CN117586596A - Water-based epoxy modified acrylic resin and preparation method thereof - Google Patents
Water-based epoxy modified acrylic resin and preparation method thereof Download PDFInfo
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- CN117586596A CN117586596A CN202311655053.2A CN202311655053A CN117586596A CN 117586596 A CN117586596 A CN 117586596A CN 202311655053 A CN202311655053 A CN 202311655053A CN 117586596 A CN117586596 A CN 117586596A
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- acrylic resin
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- epoxy
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 111
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 111
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000004593 Epoxy Substances 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 41
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 27
- 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 claims description 25
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 15
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- -1 epoxy resins E-51 Chemical compound 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 230000007613 environmental effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000373 fatty alcohol group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a water-based epoxy modified acrylic resin and a preparation method thereof, which belong to the technical field of acrylic resins and preparation methods thereof. Bisphenol A type epoxy resins such as epoxy resins E-51, E-44 and E-20 have excellent mechanical properties and chemical stability, and these properties are preserved and reinforced in the composite material.
Description
Technical Field
The invention relates to the technical field of acrylic resin and a preparation method thereof, in particular to a waterborne epoxy modified acrylic resin and a preparation method thereof.
Background
In the modern coating and adhesive industry, resins are critical components, which have a decisive influence on the properties of the products. Conventional resin materials such as pure acrylic resin and epoxy resin have advantages, but also have significant limitations. For example, acrylic resins, although fast drying and good in color, are weak in terms of mechanical strength and chemical resistance; while epoxy resins have excellent adhesion and chemical stability, the drying process is slow and the environmental suitability is limited. In addition, the conventional solvent-based resins pose a threat to the environment due to the emission of highly Volatile Organic Compounds (VOCs).
With the improvement of environmental protection standards and the increase of performance requirements, development of a novel resin material is urgently needed, which can combine the advantages of acrylic resin and epoxy resin and overcome the disadvantages thereof. In addition, the novel resin has wider application range, is suitable for various environmental conditions and meets the requirements of the current environmental protection regulations
Based on the background and the needs, the invention provides an aqueous epoxy modified acrylic resin. The resin has the advantages that the epoxy resin and the acrylic resin are compounded, and auxiliary materials such as the silane coupling agent, the emulsifier and the like are added, so that the limitation of a single resin system is innovatively solved, and the environmental protection performance and the application applicability of the resin are greatly improved. Particularly in the fields of coating materials, adhesives, composite materials and the like, the resin exhibits excellent performance including improved mechanical properties, enhanced interfacial adhesion and remarkable environmental protection properties.
Disclosure of Invention
The invention provides a waterborne epoxy modified acrylic resin and a preparation method thereof, wherein the waterborne epoxy modified acrylic resin has better stability, dispersibility and film forming property, meets the related application requirements, and has the following content;
the first object of the present invention is to provide an aqueous epoxy-modified acrylic resin, which is technically characterized by comprising, by weight, 30-50 parts of an acrylic resin, 3-5 parts of an epoxy resin, 0.5-1 part of a silane coupling agent, 3-5 parts of an emulsifier and 10-20 parts of water.
In order to better realize the technical scheme, the acrylic resin in the waterborne epoxy modified acrylic resin is prepared from the following raw materials in percentage by mass: 21.7wt% of methyl methacrylate, 6.5wt% of hydroxypropyl acrylate, 8.7wt% of acrylic acid, 13wt% of butyl acrylate, 4.3wt% of epoxy resin E-51, 0.5wt% of azobisisobutyronitrile, 34.7wt% of ethylene glycol monobutyl ether, 4.3wt% of ammonia water and 5.3wt% of deionized water.
In order to better realize the technical scheme, the preparation method of the acrylic resin in the water-based epoxy modified acrylic resin comprises the following steps:
step one, adding ethylene glycol monobutyl ether and epoxy resin E-51 into a reaction kettle, introducing nitrogen, and then heating to 80-90 ℃;
step two, uniformly mixing methyl methacrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate and part of azodiisobutyronitrile, and adding into a dripping pump;
step three, when the heating temperature of the reaction kettle in the step one is continuously up to 110-120 ℃, dropwise adding the mixture in the step two into the reaction kettle in the step one, and preserving heat for 0.5-1h after finishing dropwise adding for 2.5-3 h;
fourthly, when the heat preservation in the third step is finished, adding one part of azodiisobutyronitrile, continuing to preserve heat for 1-1.5 hours, and after the heat preservation is finished, adding one part of azodiisobutyronitrile, and continuing to preserve heat for 1-1.5 hours;
and fifthly, when the heat preservation in the step four is finished, cooling to 45-50 ℃, adding ammonia water and deionized water, adjusting to be neutral, and stirring to obtain the acrylic resin.
In order to better realize the technical scheme, the epoxy resin in the aqueous epoxy modified acrylic resin is at least one of bisphenol A type epoxy resin E-51, bisphenol A type epoxy resin E-44 and bisphenol A type epoxy resin E-20.
In order to better realize the technical scheme, the silane coupling agent in the waterborne epoxy modified acrylic resin is at least one of methyltrimethoxysilane, methyltriethoxysilane and dimethyldimethoxysilane.
In order to better realize the technical scheme, the emulsifier in the aqueous epoxy modified acrylic resin is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty alcohol polyoxyethylene ether.
The second object of the invention is to provide a preparation method of the water-based epoxy modified acrylic resin, which is technically characterized by comprising the following steps:
step one, accurately weighing acrylic resin, epoxy resin, silane coupling agent and emulsifier;
step two, uniformly mixing acrylic resin and epoxy resin, and stirring in a stirrer for 20-40min to obtain a mixture A;
step three, adding a silane coupling agent into the mixture A in the step two, and then continuously stirring for 20-40min to obtain a mixture B;
step four, adding an emulsifying agent into the mixture B in the step three, and then continuing stirring for 20-40min to obtain a mixture C;
and fifthly, adding water into the mixture C, and uniformly stirring to obtain the water-based epoxy modified acrylic resin.
In order to better solve the technical scheme, the stirring speed of the mixture A in the second step in the preparation method of the water-based epoxy modified acrylic resin is 1000-1200rmp.
In order to better solve the technical scheme, the stirring speed of the mixture B in the third step in the preparation method of the water-based epoxy modified acrylic resin is 3000-3600rmp.
In order to better solve the technical scheme, the stirring speed of the mixture C in the fourth step in the preparation method of the waterborne epoxy modified acrylic resin is 3600-4000rmp.
Compared with the prior art, the water-based epoxy modified acrylic resin and the preparation method thereof can achieve the following beneficial effects:
1. improving mechanical properties and chemical resistance: due to the addition of the epoxy resin, the modified resin has remarkable improvement in hardness, bonding strength and chemical resistance. Bisphenol A type epoxy resins such as epoxy resins E-51, E-44 and E-20 have excellent mechanical properties and chemical stability, and these properties are preserved and reinforced in the composite material.
2. Improving the environmental adaptability: by adjusting the composition of the acrylic resin (e.g., methyl methacrylate, hydroxypropyl acrylate, etc.), the characteristics of the resin can be tailored to different environmental conditions and application requirements. For example, increased weatherability, temperature resistance, or reduced VOC emissions.
3. After the acrylic resin is subjected to epoxy modification, the compatibility of the acrylic resin and the epoxy resin is improved, the mechanical property of the coating is obviously enhanced, and the acrylic resin and the epoxy resin can be mutually inserted and penetrated under the interaction of the acrylic resin and the epoxy resin to form a more compact structure, so that the overall performance of the coating is improved.
4. Enhancing interfacial adhesion: the addition of the silane coupling agent can improve the interfacial adhesion of the resin to the filler or the substrate. Silane coupling agents such as methyltrimethoxysilane, etc., enhance the overall structural integrity of the material by chemically reacting with the resin and the substrate surface.
5. The environmental protection performance is enhanced: because water is used as a solvent, the waterborne epoxy modified acrylic resin has less influence on the environment compared with the traditional solvent type epoxy resin. The VOC emission is reduced, and the environment protection requirement is met.
6. High efficiency of the preparation method: by precisely controlling the reaction conditions (such as temperature, stirring speed, etc.) and the ratio of raw materials, a resin having consistent properties can be efficiently and stably produced, which is particularly important for industrial-scale production.
7. Wide application field: due to the excellent comprehensive properties, the modified resin is suitable for the fields of various coatings, adhesives, composite materials and the like, and is particularly suitable for application occasions requiring high weather resistance, chemical resistance and environmental protection.
In summary, the waterborne epoxy modified acrylic resin provided by the invention improves the performance, also considers the environmental protection and the production efficiency, and is suitable for various high-requirement industrial applications.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An aqueous silicon-containing epoxy modified acrylic tree comprises 40kg of acrylic resin, 3kg of epoxy resin, 0.75kg of silane coupling agent, 4g of emulsifier and 15kg of water.
Further, the acrylic resin in the aqueous epoxy modified acrylic resin of the embodiment is prepared from the following raw materials in percentage by mass: 21.7wt% of methyl methacrylate, 6.5wt% of hydroxypropyl acrylate, 8.7wt% of acrylic acid, 13wt% of butyl acrylate, 4.3wt% of epoxy resin E-51, 0.5wt% of azobisisobutyronitrile, 34.7wt% of ethylene glycol monobutyl ether, 4.3wt% of ammonia water and 5.3wt% of deionized water.
Further, the preparation method of the acrylic resin in the aqueous epoxy modified acrylic resin in the embodiment is as follows:
step one, adding ethylene glycol monobutyl ether and epoxy resin E-51 into a reaction kettle, introducing nitrogen, and then heating to 80 ℃;
step two, uniformly mixing methyl methacrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate and part of azodiisobutyronitrile, and adding into a dripping pump;
step three, after the temperature of the reaction kettle in the step one is continuously increased to 110 ℃, dropwise adding the mixture in the step two into the reaction kettle in the step one, and preserving heat for 1h after 2.5h of dropwise adding;
step four, when the heat preservation in the step three is finished, adding one part of azodiisobutyronitrile, continuing to preserve heat for 1h, and after the heat preservation is finished, adding one part of azodiisobutyronitrile, and continuing to preserve heat for 1h;
and fifthly, when the heat preservation in the step four is finished, cooling to 47.5 ℃, adding ammonia water and deionized water, and stirring to obtain the acrylic resin.
Further, the epoxy resin in the aqueous epoxy modified acrylic resin of the embodiment is bisphenol A type epoxy resin E-51.
Further, the silane coupling agent in the aqueous epoxy modified acrylic resin of the embodiment is methyltrimethoxysilane.
Further, an emulsifier in the aqueous epoxy modified acrylic resin of this embodiment is sodium dodecyl sulfate.
According to the formula, the preparation method of the waterborne epoxy modified acrylic resin comprises the following steps:
step one, accurately weighing acrylic resin, epoxy resin, silane coupling agent and emulsifier;
step two, uniformly mixing acrylic resin and epoxy resin, and stirring in a stirrer for 30min to obtain a mixture A;
step three, adding a silane coupling agent into the mixture A in the step two, and then continuously stirring for 30min to obtain a mixture B;
step four, adding an emulsifying agent into the mixture B in the step three, and then continuing stirring for 30min to obtain a mixture C;
and fifthly, adding water into the mixture C, and uniformly stirring to obtain the water-based epoxy modified acrylic resin.
Further, in the preparation method of the aqueous epoxy modified acrylic resin of the embodiment, the stirring speed of the mixture A in the second step is 1100rmp.
Further, the stirring speed of the mixture B in the third step in the preparation method of the aqueous epoxy-modified acrylic resin of this example was 3400rmp.
Further, in the preparation method of the aqueous epoxy-modified acrylic resin of the present embodiment, the stirring speed of the mixture C in the fourth step was 3800rmp.
Example 2
An aqueous silicon-containing epoxy modified acrylic tree comprises 30kg of acrylic resin, 4kg of epoxy resin, 0.5kg of silane coupling agent, 3kg of emulsifier and 10kg of water.
Further, the acrylic resin in the aqueous epoxy modified acrylic resin of the embodiment is prepared from the following raw materials in percentage by mass: 21.7wt% of methyl methacrylate, 6.5wt% of hydroxypropyl acrylate, 8.7wt% of acrylic acid, 13wt% of butyl acrylate, 4.3wt% of epoxy resin E-51, 0.5wt% of azobisisobutyronitrile, 34.7wt% of ethylene glycol monobutyl ether, 4.3wt% of ammonia water and 5.3wt% of deionized water.
Further, the preparation method of the acrylic resin in the aqueous epoxy modified acrylic resin in the embodiment is as follows:
step one, adding ethylene glycol monobutyl ether and epoxy resin E-51 into a reaction kettle, introducing nitrogen, and then heating to 85 ℃;
step two, uniformly mixing methyl methacrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate and part of azodiisobutyronitrile, and adding into a dripping pump;
step three, after the temperature of the reaction kettle in the step one is continuously increased to 115 ℃, dropwise adding the mixture in the step two into the reaction kettle in the step one, and preserving heat for 0.5h after 3h of dropwise adding;
step four, when the heat preservation in the step three is finished, adding one part of azodiisobutyronitrile, continuing to preserve heat for 1.5 hours, and after the heat preservation is finished, adding one part of azodiisobutyronitrile, and continuing to preserve heat for 1.5 hours;
and fifthly, when the heat preservation in the step four is finished, cooling to 45 ℃, adding ammonia water and deionized water, and stirring to obtain the acrylic resin.
Further, the epoxy resin in the aqueous epoxy modified acrylic resin of the embodiment is bisphenol A type epoxy resin E-44.
Further, in the aqueous epoxy modified acrylic resin of this embodiment, the silane coupling agent is methyltriethoxysilane.
Further, an emulsifier in the aqueous epoxy modified acrylic resin of the embodiment is sodium dodecyl benzene sulfonate.
According to the formula, the preparation method of the waterborne epoxy modified acrylic resin comprises the following steps:
step one, accurately weighing acrylic resin, epoxy resin, silane coupling agent and emulsifier;
step two, uniformly mixing acrylic resin and epoxy resin, and stirring in a stirrer for 20min to obtain a mixture A;
step three, adding a silane coupling agent into the mixture A in the step two, and continuously stirring for 20 minutes to obtain a mixture B;
step four, adding an emulsifying agent into the mixture B in the step three, and then continuing stirring for 20min to obtain a mixture C;
and fifthly, adding water into the mixture C, and uniformly stirring to obtain the water-based epoxy modified acrylic resin.
Further, in the preparation method of the aqueous epoxy modified acrylic resin of the present embodiment, the stirring speed of the mixture A in the second step is 1000rmp.
Further, in the preparation method of the aqueous epoxy modified acrylic resin of the present embodiment, the stirring speed of the mixture B in the third step is 3000rmp.
Further, in the method for producing an aqueous epoxy-modified acrylic resin of this embodiment, the stirring speed of the mixture C in the fourth step was 3600rmp.
Example 3
An aqueous silicon-containing epoxy modified acrylic tree comprises 50kg of acrylic resin, 5kg of epoxy resin, 1kg of silane coupling agent, 5kg of emulsifier and 20kg of water.
Further, the acrylic resin in the aqueous epoxy modified acrylic resin of the embodiment is prepared from the following raw materials in percentage by mass: 21.7wt% of methyl methacrylate, 6.5wt% of hydroxypropyl acrylate, 8.7wt% of acrylic acid, 13wt% of butyl acrylate, 4.3wt% of epoxy resin E-51, 0.5wt% of azobisisobutyronitrile, 34.7wt% of ethylene glycol monobutyl ether, 4.3wt% of ammonia water and 5.3wt% of deionized water.
Further, the preparation method of the acrylic resin in the aqueous epoxy modified acrylic resin in the embodiment is as follows:
step one, adding ethylene glycol monobutyl ether and epoxy resin E-51 into a reaction kettle, introducing nitrogen, and then heating to 90 ℃;
step two, uniformly mixing methyl methacrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate and part of azodiisobutyronitrile, and adding into a dripping pump;
step three, after the temperature of the reaction kettle in the step one is continuously increased to 120 ℃, dropwise adding the mixture in the step two into the reaction kettle in the step one, and preserving heat for 0.5h after 2.5h of dropwise adding;
step four, when the heat preservation in the step three is finished, adding one part of azodiisobutyronitrile, continuing to preserve heat for 1.5 hours, and after the heat preservation is finished, adding one part of azodiisobutyronitrile, and continuing to preserve heat for 1.5 hours;
and fifthly, when the heat preservation in the step four is finished, cooling to 50 ℃, adding ammonia water and deionized water, and stirring to obtain the acrylic resin.
Further, the epoxy resin in the aqueous epoxy modified acrylic resin of the embodiment is bisphenol A type epoxy resin E-20.
Further, the silane coupling agent in the aqueous epoxy modified acrylic resin of the embodiment is dimethyl dimethoxy silane.
Further, an emulsifier in the aqueous epoxy modified acrylic resin of the embodiment is fatty alcohol polyoxyethylene ether.
According to the formula, the preparation method of the waterborne epoxy modified acrylic resin comprises the following steps:
step one, accurately weighing acrylic resin, epoxy resin, silane coupling agent and emulsifier;
step two, uniformly mixing acrylic resin and epoxy resin, and stirring in a stirrer for 40min to obtain a mixture A;
step three, adding a silane coupling agent into the mixture A in the step two, and then continuously stirring for 40min to obtain a mixture B;
step four, adding an emulsifying agent into the mixture B in the step three, and then continuously stirring for 0-40min to obtain a mixture C;
and fifthly, adding water into the mixture C, and uniformly stirring to obtain the water-based epoxy modified acrylic resin.
Further, in the preparation method of the aqueous epoxy modified acrylic resin of the embodiment, the stirring speed of the mixture A in the second step is 1200rmp.
Further, in the preparation method of the aqueous epoxy modified acrylic resin of the present embodiment, the stirring speed of the mixture B in the third step was 3600rmp.
Further, in the preparation method of the aqueous epoxy-modified acrylic resin of the present embodiment, the stirring speed of the mixture C in the fourth step is 4000rmp.
Comparative example 1
The procedure of example 1 was repeated except that "40kg of acrylic resin, 3kg of epoxy resin, 0.75kg of silane coupling agent, 4g of emulsifier and 15kg of water" in example 1 was changed to "40kg of acrylic resin, 2kg of epoxy resin, 4kg of silane coupling agent, 5kg of emulsifier and 15kg of water", and the acrylic resin in the comparative example was not modified.
Comparative example 2
"40kg of acrylic resin, 3kg of epoxy resin, 0.75kg of silane coupling agent, 4g of emulsifier and 15kg of water" in example 1 was "changed to" 40kg of acrylic resin, 6kg of epoxy resin, 0.75kg of silane coupling agent, 4g of emulsifier and 15kg of water ", and the acrylic resin in the comparative example was not modified, and the rest was the same as in example 1.
Test examples
The aqueous epoxy-modified acrylic resins prepared in examples 1 to 3 and comparative examples 1 to 2 were prepared by mixing 85 parts by weight of an aqueous cured varnish, 0.3 part by weight of a defoaming agent Tego 810, 0.2 part by weight of a wetting agent Tego245, 0.5 part by weight of a thickener 1 mm 2020, 0.5 part by weight of a thickener 2pur40, 10 parts by weight of an isocyanate curing agent BAYER 305 and 13.5 parts by weight of water, and then performing performance tests, the test results are shown in table 1:
TABLE 1
| Stability of | Hardness of | Adhesion force | |
| Example 1 | 5 | 2H | 0 |
| Example 2 | 5 | 2H | 0 |
| Example 3 | 5 | 2H | 0 |
| Comparative example 1 | 4 | 2B | 1 |
| Comparative example 2 | 4 | 2H | 3 |
As is clear from Table 1, the aqueous epoxy-modified acrylic resin of example 13 of the present invention has excellent physical properties, stability, hardness and adhesion, and when the amount of the epoxy resin is less than 3 parts by weight, the hardness of the prepared aqueous cured varnish is deteriorated, and when the amount of the epoxy resin is more than 5 parts by weight, the coating adhesion and stability are also deteriorated, although the hardness and other properties can be improved by increasing the content of the epoxy resin.
The foregoing is merely exemplary of the present invention and is not intended to limit the present invention. Various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are to be included in the scope of the claims of the present invention.
Claims (10)
1. The water-based epoxy modified acrylic resin is characterized by comprising, by weight, 30-50 parts of acrylic resin, 3-5 parts of epoxy resin, 0.5-1 part of silane coupling agent, 3-5 parts of emulsifier and 10-20 parts of water.
2. The aqueous epoxy modified acrylic resin according to claim 1, wherein the acrylic resin is prepared from the following raw materials in percentage by mass: 21.7wt% of methyl methacrylate, 6.5wt% of hydroxypropyl acrylate, 8.7wt% of acrylic acid, 13wt% of butyl acrylate, 4.3wt% of epoxy resin E-51, 0.5wt% of azobisisobutyronitrile, 34.7wt% of ethylene glycol monobutyl ether, 4.3wt% of ammonia water and 5.3wt% of deionized water.
3. The aqueous epoxy modified acrylic resin according to claim 2, wherein the acrylic resin is prepared by the following method:
step one, adding ethylene glycol monobutyl ether and epoxy resin E-51 into a reaction kettle, introducing nitrogen, and then heating to 80-90 ℃;
step two, uniformly mixing methyl methacrylate, hydroxypropyl acrylate, acrylic acid, butyl acrylate and part of azodiisobutyronitrile, and adding into a dripping pump;
step three, when the heating temperature of the reaction kettle in the step one is continuously up to 110-120 ℃, dropwise adding the mixture in the step two into the reaction kettle in the step one, and preserving heat for 0.5-1h after finishing dropwise adding for 2.5-3 h;
fourthly, when the heat preservation in the third step is finished, adding one part of azodiisobutyronitrile, continuing to preserve heat for 1-1.5 hours, and after the heat preservation is finished, adding one part of azodiisobutyronitrile, and continuing to preserve heat for 1-1.5 hours;
and fifthly, when the heat preservation in the step four is finished, cooling to 45-50 ℃, adding ammonia water and deionized water, adjusting to be neutral, and stirring to obtain the acrylic resin.
4. The aqueous epoxy modified acrylic resin according to claim 1, wherein the epoxy resin is at least one of bisphenol a type epoxy resin E-51, bisphenol a type epoxy resin E-44 and bisphenol a type epoxy resin E-20.
5. The aqueous epoxy-modified acrylic resin according to claim 1, wherein the silane coupling agent is at least one of methyltrimethoxysilane, methyltriethoxysilane and dimethyldimethoxysilane.
6. The aqueous epoxy modified acrylic resin according to claim 1, wherein the emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and fatty alcohol polyoxyethylene ether.
7. The method for producing an aqueous epoxy-modified acrylic resin according to any one of claims 1 to 6, comprising the steps of:
step one, accurately weighing acrylic resin, epoxy resin, silane coupling agent and emulsifier;
step two, uniformly mixing acrylic resin and epoxy resin, and stirring in a stirrer for 20-40min to obtain a mixture A;
step three, adding a silane coupling agent into the mixture A in the step two, and then continuously stirring for 20-40min to obtain a mixture B;
step four, adding an emulsifying agent into the mixture B in the step three, and then continuing stirring for 20-40min to obtain a mixture C;
and fifthly, adding water into the mixture C, and uniformly stirring to obtain the water-based epoxy modified acrylic resin.
8. The method for producing an aqueous epoxy-modified acrylic resin according to claim 7, wherein the stirring speed of the mixture A in the second step is 1000 to 1200rmp.
9. The method for producing an aqueous epoxy-modified acrylic resin according to claim 7, wherein the stirring speed of the mixture B in the third step is 3000 to 3600rmp.
10. The method for producing an aqueous epoxy-modified acrylic resin according to claim 7, wherein the stirring speed of the mixture C in the fourth step is 3600 to 4000rmp.
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