CN103059235B - Epoxy modified water-soluble acrylic resin, and preparation method and application thereof - Google Patents
Epoxy modified water-soluble acrylic resin, and preparation method and application thereof Download PDFInfo
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- CN103059235B CN103059235B CN201310035655.8A CN201310035655A CN103059235B CN 103059235 B CN103059235 B CN 103059235B CN 201310035655 A CN201310035655 A CN 201310035655A CN 103059235 B CN103059235 B CN 103059235B
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 53
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004593 Epoxy Substances 0.000 title abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 150000002924 oxiranes Chemical class 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 13
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 10
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 abstract description 13
- 239000012986 chain transfer agent Substances 0.000 abstract description 10
- 239000003999 initiator Substances 0.000 abstract description 9
- 150000001412 amines Chemical class 0.000 abstract description 7
- 238000007385 chemical modification Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 6
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical group CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229920003180 amino resin Polymers 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an epoxy modified water-soluble acrylic resin, and a preparation method and application thereof. The preparation method of the epoxy modified water-soluble acrylic resin comprises the following steps: adding organic solvent, methyl methacrylate, butyl acrylate, methacrylic acid, 2-hydroxyethyl acrylate, chain-transfer agent and initiator into a reaction kettle, and heating to react; and adding organic solvent, methyl methacrylate, butyl acrylate, unsaturated double-bond terminated epoxy resin, methacrylic acid, 2-hydroxyethyl acrylate, chain-transfer agent and initiator into a dropwise addition tank, uniformly stirring, dropwisely adding into the reaction kettle, keeping the temperature, cooling, and adding an amine neutralizer for neutralization, thereby obtaining the epoxy modified water-soluble acrylic resin. The epoxy resin is introduced to the chain segment of the water-soluble acrylic resin by chemical modification, so that the epoxy modified water-soluble acrylic resin has better comprehensive properties, and better satisfies the requirements of customers.
Description
Technical field
The invention belongs to field of surface coatings, particularly relate to a kind of epoxide modified water soluble acrylic resin and its preparation method and application.
Background technology
Along with the pay attention to day by day of people's environmental pollution, resource consumption problem, many producers are also stricter to the requirement of water-based industrial paint.Traditional water soluble acrylic resin's coating has the advantages such as gloss is high, good weatherability, but also there are some defects such as chemicals-resistant, poor adhesive force.Therefore, prior art has yet to be improved and developed.In order to improve the performance of coating further, water-borne acrylic resin is more by adopting other resins or monomer to carry out modification to it.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of epoxide modified water soluble acrylic resin and its preparation method and application.For current water soluble acrylic resin patience, adhere to hypodynamic shortcoming, develop a kind of there is the advantages such as good chemical proofing, salt spray resistance, sticking power is good nontoxic, odorless, the water soluble acrylic resin of environment-friendly epoxy modification of not firing.
Technical scheme of the present invention is as follows:
An epoxide modified water soluble acrylic resin's preparation method, wherein, comprises the following steps:
In a kettle., add organic solvent 30 ~ 35 parts, methyl methacrylate 1 ~ 2 part, butyl acrylate 2-5 part, methacrylic acid 0.1-0.5 part, Hydroxyethyl acrylate 0.27-0.45 part, chain-transfer agent 0.04-0.12 part, initiator 0.08-0.2 part, is warming up to 70 ~ 85 DEG C of reaction 15-20 minute;
In dropping cylinder, add organic solvent 15-20 part, methyl methacrylate 9-18 part, butyl acrylate 13-20, epoxy resin 5-15 part of unsaturated double-bond end-blocking, methacrylic acid 1.9-4.5 part, Hydroxyethyl acrylate 2.73-4.55 part, chain-transfer agent 0.06-0.18 part, initiator 0.12-0.3 part, stir, dropped in 3 ~ 4 hours in reactor, at 80 ~ 85 DEG C, continue insulation 1-3 hour, be cooled to 50 ~ 60 DEG C, add the neutralization of 2-5 part amine neutralizing agent, obtain epoxide modified water soluble acrylic resin.
The preparation method of described epoxide modified water soluble acrylic resin, wherein, described chain-transfer agent is mercaptoethanol or lauryl mercaptan.
The preparation method of described epoxide modified water soluble acrylic resin, wherein, described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate.
The preparation method of described epoxide modified water soluble acrylic resin, wherein, described amine neutralizing agent is triethylamine or N, N-dimethylethanolamine.
The preparation method of described epoxide modified water soluble acrylic resin, wherein, described organic solvent is propylene glycol monobutyl ether or diethylene glycol monobutyl ether.
A kind of epoxide modified water soluble acrylic resin, wherein, described epoxide modified water soluble acrylic resin adopts the preparation method of epoxide modified water soluble acrylic resin as above to prepare.
An epoxide modified water soluble acrylic resin's as above application, wherein, by described epoxide modified water soluble acrylic resin for the preparation of coating.
Beneficial effect: by the method for chemical modification, epoxy resin is incorporated on water soluble acrylic resin's segment in the present invention, thus epoxy resin chemical resistance is good, sticking power good and acrylic resin good weatherability, second-order transition temperature is adjustable, glossiness is good etc., and advantages is got up, make its over-all properties more excellent, better meet the demand in market.
Accompanying drawing explanation
Fig. 1 is the preparation flow of the epoxy resin of unsaturated double-bond end-blocking in the present invention.
Embodiment
The invention provides a kind of epoxide modified water soluble acrylic resin and its preparation method and application, for making object of the present invention, technical scheme and effect clearly, clearly, the present invention is described in more detail below.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Epoxy resin is because of the not aliphatic hydroxide radical of facile hydrolysis and ehter bond containing polarity is high, " hygrometric state " strong adhesion after film forming, chemical-resistant are good, and on conventional epoxy molecule main chain, rigid phenyl group and flexible hydroxyl are alternately arranged, and have the features such as good temperature tolerance, dimensional stability, Physical Mechanical after film forming.So epoxy resin is incorporated on water soluble acrylic resin's segment by the method for chemical modification in the present invention, thus epoxy resin chemical resistance is good, sticking power good and acrylic resin good weatherability, second-order transition temperature is adjustable, glossiness is good etc., and advantages is got up, make its over-all properties more excellent, meet the demand in market better.
Particularly, the present invention introduces polymerisable epoxy resin in the process of Acrylic Acid Monomer radical polymerization, thus imparts the chemical proof, tack etc. of acrylic resin brilliance.Epoxy resin adopted in the present invention is the epoxy resin of self-control unsaturated double-bond end-blocking, and as shown in Figure 1, wherein n is 2-10 to its preparation process.In the preparation process of the epoxy resin of described unsaturated double-bond end-blocking, the epoxy resin adopted is E-44 or E-51, the unsaturated acid adopted is methacrylic acid or vinylformic acid, the catalyzer adopted is N, N-dimethylethanolamine, Tetrabutyl amonium bromide, triethylamine or trolamine, the organic solvent of described employing is propyl carbinol, diethylene glycol monobutyl ether or propylene glycol monobutyl ether.
Particularly, its preparation process of epoxy resin of self-control unsaturated double-bond end-blocking provided by the present invention is as follows:
In a kettle., add epoxy resin 60 ~ 70 parts in advance, organic solvent 10 ~ 15 parts, after stirring at being heated to 60 ~ 70 DEG C, be warming up to 100 ~ 120 DEG C; In dropping cylinder, catalyzer 0.3 ~ 0.5 part; Unsaturated acid 10 ~ 15 parts; Organic solvent 10 ~ 15 parts, after stirring, dropped in reactor in 1 ~ 3 hour, insulation reaction is continued 1 ~ 2 hour at 100 ~ 120 DEG C, stopped reaction when system acid number does not change substantially, is cooled to room temperature, i.e. the epoxy resin of obtained unsaturated double-bond end-blocking.
Epoxide modified water soluble acrylic resin provided by the present invention counts by weight, is made up of following component:
The epoxy resin of unsaturated double-bond end-blocking 5 ~ 15 parts; Methyl methacrylate 10 ~ 20 parts; Butyl acrylate 15 ~ 25 parts; Methacrylic acid 2 ~ 5 parts; Hydroxyethyl acrylate 3 ~ 5 parts; Chain-transfer agent 0.1 ~ 0.3 part; Initiator 0.2 ~ 0.5 part; Amine neutralizing agent 2 ~ 5 parts; Organic solvent 45 ~ 55 parts.
Wherein, described chain-transfer agent can be mercaptoethanol or lauryl mercaptan, and described initiator can be peroxidation (two) benzoyl (BPO) or Diisopropyl azodicarboxylate (AIBN).Described amine neutralizing agent can be triethylamine or N, N-dimethylethanolamine, and described organic solvent can be propylene glycol monobutyl ether or diethylene glycol monobutyl ether.
The preparation of described epoxide modified water soluble acrylic resin uses the epoxy resin of unsaturated double-bond end-blocking, acrylate monomer, functional monomer and chain-transfer agent free-radical polymerized in organic solvent, and then with the neutralization of amine neutralizing agent, its concrete steps are as follows:
In a kettle., add organic solvent 30 ~ 35 parts, methyl methacrylate 1 ~ 2 part, butyl acrylate 2-5 part, methacrylic acid 0.1-0.5 part, Hydroxyethyl acrylate 0.27-0.45 part, chain-transfer agent 0.04-0.12 part, initiator 0.08-0.2 part, is warming up to 70 ~ 85 DEG C of reaction 15-20 minute;
In dropping cylinder, add organic solvent 15-20 part, methyl methacrylate 9-18 part, butyl acrylate 13-20, epoxy resin 5-15 part of unsaturated double-bond end-blocking, methacrylic acid 1.9-4.5 part, Hydroxyethyl acrylate 2.73-4.55 part, chain-transfer agent 0.06-0.18 part, initiator 0.12-0.3 part, stir, dropped in 3 ~ 4 hours in reactor, at 80 ~ 85 DEG C, continue insulation 1-3 hour, be cooled to 50 ~ 60 DEG C, add the neutralization of 2-5 part amine neutralizing agent, obtain epoxide modified water soluble acrylic resin.
The epoxide modified water soluble acrylic resin's tool prepared by method provided by the present invention is had the following advantages: (1) smell is little, environmental pollution is little; (2) excellent chemical-resistant, tack; (3) excellent salt fog resistance, acid-fast alkali-proof.
The application of described epoxide modified water soluble acrylic resin is also provided, by described epoxide modified water soluble acrylic resin for the preparation of coating in the present invention.Also provide a kind of in the present invention and be prepared from coating with described epoxide modified water soluble acrylic resin, described coating is counted by weight, comprises following component:
Epoxide modified water soluble acrylic resin 40-60 part, water-compatible amino resin 5-15 part, pigment 20-40 part, dispersion agent 0.4-0.5 part, wetting agent 0.1-0.3 part, defoamer 0.1-0.2 part, flow agent 0.1-0.3 part, deionized water 10-20 part.
Above-mentioned materials is joined in container successively, stirs and can obtain described coating.This epoxide modified water soluble acrylic resin and water-compatible amino resin with the use of, use front dilute with water to disperse, be mainly used in the application of structural metal section bar, glass, during use, volatile matter major part is water, is environmentally friendly machine.Described epoxide modified water soluble acrylic resin is adopted to be prepared from coating after 150 DEG C are toasted 30 minutes, poach 2 hours paint films are non-foaming, do not come off, salt spray resistance 240h change without exception, coating acid resistance, alkali resistance, water tolerance, ageing resistance are excellent, and its excellent combination property, has higher cost performance, and coating of the present invention is water-soluble products, has environment-friendly advantage.
In order to more detailed description preparation method of the present invention, below enumerate several embodiment further description.
Embodiment 1
Prepare the epoxy resin of unsaturated double-bond end-blocking: in a kettle., add E-44 epoxy resin 60 parts in advance, propyl carbinol 13 parts, after stirring at being heated to 70 DEG C, be warming up to 120 DEG C; In dropping cylinder, N, N-dimethylethanolamine 0.3 part; Methacrylic acid 15 parts; Propyl carbinol 10 parts, after stirring, dropped in reactor in 1 hour, and at 100 DEG C, continue insulation reaction 1 hour, stopped reaction when system acid number does not change substantially, is cooled to room temperature, i.e. the epoxy resin of obtained unsaturated double-bond end-blocking.
In another reactor, add diethylene glycol monobutyl ether 30 parts in advance; Methyl methacrylate 1.2 parts; Butyl acrylate 2.9 parts; Methacrylic acid 0.3 part; Hydroxyethyl acrylate 0.39 part; Mercaptoethanol 0.1 part; Benzoyl peroxide 0.2 part, is warming up to 85 DEG C of reactions 15 minutes.
In dropping cylinder, add diethylene glycol monobutyl ether 20 parts; Methyl methacrylate 13.8 parts; Butyl acrylate 17.1 parts; The epoxy resin 5 parts of self-control unsaturated double-bond end-blocking; Methacrylic acid 2.8 parts; Hydroxyethyl acrylate 3.76 parts; Mercaptoethanol 0.15 part; Benzoyl peroxide 0.3 part, stirs, and drops in reactor in 3 ~ 4 hours, continues insulation 1 hour, be cooled to 50 ~ 60 DEG C at 80 ~ 85 DEG C, adds 2 parts of N, N-dimethylethanolamine neutralizations, obtains epoxide modified water soluble acrylic resin.
Embodiment 2
Prepare the epoxy resin of unsaturated double-bond end-blocking: in a kettle., add E-51 epoxy resin 65 parts in advance, diethylene glycol monobutyl ether 10 parts, after stirring at being heated to 65 DEG C, be warming up to 100 DEG C; In dropping cylinder, Tetrabutyl amonium bromide 0.4 part; Methacrylic acid 10 parts; Diethylene glycol monobutyl ether 12 parts, after stirring, dropped in reactor in 2 hours, insulation reaction is continued 1.5 hours at 110 DEG C, stopped reaction when system acid number does not change substantially, is cooled to room temperature, i.e. the epoxy resin of obtained unsaturated double-bond end-blocking.
In reactor, add diethylene glycol monobutyl ether 35 parts in advance; Methyl methacrylate 2 parts; Butyl acrylate 3.9 parts; Methacrylic acid 0.5 part; Hydroxyethyl acrylate 0.45 part; Mercaptoethanol 0.12 part; Benzoyl peroxide 0.08 part, is warming up to 85 DEG C of reactions 15 minutes.
In dropping cylinder, add diethylene glycol monobutyl ether 15 parts; Methyl methacrylate 18 parts; Butyl acrylate 14.1 parts; The epoxy resin 10 parts of self-control unsaturated double-bond end-blocking; Methacrylic acid 4.5 parts; Hydroxyethyl acrylate 4.55 parts; Mercaptoethanol 0.18 part; Benzoyl peroxide 0.12 part, stirs, and drops in reactor in 3 ~ 4 hours, continues insulation 1 hour, be cooled to 50 ~ 60 DEG C at 80 ~ 85 DEG C, adds 3.2 parts of N, N-dimethylethanolamine neutralizations, obtains epoxide modified water soluble acrylic resin.
Embodiment 3
Prepare the epoxy resin of unsaturated double-bond end-blocking: in a kettle., add E-44 epoxy resin 70 parts in advance, propylene glycol monobutyl ether 15 parts, after stirring at being heated to 60 DEG C, be warming up to 110 DEG C; In dropping cylinder, triethylamine 0.5 part; 12 parts, vinylformic acid; Propylene glycol monobutyl ether 15 parts, after stirring, dropped in reactor in 3 hours, and at 120 DEG C, continue insulation reaction 2 hours, stopped reaction when system acid number does not change substantially, is cooled to room temperature, i.e. the epoxy resin of obtained unsaturated double-bond end-blocking.
In reactor, add diethylene glycol monobutyl ether 30 parts in advance; Methyl methacrylate 1.2 parts; Butyl acrylate 2.9 parts; Methacrylic acid 0.3 part; Hydroxyethyl acrylate 0.27 part; Mercaptoethanol 0.04 part; Benzoyl peroxide 0.1 part, is warming up to 85 DEG C of reactions 15 minutes.
In dropping cylinder, add diethylene glycol monobutyl ether 15 parts; Methyl methacrylate 9.8 parts; Butyl acrylate 13.1 parts; The epoxy resin 15 parts of self-control unsaturated double-bond end-blocking; Methacrylic acid 2.8 parts; Hydroxyethyl acrylate 2.73 parts; Mercaptoethanol 0.06 part; Benzoyl peroxide 0.2 part, stirs, and drops in reactor in 3 ~ 4 hours, continues insulation 1 hour, be cooled to 50 ~ 60 DEG C at 80 ~ 85 DEG C, adds 2 parts of N, N-dimethylethanolamine neutralizations, obtains epoxide modified water soluble acrylic resin.
Embodiment 4
Be respectively used to prepare coating 1,2,3 with the epoxide modified water soluble acrylic resin of embodiment 1 ~ 3 gained, wherein, the formula of coating is as shown in table 1.
The formula (kg) of table 1 coating
| Material name | Coating 1 | Coating 2 | Coating 3 |
| Epoxide modified water soluble acrylic resin | 50 | 60 | 40 |
| Water-compatible amino resin (Ineos 717) | 10 | 15 | 5 |
| R902 titanium white | 30 | 25 | 35 |
| 5040(dispersion agent) | 0.45 | 0.4 | 0.5 |
| 875(wetting agent) | 0.2 | 0.1 | 0.3 |
| Tego810 (defoamer) | 0.15 | 0.1 | 0.2 |
| BYK333(flow agent) | 0.2 | 0.3 | 0.1 |
| Deionized water | 15 | 10 | 20 |
The Performance Detection of coating 1 ~ 3 is as shown in table 2, and wherein, baking condition is 150 DEG C, 30 minutes.
The performance test results of table 2 coating
| Test item | Index | Coating 1 | Coating 2 | Coating 3 |
| Sticking power (cross-hatching) | ≤1 | 0 | 0 | 0 |
| Hardness | ≥1H | 2H | 2H | 3H |
| Resistance to bend(ing) | ≤2 | 1 | 2 | 2 |
| Shock-resistance/cm | 50 | 50 | 50 | 50 |
| Acid resistance (2%H2SO4,24h) | Non-foaming, do not come off | Pass through | Pass through | Pass through |
| Alkali resistance (5%NaOH, 24h) | Non-foaming, do not come off | Pass through | Pass through | Pass through |
| Water tolerance (150h) | Non-foaming, do not come off | Pass through | Pass through | Pass through |
| Poach (100 DEG C) | >=2h, non-foaming, do not come off | Pass through | Pass through | Pass through |
| Salt fog resistance | 240h is non-foaming, does not come off, non-corrosive | Pass through | Pass through | Pass through |
| Ageing resistance (1000h, gloss loss) | ≤10% | Pass through | Pass through | Pass through |
From the test result in table 2, the coating that epoxide modified water soluble acrylic resin of the present invention joins is after 150 DEG C are toasted 30 minutes, poach 2 hours paint films are non-foaming, do not come off, salt spray resistance change without exception in 240 hours, coating acid resistance, alkali resistance, water tolerance, ageing resistance can be passed through, its excellent combination property, there is higher cost performance, and the present invention is water-soluble products, has environment-friendly advantage.
Should be understood that, application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (3)
1. an epoxide modified water soluble acrylic resin's preparation method, is characterized in that, comprises the following steps:
Prepare the epoxy resin of unsaturated double-bond end-blocking: in a kettle., add E-44 epoxy resin 60 parts in advance, propyl carbinol 13 parts, after stirring at being heated to 70 DEG C, be warming up to 120 DEG C; In dropping cylinder, N, N-dimethylethanolamine 0.3 part; Methacrylic acid 15 parts; Propyl carbinol 10 parts, after stirring, dropped in reactor in 1 hour, and at 100 DEG C, continue insulation reaction 1 hour, stopped reaction when system acid number does not change substantially, is cooled to room temperature, i.e. the epoxy resin of obtained unsaturated double-bond end-blocking;
In another reactor, add diethylene glycol monobutyl ether 30 parts, methyl methacrylate 1.2 parts, butyl acrylate 2.9 parts, methacrylic acid 0.3 part, Hydroxyethyl acrylate 0.39 part, mercaptoethanol 0.1 part, benzoyl peroxide 0.2 part, is warming up to 85 DEG C of reactions 15 minutes;
In dropping cylinder, add diethylene glycol monobutyl ether 20 parts, methyl methacrylate 13.8 parts, butyl acrylate 17.1, the epoxy resin of unsaturated double-bond end-blocking 5 parts, methacrylic acid 2.8 parts, Hydroxyethyl acrylate 3.76 parts, mercaptoethanol 0.15 part, benzoyl peroxide 0.3 part, stir, dropped in 3 ~ 4 hours in reactor, at 80 ~ 85 DEG C, continue insulation 1 hour, be cooled to 50 ~ 60 DEG C, add 2 parts of N, N-dimethylethanolamine neutralizations, obtain epoxide modified water soluble acrylic resin.
2. an epoxide modified water soluble acrylic resin, is characterized in that, described epoxide modified water soluble acrylic resin adopts the preparation method of epoxide modified water soluble acrylic resin as claimed in claim 1 to prepare.
3. an epoxide modified water soluble acrylic resin's as claimed in claim 2 application, is characterized in that, by described epoxide modified water soluble acrylic resin for the preparation of coating.
Priority Applications (1)
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| CN103910825B (en) * | 2014-03-28 | 2016-11-23 | 江门市三木化工有限公司 | A kind of resin and preparation method thereof |
| CN104513344A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Waterborne epoxy modified acrylic resin and aqueous dispersion thereof |
| CN105524231A (en) * | 2015-12-21 | 2016-04-27 | 桂林市和鑫防水装饰材料有限公司 | Epoxy modified acrylic resin for sealant and preparing method thereof |
| CN106366987A (en) * | 2016-08-25 | 2017-02-01 | 安徽大松树脂有限公司 | High-elasticity wear-resistant modified adhesive and preparation method thereof |
| CN106905467B (en) * | 2017-03-22 | 2021-09-03 | 上海展辰涂料有限公司 | Preparation method of self-drying epoxy group water-soluble acrylic resin |
| CN108467452A (en) * | 2018-02-09 | 2018-08-31 | 宁波安工电子有限公司 | A kind of acrylic acid fluororesin and preparation method thereof |
| CN113461874A (en) * | 2021-07-27 | 2021-10-01 | 珠海市卓和化工科技有限公司 | Synthetic method of epoxy modified thermoplastic acrylic resin |
| CN115651504B (en) * | 2022-11-15 | 2023-07-14 | 东莞中瀛涂料有限公司 | Low-VOC primer and preparation method and application thereof |
| CN115873184A (en) * | 2023-01-03 | 2023-03-31 | 郑州中科新兴产业技术研究院 | Epoxy resin modified waterborne acrylic resin dispersion and preparation method thereof |
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| CN101429267A (en) * | 2008-12-25 | 2009-05-13 | 海洋化工研究院 | Preparation and uses of epoxy/acrylic acid hybridisation emulsion |
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