CN117603386A - Water-soluble cationic acrylic resin and preparation method and application thereof - Google Patents
Water-soluble cationic acrylic resin and preparation method and application thereof Download PDFInfo
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- CN117603386A CN117603386A CN202311509383.0A CN202311509383A CN117603386A CN 117603386 A CN117603386 A CN 117603386A CN 202311509383 A CN202311509383 A CN 202311509383A CN 117603386 A CN117603386 A CN 117603386A
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 43
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 43
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 acrylic ester Chemical class 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims description 17
- 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 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- 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 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 4
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 4
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 claims description 3
- ZGCZDEVLEULNLJ-UHFFFAOYSA-M benzyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C=CC(=O)OCC[N+](C)(C)CC1=CC=CC=C1 ZGCZDEVLEULNLJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000010985 leather Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- CRGOPMLUWCMMCK-UHFFFAOYSA-M benzyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)CC1=CC=CC=C1 CRGOPMLUWCMMCK-UHFFFAOYSA-M 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 239000003995 emulsifying agent Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a water-soluble cationic acrylic resin, a preparation method and application thereof. The water-soluble cationic acrylic resin comprises the following components in percentage by weight: 5-10% of acrylic acid cationic monomer, 10-20% of acrylic ester, 20-30% of water-soluble organic alcohol, 1-3% of initiator and 40-60% of water. The performance of the aqueous acrylic resin prepared by the invention completely reaches the performance of solvent type acrylic resin prepared by aromatic hydrocarbon solvent. Meanwhile, the preparation method does not need to use an emulsifying agent and an aromatic hydrocarbon solvent, which is beneficial to further improving the performance of the water-soluble cationic acrylic resin.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a water-soluble cationic acrylic resin, a preparation method and application thereof.
Background
The acrylic resin has excellent weather resistance, transparency, chemical resistance and mechanical strength, and is widely applied to the fields of automobiles, buildings, machinery, electric appliances, leather, textile printing and dyeing, papermaking and the like. Acrylic resins are mainly classified into solvent-based and aqueous-based types. The solvent-based resin has excellent performance, but the solvent-based resin (mainly aromatic hydrocarbon) has great influence on human bodies and environment, while the aqueous solution-based resin has little influence on human bodies and environment, the traditional preparation method needs to be prepared under the condition of high acrylic acid content or the addition of an emulsifying agent, thereby having great influence on the final resin performance and limiting the application range of the resin.
Disclosure of Invention
The invention aims to provide a water-soluble cationic acrylic resin, a preparation method and application thereof. The performance of the aqueous acrylic resin prepared by the invention completely reaches the performance of solvent type acrylic resin prepared by aromatic hydrocarbon solvent. Meanwhile, the preparation method does not need to use an emulsifying agent and an aromatic hydrocarbon solvent, which is beneficial to further improving the performance of the water-soluble cationic acrylic resin.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the water-soluble cationic acrylic resin comprises the following components in percentage by weight: 5-10% of acrylic acid cationic monomer, 10-20% of acrylic ester, 20-30% of water-soluble organic alcohol, 1-3% of initiator and 40-60% of water.
Preferably, the water-soluble cationic acrylic resin comprises the following components in percentage by weight: 8 to 10 percent of acrylic acid cationic monomer, 10 to 15 percent of acrylic ester, 20 to 25 percent of water-soluble organic alcohol, 1 to 1.5 percent of initiator and 45 to 60 percent of water.
Preferably, the acrylic cationic monomer comprises at least one of dimethyldiallylammonium chloride, diallylamine, triallylammonium, tetraallylammonium, acryloxyethyltrimethylammonium chloride, methacryloxyethyltrimethylammonium chloride, acryloxyethyldimethylbenzyl ammonium chloride, methacryloxyethyldimethylbenzyl ammonium chloride, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, acryloxyethyldimethylaminoethyl ester, methacryloxyethyldimethylaminoethyl ester.
Preferably, the water-soluble organic alcohol comprises one or a mixture of several of methanol, ethanol and isopropanol.
Preferably, the initiator comprises at least one of azobisisobutyronitrile, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide.
The acrylic acid ester selected in the present invention may be at least one of acrylic acid ester components commonly used in the art such as ethyl acrylate, methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate, ethyl methacrylate, isooctyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, hydroxypropyl methacrylate, etc.
The invention also claims a preparation method of the water-soluble cationic acrylic resin, which comprises the following steps:
mixing acrylic acid cationic monomer, acrylic ester and water-soluble organic alcohol, adding part of initiator, heating, refluxing, adding the rest of initiator, heating, continuing to react to obtain polymer mixed solution, cooling, finally adding water, adjusting pH value with acid to make it become transparent solution, and obtaining the water-soluble cationic acrylic resin.
In the preparation method of the water-soluble cationic acrylic resin, the rest of the initiator can be added first and then heated for continuous reaction, or the rest of the initiator can be added after the temperature is raised first, and the sequence of the two can not obviously influence the performance of the final water-soluble cationic acrylic resin.
Preferably, the concentration of the solution prepared by mixing the acrylic acid cationic monomer, the acrylic ester and the water-soluble organic alcohol is 40-60%.
Preferably, the partial initiator is used in an amount of 2/3 of the total mass of the initiator.
Preferably, the water-soluble cationic acrylic resin has a solid content of 10 to 40%.
Preferably, the temperature rise after the addition of part of the initiator is such that the temperature is raised to 70-80 ℃.
Preferably, the reflux time is 1-2 hours.
Preferably, the temperature increase after the addition of the remaining initiator is such that the temperature is increased to 85-90 ℃.
Preferably, the time for continuing the reaction is 1 to 2 hours.
Preferably, the pH value is adjusted to 3-6.
Preferably, the pH-adjusting solvent may be H 2 SO 4 The inorganic acid such as HCl can be one or more of organic acids such as acetic acid (HAC) and citric acid. The invention forms the quaternary ammonium salt by the cationic acrylic acid monomer and the acid, and the quaternary ammonium salt plays the role of an emulsifier and does not need a solvent.
The invention also claims the application of the water-soluble cationic acrylic resin in preparing fiber fabric coatings, leather finishing agents, adhesives and fabric deepening agents.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the performance of the prepared aqueous acrylic resin completely reaches the performance of solvent type acrylic resin prepared by using the aromatic hydrocarbon solvent through the hydrophilic alcohol solvent without using an emulsifier and the aromatic hydrocarbon solvent.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. 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.
In the examples and comparative examples, the experimental methods used were conventional methods, and the materials, reagents and the like used were commercially available, unless otherwise specified.
Example 1
21g of acryloyloxyethyl dimethylaminoethyl ester, 30g of ethyl acrylate, 20g of methyl methacrylate, 30g of butyl acrylate, 100g of ethanol and 4g of azobisisobutyronitrile are added into a 500ml three-port reaction kettle with a reflux device, stirred and heated to 75 ℃, kept in a reflux state for reaction for 3 hours, then heated to 85 ℃,1g of azobisisobutyronitrile is added, the reaction is continued for 1 hour, the temperature is reduced, 200g of deionized water is added, the PH value is regulated to 3-4 by citric acid, and the transparent water-based cationic acrylic resin is prepared, and the concentration (solid content) is about 25%.
Example 2
In a 500ml three-port reaction kettle with a reflux device, 30g of acryloyloxyethyl trimethyl ammonium chloride, 18g of hydroxypropyl acrylate, 32g of butyl acrylate, 20g of acrylonitrile, 100g of isopropyl alcohol and 3g of benzoyl peroxide are added, stirring and heating to 80 ℃, keeping a reflux state for reaction for 3 hours, heating to 90 ℃, adding 1g of benzoyl peroxide, continuing to react for 1 hour, cooling, adding 150g of deionized water, and regulating the PH value to 3-4 by using HAC to prepare the transparent water-based cationic acrylic resin, wherein the concentration (solid content) is about 33%.
Example 3
Adding 40g of acryloyloxyethyl dimethyl benzyl ammonium chloride, 20g of hydroxyethyl methacrylate, 30g of isobutyl acrylate, 10g of isooctyl acrylate, 50g of ethanol and 55g of isopropanol into a 500ml three-port reaction kettle with a reflux device, adding 5g of tert-butyl hydroperoxide, heating to 80 ℃, carrying out polymerization reaction for 3 hours, heating to 85 ℃, adding 1g of tert-butyl hydroperoxide, continuing to carry out polymerization reaction for 1 hour, cooling, adding 300g of deionized water, and regulating the PH value to 4-5 by using glycolic acid to prepare the transparent water-based cationic acrylic resin, wherein the concentration (solid content) is about 20%.
Example 4
Adding 40g of methacryloxyethyl trimethyl ammonium chloride, 18g of ethyl methacrylate, 32g of isobutyl acrylate, 10g of dodecyl acrylate and 100g of methanol into a 500ml three-port reaction kettle with a reflux device, adding 4g of cumene hydroperoxide, heating to 75 ℃, keeping a reflux state, reacting for 3H, heating to 90 ℃, adding 1g of cumene hydroperoxide, continuing to react for 1H, cooling, adding 200g of deionized water, and using H 2 SO 4 Adjusting the PH value to 4-5 to prepare the transparent water-based cationic acrylic treeThe concentration (solids content) of fat was about 25%.
Example 5
50g of dimethylaminopropyl methacrylamide, 30g of ethyl acrylate, 10g of octadecyl acrylate, 15g of hydroxypropyl methacrylate, 105g of isopropanol are added into a 500ml three-port reaction kettle with a reflux device, the temperature is raised to 75-80 ℃,2g of azobisisobutyronitrile and 2g of benzoyl peroxide are added, the reflux state is kept, the reaction is carried out for 3 hours, 1g of azobisisobutyronitrile is added, 1g of benzoyl peroxide is raised to 85-90 ℃, the reaction is continued for 1 hour, the temperature is reduced, 300g of deionized water is added, the PH value is regulated to 4-5 by HCl, and the transparent water-based cationic acrylic resin with the concentration (solid content) of about 22% is prepared.
Example 6
Adding 30g of acryloyloxyethyl dimethylaminoethyl ester, 80g of ethyl acrylate, 100g of ethanol and 2g of azobisisobutyronitrile into a 500ml three-port reaction kettle with a reflux device, stirring and heating to 75 ℃, keeping the reflux state for reaction for 3 hours, heating to 85 ℃, adding 1g of azobisisobutyronitrile, continuing to react for 1 hour, cooling, adding 200g of deionized water, and regulating the PH value to 3-4 by using citric acid to prepare the transparent water-based cationic acrylic resin, wherein the concentration (solid content) is about 25%.
Comparative example 1
The only difference between this comparative example and example 2 is that the same amount of ethylene glycol was used instead of ethanol.
The preparation method is described in example 2.
Comparative example 2
10g of acryloyloxyethyl trimethyl ammonium chloride, 18g of hydroxypropyl acrylate, 32g of butyl acrylate, 20g of acrylonitrile, 100g of isopropyl alcohol and 3g of benzoyl peroxide are added into a 500ml three-port reaction kettle with a reflux device, stirred and heated to 80 ℃, the mixture is kept in a reflux state for reaction for 3 hours, then heated to 90 ℃,1g of benzoyl peroxide is added, the reaction is continued for 1 hour, the temperature is reduced, 150g of deionized water is added, and the PH value is regulated to 3-4 by HAC, so that the semitransparent aqueous cationic acrylic resin with the concentration (solid content) of about 28.6% is prepared.
The difference between this comparative example and example 2 is that the mass of acryloyloxyethyl dimethylaminoethyl ester was 10g. Below 5% cationic monomer can affect the clarity of the final aqueous resin.
Effect example
The aqueous cationic acrylic resins prepared in examples and comparative examples were brushed onto ABS engineering plastic plates, the substrate was heated to 80 ℃ and the curing time was tested, and at the same time, the stability test was performed on the aqueous cationic acrylic resins prepared at normal temperature, the time for occurrence of delamination and the like was recorded, and the test results are shown in table 1.
TABLE 1
| Group of | Curing time/min | Storage stability Properties |
| Example 1 | 50 | >For 12 months |
| Example 2 | 60 | >For 12 months |
| Example 3 | 50 | >For 12 months |
| Example 4 | 46 | >For 12 months |
| Example 5 | 65 | >For 12 months |
| Example 6 | 56 | >For 12 months |
| Comparative example 1 | >180 | <1 month |
| Comparative example 2 | 120 | <For 3 months |
From the data in Table 1, it can be seen that the aqueous cationic acrylic resin prepared in the examples of the present invention has a short curing time and good stability.
The solvent component selected in comparative example 1 was unsuitable as compared with example 2, and the resulting acrylic resin had significantly deteriorated curability and storage stability; the acrylic resin obtained by adding too little acrylic cationic monomer in comparative example 2 had inferior curability and storage stability to those of examples.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (8)
1. The water-soluble cationic acrylic resin is characterized by comprising the following components in percentage by weight: 5-10% of acrylic acid cationic monomer, 10-20% of acrylic ester, 20-30% of water-soluble organic alcohol, 1-3% of initiator and 40-60% of water.
2. The water-soluble cationic acrylic resin of claim 1, wherein the acrylic cationic monomer comprises at least one of dimethyldiallylammonium chloride, diallylamine, triallylammonium, tetraallylammonium, acryloxyethyltrimethylammonium chloride, methacryloxyethyltrimethylammonium chloride, acryloxyethyldimethylbenzyl ammonium chloride, methacryloxyethyldimethylbenzyl ammonium chloride, dimethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, acryloxyethyldimethylaminoethyl ester, methacryloxyethyldimethylaminoethyl ester.
3. The water-soluble cationic acrylic resin according to claim 1, wherein the water-soluble organic alcohol comprises one or a mixture of several of methanol, ethanol, isopropanol.
4. The water-soluble cationic acrylic resin according to claim 1, wherein the initiator comprises at least one of azobisisobutyronitrile, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide.
5. A process for producing the water-soluble cationic acrylic resin according to any one of claims 1 to 4, comprising the steps of:
mixing acrylic acid cationic monomer, acrylic ester and water-soluble organic alcohol, adding part of initiator, heating, refluxing, adding the rest of initiator, heating, continuing to react to obtain polymer mixed solution, cooling, finally adding water, and regulating pH value to obtain the water-soluble cationic acrylic resin.
6. The method according to claim 5, comprising at least one of the following (1) to (2):
(1) The dosage of the partial initiator is 2/3 of the total mass of the initiator;
(2) The solid content of the water-soluble cationic acrylic resin is 10-40%.
7. The method of claim 5, comprising at least one of the following (1) to (5):
(1) The temperature is raised to 70-80 ℃ after part of initiator is added;
(2) The reflux time is 1-2 h;
(3) The temperature is raised to 85-90 ℃ after the rest initiator is added;
(4) The continuous reaction time is 1-2 h;
(5) The pH value is adjusted to 3-6.
8. Use of a water-soluble cationic acrylic resin according to any one of claims 1 to 4 for the preparation of fibrous textile coatings, leather finishes, adhesives, textile deepeners.
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