CN103059235A - 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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- CN103059235A CN103059235A CN2013100356558A CN201310035655A CN103059235A CN 103059235 A CN103059235 A CN 103059235A CN 2013100356558 A CN2013100356558 A CN 2013100356558A CN 201310035655 A CN201310035655 A CN 201310035655A CN 103059235 A CN103059235 A CN 103059235A
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- acrylic resin
- soluble acrylic
- modified water
- water soluble
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 57
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 57
- 239000004593 Epoxy Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 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
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 10
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 9
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 7
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical group CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims 11
- 238000007385 chemical modification Methods 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract 2
- 229920000647 polyepoxide Polymers 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 150000002924 oxiranes Chemical class 0.000 description 31
- 239000002253 acid Substances 0.000 description 9
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical class CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000005395 methacrylic acid group Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 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
- 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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient 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
- 230000006872 improvement Effects 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
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
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- 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, relate in particular 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 has some defectives such as chemicals-resistant, poor adhesive force.Therefore, prior art has yet to be improved and developed.In order further to improve the performance of coating, water-borne acrylic resin more is by adopting other resins or monomer that it is carried out modification.
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 present water soluble acrylic resin's patience, adhere to hypodynamic shortcoming, the water soluble acrylic resin of the environment-friendly epoxy modification of developed a kind of nontoxic, odorless with advantages such as good chemical proofing, salt spray resistance, sticking power are good, not firing.
Technical scheme of the present invention is as follows:
A kind of epoxide modified water soluble acrylic resin's preparation method wherein, may further comprise the steps:
In reactor, add 30 ~ 35 parts of organic solvents, 1 ~ 2 part of methyl methacrylate, 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 ℃ of reactions 15-20 minute;
In dripping cylinder, add organic solvent 15-20 part, methyl methacrylate 9-18 part, butyl acrylate 13-20, Resins, epoxy 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, in 3～4 hours, drop in the reactor, be incubated 1-3 hour 80～85 ℃ of lower continuation, be cooled to 50～60 ℃, add the neutralization of 2-5 part amine neutralizing agent, obtain epoxide modified water soluble acrylic resin.
Described epoxide modified water soluble acrylic resin's preparation method, wherein, described chain-transfer agent is mercaptoethanol or lauryl mercaptan.
Described epoxide modified water soluble acrylic resin's preparation method, wherein, described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate.
Described epoxide modified water soluble acrylic resin's preparation method, wherein, described amine neutralizing agent is triethylamine or N, the N-dimethylethanolamine.
Described epoxide modified water soluble acrylic resin's preparation method, 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 aforesaid epoxide modified water soluble acrylic resin's preparation method to prepare.
A kind of aforesaid epoxide modified water soluble acrylic resin's application, wherein, with described epoxide modified water soluble acrylic resin for the preparation of coating.
Beneficial effect: the method by chemical modification among the present invention is incorporated into Resins, epoxy on water soluble acrylic resin's segment, thereby good the Resins, epoxy chemical resistance, sticking power is good and the 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.
Description of drawings
Fig. 1 is the preparation flow of the Resins, epoxy of the unsaturated double-bond end-blocking among the present invention.
Embodiment
The invention provides a kind of epoxide modified water soluble acrylic resin and its preparation method and application, clearer, clear and definite for making purpose of the present invention, technical scheme and effect, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Resins, epoxy is because containing aliphatic hydroxide radical and the ehter bond of the high not facile hydrolysis of polarity, " hygrometric state " strong adhesion after the film forming, chemical-resistant are good, and rigidity phenyl and flexible hydroxyl alternative arrangement on the Resins, epoxy molecular backbone chain commonly used have the characteristics such as good temperature tolerance, dimensional stability, Physical Mechanical after the film forming.So the method by chemical modification among the present invention is incorporated into Resins, epoxy on water soluble acrylic resin's segment, thereby good the Resins, epoxy chemical resistance, sticking power is good and the 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 the demand of satisfying the market.
Particularly, the present invention introduces polymerisable Resins, epoxy in the process of Acrylic Acid Monomer radical polymerization, thereby has given the chemical proof, tack etc. of acrylic resin brilliance.The Resins, epoxy that adopts in the present invention is the Resins, epoxy of self-control unsaturated double-bond end-blocking, its preparation process as shown in Figure 1, wherein n is 2-10.In the preparation process of the Resins, epoxy of described unsaturated double-bond end-blocking, the Resins, epoxy that adopts is E-44 or E-51, the unsaturated acid that adopts is methacrylic acid or vinylformic acid, the catalyzer that adopts is N, N-dimethylethanolamine, Tetrabutyl amonium bromide, triethylamine or trolamine, the organic solvent of described employing are propyl carbinol, diethylene glycol monobutyl ether or propylene glycol monobutyl ether.
Particularly, its preparation process of Resins, epoxy of self-control unsaturated double-bond end-blocking provided by the present invention is as follows:
In reactor, add in advance 60～70 parts of Resins, epoxy, 10～15 parts of organic solvents, be heated to stir under 60～70 ℃ after, be warming up to 100～120 ℃; In dripping cylinder, 0.3～0.5 part of catalyzer; 10～15 parts of unsaturated acid; 10～15 parts of organic solvents after stirring, dropped in the reactor in 1～3 hour, under 100～120 ℃, continued insulation reaction 1～2 hour, stopped reaction when the system acid number for the treatment of does not change substantially is cooled to room temperature, namely makes the Resins, epoxy of unsaturated double-bond end-blocking.
Epoxide modified water soluble acrylic resin provided by the present invention counts by weight, is made by following component:
5～15 parts of the Resins, epoxy of unsaturated double-bond end-blocking; 10～20 parts of methyl methacrylates; 15～25 parts of butyl acrylates; 2～5 parts of methacrylic acids; 3～5 parts of Hydroxyethyl acrylates; 0.1～0.3 part of chain-transfer agent; 0.2～0.5 part of initiator; 2～5 parts of amine neutralizing agents; 45 ~ 55 parts of organic solvents.
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, the N-dimethylethanolamine, and described organic solvent can be propylene glycol monobutyl ether or diethylene glycol monobutyl ether.
Described epoxide modified water soluble acrylic resin's preparation is free-radical polymerized in organic solvent with Resins, epoxy, acrylate monomer, functional monomer and the chain-transfer agent of unsaturated double-bond end-blocking, and then with the neutralization of amine neutralizing agent, its concrete steps are as follows:
In reactor, add 30 ~ 35 parts of organic solvents, 1 ~ 2 part of methyl methacrylate, 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 ℃ of reactions 15-20 minute;
In dripping cylinder, add organic solvent 15-20 part, methyl methacrylate 9-18 part, butyl acrylate 13-20, Resins, epoxy 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, in 3～4 hours, drop in the reactor, be incubated 1-3 hour 80～85 ℃ of lower continuation, be cooled to 50～60 ℃, add the neutralization of 2-5 part amine neutralizing agent, obtain epoxide modified water soluble acrylic resin.
The epoxide modified water soluble acrylic resin who prepares by method provided by the present invention has following advantage: (1) smell is little, environmental pollution is little; (2) excellent chemical-resistant, tack; (3) good salt fog resistance, acid-fast alkali-proof.
Described epoxide modified water soluble acrylic resin's application also is provided among the present invention, with described epoxide modified water soluble acrylic resin for the preparation of coating.Also provide the described epoxide modified water soluble acrylic resin of a kind of usefulness to be prepared from coating among the present invention, 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 the container successively, and stirring to obtain described coating.This epoxide modified water soluble acrylic resin and water-compatible amino resin are used in conjunction with, and dilute with water disperses before using, and is mainly used in the application of structural metal section bar, glass, and the volatile matter major part is water when using, and is environmentally friendly machine.Adopt described epoxide modified water soluble acrylic resin be prepared from coating through 150 ℃ the baking 30 minutes after, 2 hours paint films of poach are non-foaming, do not come off, salt spray resistance 240h is without unusual variation, coating acid resistance, alkali resistance, water tolerance, ageing resistance excellence, its excellent combination property has higher cost performance, and coating of the present invention is water-soluble products, has environment-friendly advantage.
For more detailed description preparation method of the present invention, below enumerate several embodiment further descriptions.
The Resins, epoxy of preparation unsaturated double-bond end-blocking: in reactor, add in advance 60 parts of E-44 Resins, epoxy, 13 parts of propyl carbinols, be heated to stir under 70 ℃ after, be warming up to 120 ℃; In dripping cylinder, N, 0.3 part of N-dimethylethanolamine; 15 parts of methacrylic acids; 10 parts of propyl carbinols after stirring, dropped in the reactor in 1 hour, continued insulation reaction 1 hour under 100 ℃, and stopped reaction when the system acid number for the treatment of does not change substantially is cooled to room temperature, namely makes the Resins, epoxy of unsaturated double-bond end-blocking.
In another reactor, add in advance 30 parts of diethylene glycol monobutyl ethers; 1.2 parts of methyl methacrylates; 2.9 parts of butyl acrylates; 0.3 part of methacrylic acid; 0.39 part of Hydroxyethyl acrylate; 0.1 part of mercaptoethanol; 0.2 part of benzoyl peroxide is warming up to 85 ℃ of reactions 15 minutes.
In dripping cylinder, add 20 parts of diethylene glycol monobutyl ethers; 13.8 parts of methyl methacrylates; 17.1 parts of butyl acrylates; 5 parts of the Resins, epoxy of self-control unsaturated double-bond end-blocking; 2.8 parts of methacrylic acids; 3.76 parts of Hydroxyethyl acrylates; 0.15 part of mercaptoethanol; 0.3 part of benzoyl peroxide stirs, and drops in the reactor in 3～4 hours, is incubated 1 hour 80～85 ℃ of lower continuation, is cooled to 50～60 ℃, adds 2 parts of N, and the neutralization of N-dimethylethanolamine obtains epoxide modified water soluble acrylic resin.
Embodiment 2
The Resins, epoxy of preparation unsaturated double-bond end-blocking: in reactor, add in advance 65 parts of E-51 Resins, epoxy, 10 parts of diethylene glycol monobutyl ethers, be heated to stir under 65 ℃ after, be warming up to 100 ℃; In dripping cylinder, 0.4 part of Tetrabutyl amonium bromide; 10 parts of methacrylic acids; 12 parts of diethylene glycol monobutyl ethers after stirring, dropped in the reactor in 2 hours, under 110 ℃, continued insulation reaction 1.5 hours, stopped reaction when the system acid number for the treatment of does not change substantially is cooled to room temperature, namely makes the Resins, epoxy of unsaturated double-bond end-blocking.
In reactor, add in advance 35 parts of diethylene glycol monobutyl ethers; 2 parts of methyl methacrylates; 3.9 parts of butyl acrylates; 0.5 part of methacrylic acid; 0.45 part of Hydroxyethyl acrylate; 0.12 part of mercaptoethanol; 0.08 part of benzoyl peroxide is warming up to 85 ℃ of reactions 15 minutes.
In dripping cylinder, add 15 parts of diethylene glycol monobutyl ethers; 18 parts of methyl methacrylates; 14.1 parts of butyl acrylates; 10 parts of the Resins, epoxy of self-control unsaturated double-bond end-blocking; 4.5 parts of methacrylic acids; 4.55 parts of Hydroxyethyl acrylates; 0.18 part of mercaptoethanol; 0.12 part of benzoyl peroxide stirs, and drops in the reactor in 3～4 hours, is incubated 1 hour 80～85 ℃ of lower continuation, is cooled to 50～60 ℃, adds 3.2 parts of N, and the neutralization of N-dimethylethanolamine obtains epoxide modified water soluble acrylic resin.
Embodiment 3
The Resins, epoxy of preparation unsaturated double-bond end-blocking: in reactor, add in advance 70 parts of E-44 Resins, epoxy, 15 parts of propylene glycol monobutyl ethers, be heated to stir under 60 ℃ after, be warming up to 110 ℃; In dripping cylinder, 0.5 part of triethylamine; 12 parts in vinylformic acid; 15 parts of propylene glycol monobutyl ethers after stirring, dropped in the reactor in 3 hours, continued insulation reaction 2 hours under 120 ℃, and stopped reaction when the system acid number for the treatment of does not change substantially is cooled to room temperature, namely makes the Resins, epoxy of unsaturated double-bond end-blocking.
In reactor, add in advance 30 parts of diethylene glycol monobutyl ethers; 1.2 parts of methyl methacrylates; 2.9 parts of butyl acrylates; 0.3 part of methacrylic acid; 0.27 part of Hydroxyethyl acrylate; 0.04 part of mercaptoethanol; 0.1 part of benzoyl peroxide is warming up to 85 ℃ of reactions 15 minutes.
In dripping cylinder, add 15 parts of diethylene glycol monobutyl ethers; 9.8 parts of methyl methacrylates; 13.1 parts of butyl acrylates; 15 parts of the Resins, epoxy of self-control unsaturated double-bond end-blocking; 2.8 parts of methacrylic acids; 2.73 parts of Hydroxyethyl acrylates; 0.06 part of mercaptoethanol; 0.2 part of benzoyl peroxide stirs, and drops in the reactor in 3～4 hours, is incubated 1 hour 80～85 ℃ of lower continuation, is cooled to 50～60 ℃, adds 2 parts of N, and the neutralization of N-dimethylethanolamine obtains epoxide modified water soluble acrylic resin.
Embodiment 4
Epoxide modified water soluble acrylic resin with embodiment 1 ~ 3 gained is respectively applied to prepare coating 1,2,3, and wherein, the prescription of coating is as shown in table 1.
The prescription of table 1 coating (kg)
| 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 |
| The R902 titanium white | 30 | 25 | 35 |
| The 5040(dispersion agent) | 0.45 | 0.4 | 0.5 |
| The 875(wetting agent) | 0.2 | 0.1 | 0.3 |
| Tego810 (defoamer) | 0.15 | 0.1 | 0.2 |
| The 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 ℃, 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 | By | By | By |
| Alkali resistance (5%NaOH, 24h) | Non-foaming, do not come off | By | By | By |
| Water tolerance (150h) | Non-foaming, do not come off | By | By | By |
| Poach (100 ℃) | 〉=2h, non-foaming, do not come off | By | By | By |
| Salt fog resistance | 240h is non-foaming, does not come off non-corrosive | By | By | By |
| Ageing resistance (1000h, loss of gloss rate) | ≤10% | By | By | By |
By the test result in the table 2 as seen, after the coating that epoxide modified water soluble acrylic resin of the present invention joins toasts 30 minutes through 150 ℃, 2 hours paint films of poach are non-foaming, do not come off, without unusual variation can pass through in 240 hours by coating acid resistance, alkali resistance, water tolerance, ageing resistance for salt spray resistance, its excellent combination property, have 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 giving an example, and for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (7)
1. an epoxide modified water soluble acrylic resin preparation method is characterized in that, may further comprise the steps:
In reactor, add 30 ~ 35 parts of organic solvents, 1 ~ 2 part of methyl methacrylate, 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 ℃ of reactions 15-20 minute;
In dripping cylinder, add organic solvent 15-20 part, methyl methacrylate 9-18 part, butyl acrylate 13-20, Resins, epoxy 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, in 3～4 hours, drop in the reactor, be incubated 1-3 hour 80～85 ℃ of lower continuation, be cooled to 50～60 ℃, add the neutralization of 2-5 part amine neutralizing agent, obtain epoxide modified water soluble acrylic resin.
2. epoxide modified water soluble acrylic resin's according to claim 1 preparation method is characterized in that, described chain-transfer agent is mercaptoethanol or lauryl mercaptan.
3. epoxide modified water soluble acrylic resin's according to claim 1 preparation method is characterized in that, described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate.
4. epoxide modified water soluble acrylic resin's according to claim 1 preparation method is characterized in that, described amine neutralizing agent is triethylamine or N, the N-dimethylethanolamine.
5. epoxide modified water soluble acrylic resin's according to claim 1 preparation method is characterized in that, described organic solvent is propylene glycol monobutyl ether or diethylene glycol monobutyl ether.
6. an epoxide modified water soluble acrylic resin is characterized in that, described epoxide modified water soluble acrylic resin adopts the preparation method such as the arbitrary described epoxide modified water soluble acrylic resin of claim 1 ~ 5 to prepare.
7. an epoxide modified water soluble acrylic resin as claimed in claim 6 application is characterized in that, with described epoxide modified water soluble acrylic resin for the preparation of coating.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103910825A (en) * | 2014-03-28 | 2014-07-09 | 江门市三木化工有限公司 | Novel 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 |
| CN106905467A (en) * | 2017-03-22 | 2017-06-30 | 上海展辰涂料有限公司 | A kind of preparation method of self-drying type epoxy radicals 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 |
| CN115651504A (en) * | 2022-11-15 | 2023-01-31 | 东莞中瀛涂料有限公司 | Low-VOC primer and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429267A (en) * | 2008-12-25 | 2009-05-13 | 海洋化工研究院 | Preparation and uses of epoxy/acrylic acid hybridisation emulsion |
-
2013
- 2013-01-30 CN CN201310035655.8A patent/CN103059235B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429267A (en) * | 2008-12-25 | 2009-05-13 | 海洋化工研究院 | Preparation and uses of epoxy/acrylic acid hybridisation emulsion |
Non-Patent Citations (1)
| Title |
|---|
| 刘旭等: "水性油墨用环氧改性水性丙烯酸树脂的合成", 《包装工程》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103910825A (en) * | 2014-03-28 | 2014-07-09 | 江门市三木化工有限公司 | Novel resin and preparation method thereof |
| 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 |
| CN106905467A (en) * | 2017-03-22 | 2017-06-30 | 上海展辰涂料有限公司 | A kind of preparation method of self-drying type epoxy radicals 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 |
| CN115651504A (en) * | 2022-11-15 | 2023-01-31 | 东莞中瀛涂料有限公司 | Low-VOC primer and preparation method and application thereof |
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| CN103059235B (en) | 2015-07-15 |
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