TVOC, is not detected out free formaldehyde, and has the characteristics of excellent anti-efflorescence property, storage stability and the like.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a modified potassium silicate styrene-acrylic emulsion, the method comprising:
(1) mixing and reacting a first part of quaternary ammonium salt containing unsaturated double bonds, organic silicon modified potassium silicate and a first part of water at the temperature of 30-40 ℃ to obtain a first mixed solution;
(2) mixing a first part of emulsifier, sodium bicarbonate, methyl methacrylate, butyl acrylate, a second part of quaternary ammonium salt containing unsaturated double bonds and styrene with the second part of water to obtain a second mixed solution;
(3) mixing the second part of emulsifier with the third part of water, controlling the system temperature to be 70-80 ℃, and then mixing the second part of emulsifier with the first part of potassium persulfate, the first part of second mixed solution and the first part of silane coupling agent to obtain a third mixed solution;
(4) dropwise adding a second part of the second mixed solution, a second part of potassium persulfate and a third part of quaternary ammonium salt containing unsaturated double bonds into the third mixed solution, preserving the temperature, and then reducing the temperature of the system to 45-55 ℃ to obtain a fourth mixed solution;
(5) dropwise adding the first mixed solution, the third part of emulsifier and the second part of silane coupling agent into the fourth mixed solution to obtain a fifth mixed solution;
(6) and cooling the fifth mixed solution to 30-35 ℃, filtering, and adding a protective adhesive to obtain the modified potassium silicate styrene-acrylic emulsion.
Preferably, in step (1), the mixing reaction is carried out for 2h to 4h, such as 3 h.
According to the invention, the quaternary ammonium salt containing unsaturated double bonds in the step (1) has the function of reacting with the organosilicon modified potassium silicate, so that the stability of the potassium silicate and a reaction system is ensured; the second part of quaternary ammonium salt containing unsaturated double bonds plays a role in step (2) by utilizing the unsaturated double bonds to participate in polymerization reaction; the third part of the quaternary ammonium salt containing unsaturated double bonds plays a role in the step (4) in participating in polymerization reaction by utilizing the unsaturated double bonds.
According to the invention, a first part of emulsifier, a second part of emulsifier and a third part of emulsifier are respectively added in the step (2), the step (3) and the step (5), the purpose of separately adding the emulsifiers is to effectively control the diameter and the distribution of the emulsion particles generated in each step, under the condition that the monomer amount is not changed, the seed emulsion is added, the particle size of the emulsion is reduced, the size distribution of the finally obtained emulsion particles is narrower, and the rheological property of the modified potassium silicate styrene-acrylic emulsion is effectively improved.
According to the invention, in step (3), the temperature of 70 ℃ to 80 ℃ is the temperature required for carrying out the polymerization.
According to the present invention, in the step (4), it is selected that the heat-retention is performed after dropping the second part of the second mixed solution, the second part of potassium persulfate, and the third part of quaternary ammonium salt having an unsaturated double bond. Preferably, the holding time is 1h to 2h to ensure the completion of the polymerization reaction.
According to the invention, in the step (4), the temperature of the system is controlled to be 45-55 ℃ after heat preservation, so as to reduce the temperature of the reaction liquid and ensure the termination of the polymerization reaction.
According to the present invention, in the step (5), after the first mixed solution, the third part of the emulsifier and the second part of the silane coupling agent are added dropwise to the fourth mixed solution, the temperature is preferably maintained at 40 ℃ to 50 ℃ for 20min to 30min, and the temperature of the reaction solution is lowered to ensure the stability of the polymer.
According to the present invention, in the step (6), it is preferable to cool the fifth mixed solution to 30 ℃ to 35 ℃ to ensure the stability of the polymer again.
The emulsifier is added in each step in order to control the polymerization rate, the number of latex particles and the size of the latex particles.
As a preferred scheme, in the preparation method of the modified potassium silicate styrene-acrylic emulsion, the dosage of each component is as follows:
10-30 parts of methyl methacrylate, 150 parts of butyl acrylate, 150 parts of styrene, 0.2-1.0 part of sodium bicarbonate, 1.0-1.6 parts of potassium persulfate, 12-27 parts of emulsifier, 1-5 parts of silane coupling agent, 10-20 parts of quaternary ammonium salt containing unsaturated double bonds, 40-60 parts of organosilicon modified potassium silicate, 10-15 parts of protective adhesive and 500 parts of water 400.
Preferably, the quaternary ammonium salt containing unsaturated double bonds comprises 10% -20% of quaternary ammonium salt containing unsaturated double bonds in the first part, 40% -50% of quaternary ammonium salt containing unsaturated double bonds in the second part and 30% -40% of quaternary ammonium salt containing unsaturated double bonds in the third part.
Preferably, the water comprises 10% -20% of first water, 30% -40% of second water and 40% -60% of third water.
Preferably, the first part of emulsifier is 5-15%, the second part of emulsifier is 30-50%, and the third part of emulsifier is 40-60%.
Preferably, the first part of the potassium persulfate is 20-40% and the second part of the potassium persulfate is 60-80%.
Preferably, the silane coupling agent comprises 30% -50% of the first part of silane coupling agent and 50% -70% of the second part of silane coupling agent.
Preferably, in the second mixed solution, the first part of the second mixed solution is 15% -25%, and the second part of the second mixed solution is 75% -85%.
Preferably, the unsaturated double bond-containing quaternary ammonium salt contains a C ═ C and/or C ═ N double bond.
Preferably, the emulsifier is selected from the group consisting of Bassfu (China) Co
At least one of FES 430 and MS-1.
Preferably, the silane coupling agent is at least one selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (. beta. -methoxyethoxy) silane.
A second aspect of the present invention provides a modified potassium silicate styrene-acrylic emulsion obtained by the above-mentioned method for preparing a modified potassium silicate styrene-acrylic emulsion. The pH value of the obtained modified potassium silicate styrene-acrylic emulsion is more than 11, the environment with the pH value more than 11 causes that microorganisms are not suitable for growth, and quaternary ammonium salt containing unsaturated double bonds is introduced in the emulsion synthesis process, so that the modified potassium silicate styrene-acrylic emulsion does not need to be additionally added with in-tank preservative and mildew preventive when in use; the addition of the monomers of methyl methacrylate and butyl acrylate with low Tg enables the modified potassium silicate styrene-acrylic emulsion to have more excellent low-temperature film-forming property.
The third aspect of the present invention provides a preservative-free and solvent-free aqueous polymer material, which comprises the following raw materials:
15-25 parts of modified potassium silicate styrene-acrylic emulsion, 35-50 parts of pigment and filler, 20-40 parts of water, 0.2-1.0 part of non-alkali swelling thickener, 0.1-1.0 part of stabilizer, 0-3.0 parts of assistant and no film-forming assistant;
the modified potassium silicate styrene-acrylic emulsion is the modified potassium silicate styrene-acrylic emulsion;
the auxiliary agent comprises at least one of a dispersing agent, an anti-settling agent, a pH regulator, a rheological auxiliary agent, an antifreeze agent and a defoaming agent.
Preferably, the pigment and filler comprises at least one of titanium dioxide, mica powder, calcium carbonate and kaolin.
Preferably, the non-alkali swelling thickener is at least one selected from hydroxyethyl cellulose and polyurethane thickener.
Preferably, the stabilizer is a cationic quaternary ammonium salt surfactant.
Preferably, the dispersant is an anionic surfactant.
Preferably, the anti-settling agent is an inorganic anti-settling agent.
Preferably, the pH regulator is an organic amine pH regulator and/or an inorganic pH regulator.
Preferably, the rheological additive is a polyurethane rheological additive, and more preferably a Dow chemical (Chinese) Co., Ltd, Asia-Leshun TM (ACRYSOL TM) RM-2100 rheology modifier.
Preferably, the antifreeze agent is a surfactant type freeze-thaw stabilizer, and more preferably, the antifreeze agent is a surfactant type freeze-thaw stabilizer
FT100XTRIM。
Preferably, the defoaming agent is a mineral oil defoaming agent and/or a silicone defoaming agent.
As a further preferred scheme, the titanium dioxide is rutile type titanium dioxide and/or anatase type titanium dioxide, and more preferably SiO2And/or Al2O3Rutile type titanium dioxide subjected to coating treatment.
As a further preferable scheme, the mica powder is wet sericite.
As a further preferable scheme, the calcium carbonate is 1000-1500 mesh heavy calcium carbonate.
As a further preferred embodiment, the kaolin is calcined kaolin.
As a further preferable mode, the non-alkali swelling thickener is hydroxyethyl cellulose.
In a further preferred embodiment, the anionic surfactant is a sodium polycarboxylate dispersant.
In a further preferred embodiment, the inorganic anti-settling agent is an organically modified purified hectorite clay. As produced by the courtesy (Shanghai) chemical Co., Ltd
DY CE organically modified refined hectorite clay.
As a further preferable embodiment, the pH adjuster is an aqueous sodium hydroxide solution, such as a 20% aqueous sodium hydroxide solution.
As a further preferred embodiment, the defoamer is a mineral oil type defoamer compounded with a C10-rich ethoxylated iso-C9-C11 alcohol and a crosslinked polymer of epichlorohydrin. Such as BASF (China) Inc
ST 2410 mineral oil type antifoaming agent.
The fourth aspect of the present invention provides a method for preparing the preservative-free and solvent-free aqueous polymer material, the method comprising:
1) uniformly mixing the first part of water, the stabilizer and the optional first part of auxiliary agent to obtain a premixed solution;
2) uniformly mixing the premixed solution with pigment, filler and non-alkali swelling thickener to obtain preservative-free solvent-free aqueous polymer material slurry;
3) uniformly mixing the preservative-free and solvent-free aqueous high polymer material slurry with the modified potassium silicate styrene-acrylic emulsion, the optional second part of auxiliary agent and the second part of water to obtain the preservative-free and solvent-free aqueous high polymer material.
According to the invention, when the addition of the auxiliary agent is selected, the addition is usually carried out in two parts, and a dispersing agent and a defoaming agent are usually selected as the first part of the addition of the auxiliary agent to assist the dispersion of the powder in the system in the next step; and a rheological additive and a defoaming agent are selected as a second part of additives to be added, and the rheological additive and the like are required to be placed after the pigment and filler are dispersed, so that the phenomenon that the rheological additive is excessively adsorbed by powder and the like to cause poor effect is avoided.
The invention has the beneficial effects that:
the preservative-free and solvent-free aqueous polymer material provided by the invention is not added with a preservative and an organic solvent, has a pH value of more than 11, a glass transition temperature Tg of 3 ℃, is extremely low in VOC, SVOC and TVOC, has no free formaldehyde detected, and has the characteristics of excellent saltpetering resistance, storage stability and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a modified potassium silicate styrene-acrylic emulsion and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing and reacting a first part of quaternary ammonium salt containing unsaturated double bonds, organic silicon modified potassium silicate and a first part of water at 35 ℃ to obtain a first mixed solution;
(2) mixing a first part of emulsifier, sodium bicarbonate, methyl methacrylate, butyl acrylate, a second part of quaternary ammonium salt containing unsaturated double bonds and styrene with the second part of water to obtain a second mixed solution;
(3) mixing a second part of emulsifier with a third part of water, controlling the system temperature to be 75 ℃, and mixing the second part of emulsifier with a first part of potassium persulfate, a first part of second mixed solution and a first part of silane coupling agent to obtain a third mixed solution;
(4) dropwise adding a second part of the second mixed solution, a second part of potassium persulfate and a third part of quaternary ammonium salt containing unsaturated double bonds into the third mixed solution, preserving the heat for 1.5h, and then controlling the system temperature to be 50 ℃ to obtain a fourth mixed solution;
(5) dropwise adding the first mixed solution, the third part of emulsifier and the second part of silane coupling agent into the fourth mixed solution, and keeping the temperature at 45 ℃ for 25min to obtain a fifth mixed solution;
(6) and cooling the fifth mixed solution to 32 ℃, filtering, and adding a protective adhesive to obtain the modified potassium silicate styrene-acrylic emulsion.
Wherein, the dosage of each component is as follows:
20 parts by weight of methyl methacrylate, 125 parts by weight of butyl acrylate, 125 parts by weight of styrene, 0.6 part by weight of sodium bicarbonate, 1.3 parts by weight of potassium persulfate, and an emulsifier (Basff (China) Co., Ltd.)
FES 430)10 parts by weight, 3 parts by weight of a silane coupling agent (vinyltriethoxysilane), and a quaternary ammonium salt having an unsaturated double bond (Toshiai (Shanghai); [2- (methacryloyloxy) ethyl ] Ether, manufactured by Industrial development Co., Ltd.)]Trimethyl ammonium methyl sulfate) 15 parts by weight, and organosilicon modified potassium silicate (produced by Shanghai Australian chemical Co., Ltd.)
K100)
50 parts by weight, 12.5 parts by weight of protective rubber (Natrosol 250HBR, Inc., invested in Asia-Hiland (China)), and 450 parts by weight of water.
The quaternary ammonium salt containing unsaturated double bonds comprises 20 percent of quaternary ammonium salt containing unsaturated double bonds in the first part, 45 percent of quaternary ammonium salt containing unsaturated double bonds in the second part and 35 percent of quaternary ammonium salt containing unsaturated double bonds in the third part;
in water, 15% of first part of water, 35% of second part of water and 50% of third part of water;
the emulsifier comprises 10% of a first part of emulsifier, 40% of a second part of emulsifier and 50% of a third part of emulsifier;
the first part of potassium persulfate is 30 percent and the second part of potassium persulfate is 70 percent;
in the silane coupling agents, the first part of silane coupling agent is 30 percent, and the second part of silane coupling agent is 70 percent;
in the second mixed solution, the first part of the second mixed solution is 20% and the second part of the second mixed solution is 80%.
Example 2 and comparative examples 1 to 5
Example 2 provides a preservative-free and solvent-free aqueous polymer material and a method for preparing the same, and comparative examples 1 to 5 provide an aqueous polymer material. The amounts of the components are shown in Table 1 (parts by weight).
TABLE 1
Comparative example 4:
the difference from the example 2 is that the modified potassium silicate acrylic emulsion is replaced by a Badfh acrylic ester emulsion RS-8098, and the in-tank antiseptic and mildew inhibitor and the film forming auxiliary agent are not added.
Comparative example 5:
the difference from the example 2 is that the modified potassium silicate acrylic emulsion is replaced by a Badfh acrylic ester emulsion RS-8098, and an in-tank antiseptic and mildew-proof agent and a film-forming assistant are added.
The preparation method of the preservative-free and solvent-free aqueous polymer material comprises the following steps:
1) under the stirring state of 400-500r/min, uniformly mixing part of deionized water, a stabilizing agent, a dispersing agent, a defoaming agent and an anti-freezing agent, and stirring for 5-10min to obtain a premixed solution.
2) Under the stirring state of 400-1500 r/min, adding the filler and the anti-settling agent into the premixed liquid, gradually increasing the rotating speed to 800-1000r/min, stirring for 5-10min to a uniform state, then adding the thickening agent, and dispersing at a high speed of 1200-1500r/min for 10-15min until the fineness is less than or equal to 50um, thus obtaining the preservative-free solvent-free aqueous polymer material slurry.
3) Adjusting the stirring speed to be 600-800r/min, adding the modified potassium silicate acrylic emulsion and the water in the rest formula amount, stirring for 5-10min, and uniformly mixing to obtain the preservative-free solvent-free aqueous polymer material.
Test example:
in this test example, the preservative-free and solvent-free aqueous polymer material provided in example 2, the preparation method thereof, and the aqueous polymer materials provided in comparative examples 1 to 5 were tested, and the test examples included: and (3) detecting the contents of heat storage stability, low-temperature film-forming property, salt-flooding resistance, VOC, SVOC, TVOC and free formaldehyde.
The thermal storage stability test method comprises the following steps: before thermal storage, the preservative-free, solvent-free, aqueous polymer materials of examples 1 to 4 were subjected to viscosity, pH, and whiteness tests, and the open can state and the test results were recorded, and then subjected to viscosity, pH, and whiteness tests after storage at 65 ℃ for 1 week, 2 weeks, and 1 month, respectively, and the open can state and the test results were recorded.
The low-temperature film forming property test method comprises the following steps: and (3) preparing a film on each sample on a glass plate by using a 400-micron wet film preparation device, immediately placing the glass plate in a 3-DEG C oven, and observing the film forming state of a paint film after 4 hours, wherein the film cracking-free condition of the paint film is 0min, and the film cracking-serious condition of the paint film is 5 min.
The anti-saltpetering and anti-saltpetering alkalinity test method was performed according to JG/T210-2018.
The detection of the content of VOC and free formaldehyde is carried out according to GB 18582-.
TVOC is carried out according to ISO-16000-3, ISO-16000-6, ISO-16000-9, ISO-16000-11 standards.
SVOC is carried out according to DIN EN ISO 11890-2: 2013.
The results of the thermal storage stability test are shown in table 2. Example 2 the storage stability is best; comparative example 1 is the worst in storage stability because the modified potassium silicate acrylic emulsion has too high content, resulting in too much potassium silicate in the system and thus significant post-thickening; comparative example 3 has a viscosity reduction phenomenon because it uses an alkali swelling thickener, which is not suitable for the present system. Comparative example 4 was not added with the in-can preservative and antifungal agent and deteriorated after being stored at 65 ℃ for one month, and comparative example 5 was a normal emulsion to which the in-can preservative and antifungal agent was added, and the storage stability was also good.
TABLE 2
The test results of the low temperature film forming properties are shown in table 3. The low-temperature film forming property test method comprises the following steps: and (3) preparing a film on each sample on a glass plate by using a 400-micron wet film preparation device, immediately placing the glass plate in a 3-DEG C oven, and observing the film forming state of a paint film after 4 hours, wherein the film cracking-free condition of the paint film is 0min, and the film cracking-serious condition of the paint film is 5 min. As can be seen from Table 3, the excellent low-temperature film forming property can be maintained in example 2 and comparative examples 1, 2, 3 and 5, and comparative example 4 has no film forming assistant and can not form a film under the condition of 3 ℃, and the paint film cracks seriously.
TABLE 3
| Performance index | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Low temperature film forming | 0 | 0 | 0 | 0 | 5 | 0 |
The results of the anti-saltpetering and salt-overtaking resistance tests are shown in Table 4. As can be seen from Table 4, comparative example 2 failed the national standard test due to the inferior performance of the bleed resistance and bleed resistance properties with lower emulsion usage. Comparative example 4 the pan-alkaline and salt-overtaking resistance of the paint film could not meet the national standard test requirements due to incomplete film formation.
TABLE 4
The VOC, TVOC, SVOC and free formaldehyde content test results are shown in Table 5. It can be seen that the VOC, TVOC, SVOC and free formaldehyde content of the samples of examples 1-4 are not detected, and the preservative-free and solvent-free aqueous polymer material of the present invention has excellent environmental protection performance. Comparative example 4 and comparative example 5 both contained TVOC and SVOC, where comparative example 5 failed to meet the DIN EN ISO 11890-2:2013 limit for SVOC content due to the higher addition of film-forming aid.
TABLE 5
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. The preparation method of the modified potassium silicate styrene-acrylic emulsion is characterized by comprising the following steps:
(1) mixing and reacting a first part of quaternary ammonium salt containing unsaturated double bonds, organic silicon modified potassium silicate and a first part of water at the temperature of 30-40 ℃ to obtain a first mixed solution;
(2) mixing a first part of emulsifier, sodium bicarbonate, methyl methacrylate, butyl acrylate, a second part of quaternary ammonium salt containing unsaturated double bonds and styrene with the second part of water to obtain a second mixed solution;
(3) mixing the second part of emulsifier with the third part of water, controlling the system temperature to be 70-80 ℃, and then mixing the second part of emulsifier with the first part of potassium persulfate, the first part of second mixed solution and the first part of silane coupling agent to obtain a third mixed solution;
(4) dropwise adding a second part of the second mixed solution, a second part of potassium persulfate and a third part of quaternary ammonium salt containing unsaturated double bonds into the third mixed solution, preserving the temperature, and then reducing the temperature of the system to 45-55 ℃ to obtain a fourth mixed solution;
(5) dropwise adding the first mixed solution, the third part of emulsifier and the second part of silane coupling agent into the fourth mixed solution to obtain a fifth mixed solution;
(6) and cooling the fifth mixed solution, filtering, and adding a protective adhesive to obtain the modified potassium silicate styrene-acrylic emulsion.
2. The preparation method of the modified potassium silicate styrene-acrylic emulsion as claimed in claim 1, wherein the dosage of each component is as follows:
10-30 parts of methyl methacrylate, 150 parts of butyl acrylate, 150 parts of styrene, 0.2-1.0 part of sodium bicarbonate, 1.0-1.6 parts of potassium persulfate, 12-27 parts of emulsifier, 1-5 parts of silane coupling agent, 10-20 parts of quaternary ammonium salt containing unsaturated double bonds, 40-60 parts of organosilicon modified potassium silicate, 10-15 parts of protective adhesive and 500 parts of water 400.
3. The method for preparing a modified potassium silicate styrene-acrylic emulsion according to claim 2,
in the quaternary ammonium salt containing unsaturated double bonds, the first part contains 10 to 20 percent of quaternary ammonium salt containing unsaturated double bonds, the second part contains 40 to 50 percent of quaternary ammonium salt containing unsaturated double bonds, and the third part contains 30 to 40 percent of quaternary ammonium salt containing unsaturated double bonds;
in the water, the first part of water accounts for 10% -20%, the second part of water accounts for 30% -40% and the third part of water accounts for 40% -60%;
in the emulsifiers, a first part of emulsifier is 5-15%, a second part of emulsifier is 30-50%, and a third part of emulsifier is 40-60%;
in the potassium persulfate, the first part of potassium persulfate is 20-40%, and the second part of potassium persulfate is 60-80%;
in the silane coupling agent, 30-50% of the first part of silane coupling agent and 50-70% of the second part of silane coupling agent;
in the second mixed solution, 15% -25% of the first part of the second mixed solution and 75% -85% of the second part of the second mixed solution.
4. The method for preparing a modified potassium silicate styrene-acrylic emulsion according to claim 1,
the quaternary ammonium salt containing an unsaturated double bond contains a C ═ C and/or C ═ N double bond;
the emulsifier is selected from Basff (China) Co., Ltd
At least one of FES 430 and MS-1;
the silane coupling agent is at least one selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (. beta. -methoxyethoxy) silane.
5. The method for preparing a modified potassium silicate styrene-acrylic emulsion according to claim 1,
in the step (4), preserving heat for 1-2 h;
in the step (5), after the first mixed solution, the third part of emulsifier and the second part of silane coupling agent are added dropwise into the fourth mixed solution, the method further comprises the following steps: preserving the heat at 40-50 ℃ for 20-30 min;
in the step (6), the temperature of the fifth mixed solution is reduced to 30-35 ℃.
6. A modified potassium silicate styrene-acrylic emulsion obtained by the method for preparing a modified potassium silicate styrene-acrylic emulsion according to any one of claims 1 to 5.
7. The preservative-free and solvent-free aqueous polymer material is characterized by comprising the following raw materials:
15-25 parts of modified potassium silicate styrene-acrylic emulsion, 35-50 parts of pigment and filler, 20-40 parts of water, 0.2-1.0 part of non-alkali swelling thickener, 0.1-1.0 part of stabilizer, 0-3.0 parts of assistant and no film-forming assistant;
the modified potassium silicate styrene-acrylic emulsion is the modified potassium silicate styrene-acrylic emulsion of claim 6;
the auxiliary agent comprises at least one of a dispersing agent, an anti-settling agent, a pH regulator, a rheological auxiliary agent, an antifreeze agent and a defoaming agent.
8. The preservative-free, solvent-free aqueous polymeric material of claim 7,
the pigment and filler comprises at least one of titanium dioxide, mica powder, calcium carbonate and kaolin;
the non-alkali swelling thickener is at least one of hydroxyethyl cellulose and polyurethane thickener;
the stabilizer is a cationic quaternary ammonium salt surfactant;
the dispersant is an anionic surfactant;
the anti-settling agent is an inorganic anti-settling agent;
the pH regulator is an organic amine pH regulator and/or an inorganic pH regulator;
the rheological additive is a polyurethane rheological additive;
the antifreeze is a surfactant type freeze-thaw stabilizer;
the defoaming agent is a mineral oil defoaming agent and/or an organic silicon defoaming agent.
9. The preservative-free, solvent-free aqueous polymeric material of claim 8,
the titanium dioxide is rutile type titanium dioxide and/or anatase type titanium dioxide, preferably SiO2And/or Al2O3Coating the rutile type titanium dioxide;
the mica powder is wet sericite;
the calcium carbonate is 1000-mesh 1500-mesh coarse whiting;
the kaolin is calcined kaolin;
the non-alkali swelling thickener is hydroxyethyl cellulose;
the anionic surfactant is a sodium polycarboxylate dispersant;
the inorganic anti-settling agent is organic modified refined hectorite clay;
the pH regulator is sodium hydroxide aqueous solution;
the defoamer is a mineral oil type defoamer rich in C10 ethoxylated iso-C9-C11 alcohol compounded with a crosslinked polymer of epichlorohydrin.
10. The method for preparing the preservative-free and solvent-free aqueous polymer material according to any one of claims 7 to 9, wherein the method comprises:
1) uniformly mixing the first part of water, the stabilizer and the optional first part of auxiliary agent to obtain a premixed solution;
2) uniformly mixing the premixed solution with pigment, filler and non-alkali swelling thickener to obtain preservative-free solvent-free aqueous polymer material slurry;
3) uniformly mixing the preservative-free and solvent-free aqueous high polymer material slurry with the modified potassium silicate styrene-acrylic emulsion, the optional second part of auxiliary agent and the second part of water to obtain the preservative-free and solvent-free aqueous high polymer material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111646742.8A CN114195930A (en) | 2021-12-29 | 2021-12-29 | Modified potassium silicate styrene-acrylic emulsion and preparation method thereof, and preservative-free and solvent-free aqueous polymer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111646742.8A CN114195930A (en) | 2021-12-29 | 2021-12-29 | Modified potassium silicate styrene-acrylic emulsion and preparation method thereof, and preservative-free and solvent-free aqueous polymer material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114195930A true CN114195930A (en) | 2022-03-18 |
Family
ID=80657358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111646742.8A Pending CN114195930A (en) | 2021-12-29 | 2021-12-29 | Modified potassium silicate styrene-acrylic emulsion and preparation method thereof, and preservative-free and solvent-free aqueous polymer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114195930A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124666A (en) * | 2022-07-12 | 2022-09-30 | 德爱威（中国）有限公司 | Acrylic acid-potassium silicate copolymer emulsion, preparation and application thereof, breathable flame-retardant weather-resistant inorganic coating for exterior wall and preparation thereof |
| CN116554741A (en) * | 2023-05-25 | 2023-08-08 | 广东嘉宝莉科技材料有限公司 | Emulsion paint capable of being rolled and coated once and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2530257A1 (en) * | 1982-07-15 | 1984-01-20 | Centre Nat Etd Spatiales | Improved paints containing potassium silicate |
| CN108676117A (en) * | 2018-05-25 | 2018-10-19 | 北京化工大学 | Waterborne self-crosslinkable cationic copolymer emulsion and its preparation method and application |
| CN109705692A (en) * | 2018-12-31 | 2019-05-03 | 中山市巴德富化工科技有限公司 | A kind of elastic compounded emulsion and preparation method thereof with super contaminated resistance |
| CN110256881A (en) * | 2019-06-21 | 2019-09-20 | 东莞大宝化工制品有限公司 | Inorganic mosquito-proof coating of one kind and preparation method thereof |
-
2021
- 2021-12-29 CN CN202111646742.8A patent/CN114195930A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2530257A1 (en) * | 1982-07-15 | 1984-01-20 | Centre Nat Etd Spatiales | Improved paints containing potassium silicate |
| CN108676117A (en) * | 2018-05-25 | 2018-10-19 | 北京化工大学 | Waterborne self-crosslinkable cationic copolymer emulsion and its preparation method and application |
| CN109705692A (en) * | 2018-12-31 | 2019-05-03 | 中山市巴德富化工科技有限公司 | A kind of elastic compounded emulsion and preparation method thereof with super contaminated resistance |
| CN110256881A (en) * | 2019-06-21 | 2019-09-20 | 东莞大宝化工制品有限公司 | Inorganic mosquito-proof coating of one kind and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115124666A (en) * | 2022-07-12 | 2022-09-30 | 德爱威（中国）有限公司 | Acrylic acid-potassium silicate copolymer emulsion, preparation and application thereof, breathable flame-retardant weather-resistant inorganic coating for exterior wall and preparation thereof |
| CN115124666B (en) * | 2022-07-12 | 2024-01-26 | 德爱威（中国）有限公司 | Acrylic acid-potassium silicate copolymer emulsion, preparation and application thereof, and breathable flame-retardant weather-resistant exterior wall inorganic coating and preparation thereof |
| CN116554741A (en) * | 2023-05-25 | 2023-08-08 | 广东嘉宝莉科技材料有限公司 | Emulsion paint capable of being rolled and coated once and preparation method thereof |
| CN116554741B (en) * | 2023-05-25 | 2024-06-18 | 广东嘉宝莉科技材料有限公司 | Emulsion paint capable of being rolled and coated once and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114195930A (en) | Modified potassium silicate styrene-acrylic emulsion and preparation method thereof, and preservative-free and solvent-free aqueous polymer material and preparation method thereof | |
| EP1749067B1 (en) | Coating agents that are devoid of preservatives, method for their production and use thereof | |
| CN109942756B (en) | Styrene-acrylic emulsion with gradient damping structure and bakeable thick-paste type water-based damping coating and preparation | |
| CN111592803B (en) | Bio-based water-based paint and preparation method and application thereof | |
| CN102020905A (en) | One-component water-based semi-gloss varnish and preparation method thereof | |
| CN111518449B (en) | Water-based epoxy hybrid acrylic acid self-crosslinking quick-drying paint used in high humidity environment and preparation method thereof | |
| CN107488375B (en) | High-filling water-based transparent putty for woodware and preparation method thereof | |
| CN106752590A (en) | A kind of anti-formaldehyde novolac of aqueous wooden ware and preparation method thereof | |
| AU2018247305A1 (en) | Coating composition with improved liquid stain repellency | |
| CN105567030A (en) | Waterborne carpentry paint | |
| CN109535973B (en) | Two-component aqueous polyurethane coating composition with thixotropic flow characteristic and preparation method thereof | |
| CN105131763A (en) | Water paint for wood furniture and preparation method thereof | |
| CN109370353B (en) | Environment-friendly fluorine modified styrene-acrylic emulsion coating used in winter and preparation method thereof | |
| CN107641402B (en) | Nano flame-retardant stone paint and preparation method thereof | |
| KR102061351B1 (en) | Thickener for Aqueous Paint with Improved Workability and Paint Properties and Aqueous Paint Containing the Same | |
| CN108276849A (en) | Anti- scribble interior wall water-in-water multicolor coating of one kind and preparation method thereof | |
| EP1706460B1 (en) | Aqueous coating substances comprising increased volumetric concentrations of pigment | |
| CN111154346B (en) | Acrylate emulsion for building interior wall coating and preparation method and application thereof | |
| CN114790352A (en) | Moisture-proof interior wall coating and preparation method thereof | |
| CN111100521B (en) | Interior wall coating with lasting mosquito repelling effect and preparation method thereof | |
| CN109897519B (en) | Water-based paint for refitted vehicle and preparation method thereof | |
| EP1481995B1 (en) | Aqueous copolymer dispersions, method for their production and coating compositions containing them | |
| KR102135600B1 (en) | Coating composition with improved liquid stain repellency and process for making the same | |
| CN115433495B (en) | Environment-friendly emulsion paint and preparation method thereof | |
| CN109627820A (en) | A kind of formula of antimicrobial form composite latex coatings |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220318 |
|
| RJ01 | Rejection of invention patent application after publication |