CN115612033A - Organic silicon modified epoxy acrylic resin emulsion and preparation method thereof - Google Patents
Organic silicon modified epoxy acrylic resin emulsion and preparation method thereof Download PDFInfo
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- CN115612033A CN115612033A CN202211312889.8A CN202211312889A CN115612033A CN 115612033 A CN115612033 A CN 115612033A CN 202211312889 A CN202211312889 A CN 202211312889A CN 115612033 A CN115612033 A CN 115612033A
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- acrylic resin
- epoxy acrylic
- organic silicon
- modified epoxy
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 72
- 239000000839 emulsion Substances 0.000 title claims abstract description 71
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 37
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 36
- 239000010703 silicon Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004945 emulsification Methods 0.000 title description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 40
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 40
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- -1 vinyl siloxane Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 23
- 229920006243 acrylic copolymer Polymers 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 5
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 claims description 3
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000003973 paint Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 12
- 230000032683 aging Effects 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Epoxy Resins (AREA)
Abstract
The application relates to the technical field of coatings, in particular to an organic silicon modified epoxy acrylic resin emulsion and a preparation method thereof. The organic silicon modified epoxy acrylic resin emulsion comprises the following raw materials: 20-30 parts of epoxy resin, 4-8 parts of vinyl siloxane, 6-12 parts of acrylic monomer, 2-4 parts of styrene, 10-15 parts of alcohol ether solvent, 0.2-0.5 part of catalyst, 0.3-0.6 part of initiator, 2-4 parts of neutralizer, 2-4 parts of emulsifier and 45-55 parts of deionized water. The application provides an organosilicon modified epoxy acrylic resin emulsion which has the advantages of high film hardness, good weather resistance, excellent heat resistance, good water resistance, strong adhesive force and the like, and the prepared emulsion has excellent comprehensive performance and greatly enlarged application range.
Description
Technical Field
The application relates to the technical field of coatings, in particular to an organic silicon modified epoxy acrylic resin emulsion and a preparation method thereof.
Background
The acrylic resin paint has good durability, transparency and stability, is widely applied in the fields of buildings, automobiles, airplanes and the like, but the pure acrylic resin emulsion has the defects of poor paint film hardness, poor heat resistance, insufficient adhesive force and the like, so that the better application of the acrylic resin emulsion is limited. The epoxy resin has the advantages of high hardness, good adhesive force and the like, and the problem of poor hardness and poor adhesive force of an acrylic resin paint film can be solved by copolymerizing the epoxy resin with the acrylic resin, but the problem of poor heat resistance of the epoxy acrylic resin still exists, so that the practical application of the epoxy acrylic resin is seriously influenced.
Disclosure of Invention
In order to solve the problem that the epoxy acrylic resin proposed in the background art has poor heat resistance, the application provides an organosilicon modified epoxy acrylic resin emulsion and a preparation method thereof.
In a first aspect, the organosilicon modified epoxy acrylic resin emulsion provided by the application adopts the following technical scheme: an organosilicon modified epoxy acrylic resin emulsion comprises the following raw materials: 20-30 parts of epoxy resin, 4-8 parts of vinyl siloxane, 6-12 parts of acrylic monomer, 2-4 parts of styrene, 10-15 parts of alcohol ether solvent, 0.2-0.5 part of catalyst, 0.3-0.6 part of initiator, 2-4 parts of neutralizer, 2-4 parts of emulsifier and 45-55 parts of deionized water.
By adopting the technical scheme, the chain end group of the epoxy resin is bonded with the alkoxy in the vinyl siloxane, so that the end part of the epoxy resin is introduced with the vinyl, and then the vinyl in the epoxy resin, the acrylic monomer and the styrene are subjected to copolymerization reaction to form a crosslinked three-dimensional network structure, so that the organosilicon modified epoxy acrylic resin is obtained. The organosilicon modified epoxy acrylic resin which combines the characteristics of siloxane resin, epoxy resin and acrylic resin has the advantages of high film hardness, good weather resistance, excellent heat resistance, good waterproofness, strong adhesive force and the like, and the prepared emulsion has excellent comprehensive performance and greatly enlarged application range.
The epoxy resin contains a benzene ring structure with better rigidity, which is beneficial to improving the rigidity of the copolymer, and the formed cross-linked network structure is also beneficial to improving the strength of the resin, so that the hardness of an emulsion paint film is greatly improved, and the vinyl siloxane has higher Si-O bond energy in molecules, so that the copolymer obtains excellent heat resistance and chemical stability, and is beneficial to expanding the temperature application range of the emulsion and the coating, and the Si-O bond has longer bond length and larger bond angle compared with a carbon-carbon bond, so that the flexibility of the copolymer can be improved. The acrylic resin has the characteristics of high transparency, good stability and the like, and various excellent properties of the acrylic resin are fully exerted in the copolymer resin by adopting the copolymerization of the acrylic monomer and the organic silicon epoxy resin, and in addition, styrene is introduced for copolymerization reaction and is a hard monomer, so that the hardness of the copolymer is favorably improved, and the production cost is reduced. The alcohol ether solvent is used as a solvent for the crosslinking reaction and the copolymerization reaction, and can dilute the concentration of reactants, so that the reactants are uniformly distributed in the solvent for reaction; the catalyst is used for providing protons, catalyzing the crosslinking reaction of the epoxy resin and the vinyl siloxane and promoting the formation of epoxy organic silicon prepolymer; the initiator is used for generating free radicals and initiating the copolymerization reaction of the epoxy organic silicon prepolymer, the acrylic monomer and the styrene; the emulsifier emulsifies and disperses the generated organic silicon modified epoxy acrylic resin in deionized water to form emulsion, and the neutralizer regulates the pH value of the emulsion to ensure that the emulsion is in a stable state.
Preferably, the vinyl siloxane is selected from one or more of vinyl triethoxysilane, vinyl trimethoxysilane, methyl vinyl dimethoxysilane, and vinyl triisopropoxysilane.
By adopting the technical scheme, the vinyltriethoxysilane, the vinyltrimethoxysilane, the methyl vinyl dimethoxysilane and the vinyl triisopropoxysilane all contain vinyl and alkoxy, the alkoxy absorbs water in the air and is hydrolyzed to generate hydroxyl, the hydroxyl is bonded and crosslinked with an epoxy group of the epoxy resin, and the vinyl is copolymerized with the acrylic monomer and the styrene, so that the vinyl siloxane can be used as a bridge to combine the epoxy resin and the acrylic monomer, and the crosslinking degree and the strength of the copolymer are favorably improved.
Preferably, the acrylic monomer comprises 4-8 parts of methacrylic acid and 2-4 parts of butyl acrylate.
By adopting the technical scheme, methacrylic acid is a hard monomer, butyl acrylate is a soft monomer, and methacrylic acid and butyl acrylate are adopted and added in the copolymerization process at the same time, so that the hardness of the copolymer can be adjusted, and the hardness of an emulsion paint film is improved; the methacrylic acid contains carboxyl, so that the methacrylic acid can be bonded with an epoxy group for reaction, and the adhesion performance of the emulsion coating can be improved.
Preferably, the alcohol ether solvent is at least one of propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether or ethylene glycol propyl ether.
By adopting the technical scheme, the alcohol ether solvents such as propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether or ethylene glycol propyl ether belong to low-toxicity alcohol ether substances, have no strong pungent smell, are safe and environment-friendly, have ether groups and hydroxyl groups in the molecular structure, have excellent solubility, can be used as a solvent for the reaction of epoxy resin and polyvinyl siloxane, reduce the viscosity of the epoxy resin, facilitate the subsequent copolymerization reaction and the emulsification step, and improve the stability of emulsion and the surface smoothness and the flatness of a paint film.
Preferably, the catalyst is boron trifluoride diethyl etherate.
Preferably, the initiator is ammonium persulfate, sodium persulfate, potassium persulfate or H 2 O 2 。
By adopting the technical scheme, the persulfate and the H 2 O 2 The initiator is a common water-soluble initiator, contains peroxy groups, is easy to generate free radicals under the heating action, and initiates unsaturated monomers to polymerize; the increase of the amount of the initiator can cause the relative molecular weight of the polymer to be reduced, the viscosity and the particle size of the emulsion to be reduced, if the amount of the initiator is too much, some properties of the emulsion can not meet practical requirements, and too much persulfate and hydrogen peroxide can cause adverse effects on human bodies and the environment, so that the control of the addition amount of the initiator has important effects on the properties of the emulsion, the human health and the environment.
Preferably, the neutralizing agent is at least one of sodium carbonate and sodium hydroxide, and the emulsifier is alkylphenol ethoxylates.
By adopting the technical scheme, the carboxylic acid is neutralized by using a neutralizing agent sodium carbonate or sodium hydroxide to form salt, so that the viscosity can be improved, and the emulsion is in an alkalescent state and is favorable for maintaining long-term stability; the alkylphenol polyoxyethylene is a nonionic surfactant, has stable chemical property and acid and alkali resistance, has both oleophilic groups and hydrophilic groups in the molecular structure, and can enable the polymer to be well dispersed in water to form oil-in-water emulsion.
In a second aspect, the preparation method provided by the present application adopts the following technical scheme:
the preparation method is used for preparing the organic silicon modified epoxy acrylic resin emulsion and comprises the following steps: preparing a prepolymer: mixing the epoxy resin, the vinyl siloxane, the alcohol ether solvent and the catalyst, and stirring and reacting at 80-100 ℃ for 3-6h to prepare an epoxy organosilicon prepolymer;
preparation of a copolymer: adding the acrylic monomer, the styrene, the initiator, the neutralizer and the emulsifier into the epoxy organic silicon prepolymer, and stirring and reacting for 4-6h at 100-110 ℃ to obtain an organic silicon epoxy acrylic copolymer; preparing an emulsion: and cooling the organic silicon epoxy acrylic copolymer to 60 ℃, adding the deionized water to disperse the organic silicon epoxy acrylic copolymer into the deionized water, and filtering to obtain the emulsion.
By adopting the technical scheme, firstly, the epoxy resin and the vinyl siloxane are dissolved in an alcohol ether solvent, and the epoxy resin and the vinyl siloxane are crosslinked to form the epoxy organic silicon prepolymer at the temperature of 80-100 ℃ under the action of a catalyst. Then adding acrylic monomers and styrene into the epoxy organic silicon prepolymer to enable the prepolymer, the acrylic monomers and the styrene to generate copolymerization reaction under the action of an initiator to prepare the organic silicon epoxy acrylic copolymer, adopting a neutralizer to control the pH value of the mixture, and uniformly mixing an emulsifier and the copolymer to be beneficial to the subsequent emulsification step. And cooling the mixture to 60 ℃ to enable the polymerization reaction to tend to be balanced and stable, and then adding deionized water and dispersing to enable the organosilicon epoxy acrylic acid copolymer to be emulsified in the deionized water to form emulsion.
Preferably, the stirring speed in the step of preparing the prepolymer is 450 to 550rpm, and the stirring speed in the step of preparing the copolymer is 500 to 650rpm; the dispersion rotation speed in the step of preparing the emulsion is 260-380rpm, and the dispersion time is 40-80min.
By adopting the technical scheme, the reaction is relatively mild when the prepolymer is prepared, the stirring speed required to be used is relatively low, the reaction is rapid when the copolymer is prepared, the stirring speed is required to be accelerated to reduce the appearance of a sudden polymerization phenomenon, and the rotating speed is reduced when the emulsion is prepared to ensure that the resin is emulsified in deionized water to form the emulsion, and the foam is not easily generated.
In summary, compared with the related art, the invention has the following beneficial effects:
1. the invention provides an organosilicon modified epoxy acrylic resin emulsion, which combines the characteristics of siloxane resin, epoxy resin and acrylic resin, has the advantages of high film hardness, good weather resistance, excellent heat resistance, good water resistance, strong adhesive force and the like, can be cured by a water-soluble or water-emulsion epoxy curing agent, has the film hardness of not less than 2H, can resist aging for 1000H, solves the problem of poor weather resistance of a common epoxy film, has excellent high temperature resistance, and can be used in the range of 150-200 ℃.
2. The invention provides a preparation method of an organosilicon modified epoxy acrylic resin emulsion, which is simple and convenient to operate, easy to control conditions and suitable for large-scale industrial production, and the prepared emulsion has excellent comprehensive performance and greatly enlarged application range.
Detailed Description
The present application will be described in further detail with reference to examples. The special description is as follows: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the starting materials used in the following examples were obtained from ordinary commercial sources unless otherwise specified.
Example 1
Preparing a prepolymer: adding E-44 type epoxy resin, vinyl siloxane, propylene glycol monomethyl ether and boron trifluoride diethyl etherate into a four-neck flask, mixing, stirring at 90 ℃ for 4 hours at the rotating speed of 500rpm, and preparing the epoxy organosilicon prepolymer.
Preparation of the copolymer: adding methacrylic acid, butyl acrylate, styrene, ammonium persulfate, sodium carbonate and alkylphenol polyoxyethylene into the epoxy organic silicon prepolymer, and stirring and reacting for 5 hours at 110 ℃ at the rotating speed of 650rpm to prepare an organic silicon epoxy acrylic copolymer;
preparing an emulsion: cooling the organosilicon epoxy acrylic copolymer to 60 ℃, adding deionized water to disperse the organosilicon epoxy acrylic copolymer into the deionized water, wherein the rotating speed is 340rpm, the dispersion time is 60min, and filtering to obtain the emulsion.
Examples 2 to 5
Examples 2-5 differ from example 1 in that: the weight parts of the raw material components are different, and the specific conditions are shown in table 1.
TABLE 1 (unit: parts by weight)
Example 6
The present example differs from example 1 in that: the selected epoxy resin is E-51 type.
Example 7
The present example differs from example 1 in that: the weight portion of the E-44 type epoxy resin is 20 portions.
Example 8
This example differs from example 1 in that: the weight portion of the E-44 type epoxy resin is 30 portions.
Example 9
The present example differs from example 1 in that: the vinyl siloxane selected is vinyl trimethoxy silane.
Example 10
This example differs from example 1 in that: the vinyl siloxane selected is methylvinyldimethoxysilane.
Example 11
The present example differs from example 1 in that: the weight portion of the vinyltriethoxysilane is 4 portions.
Example 12
This example differs from example 1 in that: the weight portion of the vinyltriethoxysilane is 8 portions.
Example 13
This example differs from example 1 in that: the butyl acrylate was replaced with an equal amount of methacrylic acid.
Example 14
This example differs from example 1 in that: methacrylic acid was replaced by the same amount of butyl acrylate.
Example 15
This example differs from example 1 in that: the weight fraction of methacrylic acid was 4 parts.
Example 16
This example differs from example 1 in that: the weight fraction of methacrylic acid was 8 parts.
Example 17
This example differs from example 1 in that: the weight fraction of styrene is 4 parts.
Example 18
Preparing a prepolymer: adding E-44 type epoxy resin, vinyl triethoxy siloxane, propylene glycol monomethyl ether and boron trifluoride diethyl etherate into a four-neck flask, mixing, stirring at 90 ℃ for 4 hours at the rotating speed of 500rpm, and preparing the epoxy organosilicon prepolymer.
Preparation of a copolymer: adding methacrylic acid, butyl acrylate, styrene, ammonium persulfate, sodium carbonate and alkylphenol polyoxyethylene into the epoxy organic silicon prepolymer, and stirring and reacting for 5 hours at 110 ℃ at the rotating speed of 450rpm to prepare an organic silicon epoxy acrylic copolymer;
preparing an emulsion: cooling the organic silicon epoxy acrylic copolymer to 60 ℃, adding deionized water to disperse the organic silicon epoxy acrylic copolymer into the deionized water, wherein the rotating speed is 340rpm, the dispersion time is 60min, and filtering to obtain the emulsion.
Example 19
Preparing a prepolymer: adding E-44 type epoxy resin, vinyl triethoxy siloxane, propylene glycol monomethyl ether and boron trifluoride diethyl etherate into a four-neck flask, mixing, stirring at 90 ℃ for 4 hours at the rotating speed of 500rpm, and preparing the epoxy organosilicon prepolymer.
Preparation of the copolymer: adding methacrylic acid, butyl acrylate, styrene, ammonium persulfate, sodium carbonate and alkylphenol polyoxyethylene into the epoxy organic silicon prepolymer, and stirring and reacting for 5 hours at 110 ℃ at the rotating speed of 650rpm to prepare an organic silicon epoxy acrylic copolymer;
preparing an emulsion: cooling the organic silicon epoxy acrylic copolymer to 60 ℃, adding deionized water to disperse the organic silicon epoxy acrylic copolymer into the deionized water, wherein the rotating speed is 340rpm, the dispersion time is 35min, and filtering to obtain the emulsion.
Example 20
Preparing a prepolymer: adding E-44 type epoxy resin, vinyl triethoxy siloxane, propylene glycol monomethyl ether and boron trifluoride diethyl etherate into a four-neck flask, mixing, stirring at 90 ℃ for 4 hours at the rotating speed of 500rpm, and preparing the epoxy organosilicon prepolymer.
Preparation of a copolymer: adding methacrylic acid, butyl acrylate, styrene, ammonium persulfate, sodium carbonate and alkylphenol polyoxyethylene into the epoxy organic silicon prepolymer, and stirring and reacting for 5 hours at 110 ℃ at the rotating speed of 650rpm to prepare an organic silicon epoxy acrylic copolymer;
preparing an emulsion: cooling the organic silicon epoxy acrylic copolymer to 60 ℃, adding deionized water to disperse the organic silicon epoxy acrylic copolymer into the deionized water, wherein the rotating speed is 340rpm, the dispersion time is 80min, and filtering to obtain the emulsion.
Comparative example 1
Preparation of the copolymer: adding E-44 type epoxy resin, vinyl triethoxy siloxane, propylene glycol methyl ether, boron trifluoride ethyl ether, methacrylic acid, butyl acrylate, styrene, ammonium persulfate, sodium carbonate and alkylphenol polyoxyethylene ether into a four-neck flask, mixing, stirring at 110 ℃ for reacting for 8 hours at the rotating speed of 650rpm, and preparing the organosilicon epoxy acrylic copolymer;
preparing an emulsion: cooling the organosilicon epoxy acrylic copolymer to 60 ℃, adding deionized water to disperse the organosilicon epoxy acrylic copolymer into the deionized water, wherein the rotating speed is 340rpm, the dispersion time is 60min, and filtering to obtain the emulsion.
Comparative example 2
This comparative example differs from example 1 in that: the weight portion of the E-44 type epoxy resin is 10 portions.
Comparative example 3
The comparative example differs from example 1 in that: the weight portion of the E-44 type epoxy resin is 35 portions.
Comparative example 4
The comparative example differs from example 1 in that: the weight portion of the vinyltriethoxysilane is 2 portions.
Comparative example 5
This comparative example differs from example 1 in that: the weight portion of the vinyltriethoxysilane is 10 portions.
Performance detection test:
after surface treatment was carried out on a steel plate (150 mm. Times.70 mm. Times.3 mm) as a substrate, the emulsions prepared in examples 1 to 20 and comparative examples 1 to 5 were sprayed on the surface of the steel plate as a test plate with a paint film thickness of 10 to 300. Mu.m. After the test boards were maintained for a certain period of time, performance tests were carried out according to the following test standards, the results of which are shown in Table 2.
After the test board is maintained for 168 hours, QUV artificial aging test is carried out: GB/T1767-1989, the longer the time is, the better the ageing resistance is;
maintaining the test board for 48h, and then carrying out paint film hardness test, wherein GB 6739-2006 has the highest hardness range of 9B-9H and 9H;
and (3) maintaining the test board for 168h, and then performing a high-temperature resistance test: GB/T1740-2007, the grade is 0-3, and the 0 grade has the best high temperature resistance;
and (3) carrying out adhesion test after the test board is maintained for 48 hours: GB/T9286-1998, the grade is 0-5, and the best adhesive force is 0.
TABLE 2
According to the embodiments 1-20 and the combination of the table 2, the organosilicon modified epoxy acrylic resin emulsion prepared by the method combines the characteristics of siloxane resin, epoxy resin and acrylic resin, has the advantages of high film hardness, good weather resistance, excellent heat resistance, strong adhesive force and the like, can form a film with hardness of more than or equal to 2H, can resist aging for 1000H, solves the problem of poor weather resistance of common epoxy films, and has excellent high temperature resistance.
Specifically, the E-51 type epoxy resin is adopted in the example 6, and compared with the E-44 type epoxy resin adopted in the example 1, the aging resistance of the prepared emulsion paint film is reduced, the hardness of the paint film is improved, probably because the epoxy degree of the E-51 type epoxy resin is higher, the epoxy group is easy to oxidize, and the annular structure of the epoxy group is beneficial to improving the rigidity of the paint film. Compared with the embodiment 1, the addition amount of the epoxy resin in the embodiment 7 is reduced, the hardness of the emulsion paint film is reduced and the adhesive force is also reduced due to the reduction of the cyclic structures such as benzene rings and the like, but the high temperature resistance of the low molecular weight bisphenol A epoxy resin is not good, the epoxy component is reduced, and the high temperature resistance of the emulsion paint film is enhanced by increasing other components; in example 8, the addition amount of the epoxy resin is increased, and the hardness of the emulsion paint film is correspondingly increased, but the aging resistance is weakened; on the basis of comparison examples 2 and 3, the more the addition amount of the epoxy resin is, the poorer the aging resistance and the high temperature resistance of the paint film is, and the higher the hardness of the paint film is, the better the adhesion is.
Example 9 the vinyltrimethoxysilane is adopted to replace the vinyltriethoxysilane in example 1, and the properties of the prepared paint film are not changed greatly; example 10 using methylvinyldimethoxysilane produced coatings with reduced high temperature resistance due to reduced siloxane content compared to vinyltrimethoxysilane in example 9. According to examples 10 and 11 and comparative examples 4 and 5 in combination with Table 2, it can be seen that the higher the amount of vinyltriethoxysilane added, the higher the content of silicon-oxygen bonds in the copolymer, which leads to a consequent improvement in the high temperature resistance of the paint film, but that an excessive amount of vinyltriethoxysilane leads to a reduction in the adhesion of the paint film.
The acrylic monomer of example 13 used only the hard monomer methacrylic acid to produce an emulsion having increased film hardness, the acrylic monomer of example 14 used only the soft monomer butyl acrylate to produce an emulsion having decreased film hardness, and the absence of methacrylic acid resulted in decreased film adhesion. Combining examples 1, 15, 16 and table 2, it can be seen that the higher the amount of hard monomer methacrylic acid added, the higher the paint film hardness of the emulsion can be made. According to examples 1 and 17, the higher the hard monomer styrene content, the higher the emulsion paint film hardness and the emulsion production cost can be reduced to some extent, but the aging resistance and adhesion of the paint film will be reduced.
Compared with example 1, example 18 has a lower stirring rate in the step of preparing the copolymer, which may cause that the vinyl groups of the acrylic monomer, the styrene and the epoxy silicone prepolymer cannot be uniformly and sufficiently copolymerized, and the crosslinking degree and the network structure formation of the copolymer are influenced, thereby influencing the paint film adhesion; in example 19, the dispersion time in the emulsion preparation step is short, so that the copolymer cannot be uniformly and stably dispersed, and the aging resistance, hardness and adhesion of a paint film are reduced; the dispersion time is suitably prolonged in the step of preparing the emulsion as in example 20, which is advantageous in improving the aging resistance and adhesion of the paint film.
Comparative example 1 in the preparation of the copolymer, the epoxy resin and the siloxane were directly mixed and copolymerized without pre-polymerizing the epoxy resin and the siloxane, and thus a flash polymerization phenomenon easily occurs, and copolymerization of each reactant is seriously affected, resulting in failure to form the copolymer and the emulsion.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (9)
1. The organic silicon modified epoxy acrylic resin emulsion is characterized by comprising the following raw materials: 20-30 parts of epoxy resin, 4-8 parts of vinyl siloxane, 6-12 parts of acrylic monomer, 2-4 parts of styrene, 10-15 parts of alcohol ether solvent, 0.2-0.5 part of catalyst, 0.3-0.6 part of initiator, 2-4 parts of neutralizer, 2-4 parts of emulsifier and 45-55 parts of deionized water.
2. The silicone-modified epoxy acrylic resin emulsion according to claim 1, characterized in that: the vinyl siloxane is selected from one or more of vinyl triethoxysilane, vinyl trimethoxysilane, methyl vinyl dimethoxysilane and vinyl triisopropoxysilane.
3. The silicone-modified epoxy acrylic resin emulsion according to claim 1, characterized in that: the acrylic monomer comprises 4-8 parts of methacrylic acid and 2-4 parts of butyl acrylate.
4. The silicone-modified epoxy acrylic resin emulsion according to claim 1, characterized in that: the alcohol ether solvent is at least one of propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether or ethylene glycol propyl ether.
5. The silicone-modified epoxy acrylic resin emulsion according to claim 1, characterized in that: the catalyst is boron trifluoride diethyl etherate.
6. The silicone-modified epoxy acrylic resin emulsion according to claim 1, characterized in that: the initiator is ammonium persulfate, sodium persulfate, potassium persulfate or H 2 O 2 。
7. The silicone-modified epoxy acrylic resin emulsion according to claim 1, characterized in that: the neutralizer is at least one of sodium carbonate and sodium hydroxide, and the emulsifier is alkylphenol polyoxyethylene.
8. A preparation method for preparing the organosilicon modified epoxy acrylic resin emulsion as claimed in any one of claims 1 to 7, comprising the following steps:
preparing a prepolymer: mixing the epoxy resin, the vinyl siloxane, the alcohol ether solvent and the catalyst, and stirring and reacting at 80-100 ℃ for 3-6h to prepare an epoxy organosilicon prepolymer;
preparation of the copolymer: adding the acrylic monomer, the styrene, the initiator, the neutralizer and the emulsifier into the epoxy organic silicon prepolymer, and stirring and reacting for 4-6h at 100-110 ℃ to obtain an organic silicon epoxy acrylic copolymer;
preparing an emulsion: and cooling the organic silicon epoxy acrylic copolymer to 60 ℃, adding the deionized water to disperse the organic silicon epoxy acrylic copolymer into the deionized water, and filtering to obtain the emulsion.
9. A method of manufacturing as claimed in claim 8, wherein: the stirring speed in the step of preparing the prepolymer is 450-550rpm, and the stirring speed in the step of preparing the copolymer is 500-650rpm; the dispersion rotation speed in the step of preparing the emulsion is 260-380rpm, and the dispersion time is 40-80min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009104936A2 (en) * | 2008-02-23 | 2009-08-27 | 전북대학교산학협력단 | Water dispersible redispersible polyurethane/acryl copolymer hybrid resin composition and process for preparing same |
| CN103059313A (en) * | 2012-12-17 | 2013-04-24 | 中山大桥化工集团有限公司 | Method for preparing organosilicon modified acrylic resin |
| CN104356321A (en) * | 2014-11-13 | 2015-02-18 | 广州中国科学院工业技术研究院 | Water-based polysiloxane modified epoxy resin and preparation method thereof |
| CN105419551A (en) * | 2015-11-30 | 2016-03-23 | 何晨旭 | Epoxy resin emulsion for waterborne coating and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009104936A2 (en) * | 2008-02-23 | 2009-08-27 | 전북대학교산학협력단 | Water dispersible redispersible polyurethane/acryl copolymer hybrid resin composition and process for preparing same |
| CN103059313A (en) * | 2012-12-17 | 2013-04-24 | 中山大桥化工集团有限公司 | Method for preparing organosilicon modified acrylic resin |
| CN104356321A (en) * | 2014-11-13 | 2015-02-18 | 广州中国科学院工业技术研究院 | Water-based polysiloxane modified epoxy resin and preparation method thereof |
| CN105419551A (en) * | 2015-11-30 | 2016-03-23 | 何晨旭 | Epoxy resin emulsion for waterborne coating and preparation method thereof |
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