CN103992438A - Preparation method of acrylic polymer - Google Patents
Preparation method of acrylic polymer Download PDFInfo
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- CN103992438A CN103992438A CN201410224072.4A CN201410224072A CN103992438A CN 103992438 A CN103992438 A CN 103992438A CN 201410224072 A CN201410224072 A CN 201410224072A CN 103992438 A CN103992438 A CN 103992438A
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Abstract
The invention discloses a preparation method of an acrylic polymer. The method comprises the steps of under the protection of nitrogen, enabling dehydrated polyester polyol CMA44 to react with polyisocyanate IPDI, adding an emulsified hydrophilic reagent to perform reaction for a period of time after completing the reaction, and then cooling; adding an alkali solution to perform neutralization, then adding a dilution solvent to perform dilution, emulsifying at room temperature, and performing chain extension by using a chain extender to obtain an aqueous polyurethane dispersion; emulsifying the aqueous polyurethane dispersion and a polymerized monomer together, then performing core-shell co-polymerization, and then cooling to obtain a finished product. The preparation method of the acrylic polymer, disclosed by the invention, adopts polyisocyanate IPDI as a main component, can be used for improving the film formation performance, flexibility and air permeability of the final products, reducing the cost of the products and improving the cost-performance ratio, and has the advantages of alcohol rubbing resistance and the like.
Description
Technical field
The present invention relates to a kind of preparation method of acrylate copolymer.
Background technology
For many years, wallpaper ink mainly adopts oiliness PVC intaglio plate table printing ink, and its weak point is that oil product has solvent evaporates, not environmental protection, and production and transportation are very not convenient, and the easy dust suction of product of producing, is attached on wall, and ventilation property is poor.The progress in epoch, the qualitative change of science and technology, the improvement of living environment, the management and control of country to solvent-borne type compound, it is extremely urgent producing a kind of environment-friendly type high performance water polymer materials that can be used for wallpaper ink.
Summary of the invention
The invention provides a kind of preparation method of acrylate copolymer, adopt polyisocyanates IPDI as main component, improved film-forming properties, snappiness and the ventilation property of the finished product, reduced the cost of product, improve cost performance, there is the benefits such as ethanol-tolerant wiping.
The present invention has adopted following technical scheme: a kind of preparation method of acrylate copolymer, it comprises the following steps: step 1, choose polyisocyanates IPDI and polyester polyol CMA44 and polyester polyol CMA44 is dewatered, then under nitrogen protection, the polyester polyol CMA44 of dehydration and polyisocyanates IPDI are reacted to for some time at 70-75 ℃ of temperature, in the process of reaction, by measuring the content of NCO, judge the terminal of reaction, after reaction reaches terminal, add emulsification hydrophilic reagent reaction for some time, then lower the temperature; Step 2, adds alkaline solution to neutralize in the solution in step 1 after cooling, then adds the viscosity that diluting solvent dilutes to reduce solution after neutralization reaction, and then emulsification at normal temperatures, carries out, after chain extension, obtaining aqueous polyurethane dispersion with chainextender; Step 3, choose aqueous polyurethane dispersion, vinylbenzene, vinylformic acid, Propylene glycol monoacrylate, methyl methacrylate, butyl acrylate, emulsifying agent DBS, ammonium persulphate, hydrogen peroxide, SODIUM ISOVITAMIN C, ammoniacal liquor and water, then several persons are mixed to composition polymerization single polymerization monomer; Step 4 is carried out aqueous polyurethane dispersion core-shell copolymerizedly together with polymerization single polymerization monomer after emulsification, after then lowering the temperature, obtain polyurethane-modified acrylic polymer materials.In described step 1, polyester polyol CMA44 and polyisocyanates IPDI react 1.5 hours under the effect of catalyzer T-12, in the process of reaction, adopt titration reagent to measure the content of NCO, it when the content of NCO is the 2%-3% of reaction soln weight, is the terminal of reaction, described emulsification hydrophilic reagent is dimethylol propionic acid, adding the time of emulsification hydrophilic reagent reaction is 1 hour, the temperature of reaction is 60-65 ℃, has reacted rear temperature and has dropped to 40 ℃; Described titration reagent is Di-n-Butyl Amine; In described step 2, alkaline solution is triethylamine, and diluting solvent is water, the aqueous solution that chainextender is quadrol; In described step 3, polymerization single polymerization monomer is comprised of following component: 100 parts of aqueous polyurethane dispersion, 220 parts of vinylbenzene, 42 parts, vinylformic acid, 158 parts of Propylene glycol monoacrylates, 40 parts of methyl methacrylates, 40 parts of butyl acrylates, 20 parts of emulsifying agent DBS, 4 parts of ammonium persulphates, 2.5 parts, hydrogen peroxide, 1 part of SODIUM ISOVITAMIN C, 4 parts of ammoniacal liquor, 156 parts, water; In described step 4, to carry out core-shell copolymerized temperature be 80-82 ℃ for aqueous polyurethane dispersion and polymerization single polymerization monomer, time is 5 hours, core-shell copolymerized rear temperature is down to below 40 ℃, filters to obtain finished product, and in finished product, the solid content of polyurethane-modified acrylate copolymer is 40%.
The present invention has following beneficial effect: the present invention has adopted polyisocyanates IPDI as main component, film-forming properties, snappiness and the ventilation property of the finished product have been improved, reduced the cost of product, improved cost performance, there is the benefits such as ethanol-tolerant wiping, in polymerization single polymerization monomer, comprise Potassium Persulphate and make reaction more steady.
Embodiment
The invention provides a kind of preparation method of acrylate copolymer, it comprises the following steps: step 1, choose polyisocyanates IPDI and polyester polyol CMA44 and polyester polyol CMA44 is dewatered, then under nitrogen protection, the polyester polyol CMA44 of dehydration and polyisocyanates IPDI are reacted 1.5 hours at 70-75 ℃ of temperature, in the process of reaction, by the content that adopts titration reagent to measure NCO, judge the terminal of reaction, described titration reagent is Di-n-Butyl Amine, it when the content of NCO is the 2%-3% of reaction soln weight, is the terminal of reaction, after reaching terminal, reaction adds emulsification hydrophilic reagent reaction for some time, described emulsification hydrophilic reagent is dimethylol propionic acid, adding the time of emulsification hydrophilic reagent reaction is 1 hour, the temperature of reaction is 60-65 ℃, after having reacted, be cooled to again 40 ℃, step 2, in solution in step 1 after cooling, add alkaline solution to neutralize, add again the viscosity that diluting solvent dilutes to reduce solution after neutralization reaction, then emulsification at normal temperatures, with chainextender, carry out, after chain extension, obtaining aqueous polyurethane dispersion, described alkaline solution is triethylamine, diluting solvent is water, the aqueous solution that chainextender is quadrol, step 3, choose aqueous polyurethane dispersion, vinylbenzene, vinylformic acid, Propylene glycol monoacrylate, methyl methacrylate, butyl acrylate, emulsifying agent DBS, ammonium persulphate, hydrogen peroxide, SODIUM ISOVITAMIN C, ammoniacal liquor and water, then several persons are mixed to composition polymerization single polymerization monomer, step 4, aqueous polyurethane dispersion is carried out core-shell copolymerized together with polymerization single polymerization monomer after emulsification, core-shell copolymerized temperature is 80-82 ℃, time is 5 hours, then lower the temperature, temperature is down to 40 ℃ of following finished products that obtain polyurethane-modified acrylate copolymer after aqueous polyurethane dispersion and polymerization single polymerization monomer are filtered, and in finished product, the solid content of polyurethane-modified acrylate copolymer is 40%.
Embodiment 1: under nitrogen protection, by 195 grams of the polyester polyol CMA44 of dehydration, 82 grams of 1 gram of catalyzer T-12 and polyisocyanates IPDI react 1.5 hours under the condition of 70-75 ℃, the content of measuring NCO by Di-n-Butyl Amine in the process of reaction judges the terminal of reaction, it when the content of NCO is the 2%-3% of reaction soln weight, is the terminal of reaction, after reaching terminal, reaction adds 13 grams of reactions of dimethylol propionic acid 1 hour, the temperature of reaction is 60-65 ℃, is cooling to 40 ℃; Then add triethylamine to carry out neutralization reaction, triethylamine is 12 grams, add diluting solvent again and dilute, diluting solvent is water, 400 grams, reduce like this viscosity of solution after neutralization reaction, chainextender is the aqueous solution of quadrol, and quadrol is 8 grams, 150 grams, water, emulsification at normal temperatures and chain extension, obtain aqueous polyurethane dispersion; Choose 100 grams of aqueous polyurethane dispersion, 220 grams of vinylbenzene, 42 grams, vinylformic acid, 158 grams of Propylene glycol monoacrylates, methyl methacrylate is 40 grams, butyl acrylate is 40 grams, and water is 156 grams, 20 grams of emulsifying agent DBS, 4 grams of ammonium persulphates, 2.5 grams, hydrogen peroxide, 1 gram of SODIUM ISOVITAMIN C, 4 grams of mixing of ammoniacal liquor form polymerization single polymerization monomer; Finally aqueous polyurethane dispersion and polymerization single polymerization monomer are carried out to emulsify at a high speed, emulsification viscosity 25cps(25 ℃), again in initiator ammonium persulfate effect, under the condition of temperature 80-82 ℃, carry out core-shell copolymerized 3 hours, add redox agent (hydrogen peroxide and saccharosonic acid are received) reaction 2 hours, be then cooled to 45 ℃, add ammoniacal liquor, adjust in the scope of pH value to 7-8, obtain solid content and be 40% polyurethane-modified acrylate copolymer.
Claims (6)
1. a preparation method for acrylate copolymer, is characterized in that it comprises the following steps:
Step 1, choose polyisocyanates IPDI and polyester polyol CMA44 and polyester polyol CMA44 is dewatered, then under nitrogen protection, the polyester polyol CMA44 of dehydration and polyisocyanates IPDI are reacted to for some time at 70-75 ℃ of temperature, in the process of reaction, by measuring the content of NCO, judge the terminal of reaction, after reaction reaches terminal, add emulsification hydrophilic reagent reaction for some time, then lower the temperature;
Step 2, adds alkaline solution to neutralize in the solution in step 1 after cooling, then adds the viscosity that diluting solvent dilutes to reduce solution after neutralization reaction, and then emulsification at normal temperatures, carries out, after chain extension, obtaining aqueous polyurethane dispersion with chainextender;
Step 3, choose aqueous polyurethane dispersion, vinylbenzene, vinylformic acid, Propylene glycol monoacrylate, methyl methacrylate, butyl acrylate, emulsifying agent DBS, ammonium persulphate, hydrogen peroxide, SODIUM ISOVITAMIN C, ammoniacal liquor and water, then several persons are mixed to composition polymerization single polymerization monomer;
Step 4 is carried out aqueous polyurethane dispersion core-shell copolymerizedly together with polymerization single polymerization monomer after emulsification, after then lowering the temperature, obtain polyurethane-modified acrylic polymer materials.
2. the preparation method of a kind of acrylate copolymer according to claim 1, in step 1 described in it is characterized in that, polyester polyol CMA44 and polyisocyanates IPDI react 1.5 hours under the effect of catalyzer T-12, in the process of reaction, adopt titration reagent to measure the content of NCO, it when the content of NCO is the 2%-3% of reaction soln weight, is the terminal of reaction, described emulsification hydrophilic reagent is dimethylol propionic acid, adding the time of emulsification hydrophilic reagent reaction is 1 hour, the temperature of reaction is 60-65 ℃, has reacted rear temperature and has dropped to 40 ℃.
3. the preparation method of a kind of acrylate copolymer according to claim 2, is characterized in that described titration reagent is Di-n-Butyl Amine.
4. the preparation method of a kind of acrylate copolymer according to claim 1, is characterized in that in described step 2, alkaline solution is triethylamine, and diluting solvent is water, the aqueous solution that chainextender is quadrol.
5. the preparation method of a kind of acrylate copolymer according to claim 1, is characterized in that in described step 3, polymerization single polymerization monomer is comprised of following component: 100 parts of aqueous polyurethane dispersion, 220 parts of vinylbenzene, 42 parts, vinylformic acid, 158 parts of Propylene glycol monoacrylates, 40 parts of methyl methacrylates, 40 parts of butyl acrylates, 20 parts of emulsifying agent DBS, 4 parts of ammonium persulphates, 2.5 parts, hydrogen peroxide, 1 part of SODIUM ISOVITAMIN C, 4 parts of ammoniacal liquor, 156 parts, water.
6. the preparation method of a kind of acrylate copolymer according to claim 1, it is characterized in that in described step 4 that it is 80-82 ℃ that aqueous polyurethane dispersion and polymerization single polymerization monomer carry out core-shell copolymerized temperature, time is 5 hours, core-shell copolymerized rear temperature is down to below 40 ℃, filter to obtain finished product, in finished product, the solid content of polyurethane-modified acrylate copolymer is 40%.
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| CN201410224072.4A CN103992438A (en) | 2014-05-26 | 2014-05-26 | Preparation method of acrylic polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956824A (en) * | 2021-10-19 | 2022-01-21 | 安徽匠星联创新材料科技有限公司 | Reactive all-solid-containing cationic polyurethane-acrylate copolymer adhesive and synthesis method and application thereof |
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| CN101284980A (en) * | 2008-06-05 | 2008-10-15 | 江苏工业学院 | Preparation method of waterborne polyurethane adhesive and application in roads reflecting material |
| CN101475681A (en) * | 2008-11-25 | 2009-07-08 | 无锡博强高分子材料科技有限公司 | Synthesis of high stretching high tenacity polyurethane acrylic ester |
| CN101544738A (en) * | 2009-04-30 | 2009-09-30 | 中山大学 | Room-temperature self-crosslinking water-soluble polyurethane acrylic resin and preparation method and application thereof |
| CN102190789A (en) * | 2011-03-23 | 2011-09-21 | 安庆飞凯高分子材料有限公司 | Preparation method of polyurethane acrylate resin |
| CN102603990A (en) * | 2012-02-17 | 2012-07-25 | 周杰 | Formula and preparation method of acrylic polymer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284980A (en) * | 2008-06-05 | 2008-10-15 | 江苏工业学院 | Preparation method of waterborne polyurethane adhesive and application in roads reflecting material |
| CN101475681A (en) * | 2008-11-25 | 2009-07-08 | 无锡博强高分子材料科技有限公司 | Synthesis of high stretching high tenacity polyurethane acrylic ester |
| CN101544738A (en) * | 2009-04-30 | 2009-09-30 | 中山大学 | Room-temperature self-crosslinking water-soluble polyurethane acrylic resin and preparation method and application thereof |
| CN102190789A (en) * | 2011-03-23 | 2011-09-21 | 安庆飞凯高分子材料有限公司 | Preparation method of polyurethane acrylate resin |
| CN102603990A (en) * | 2012-02-17 | 2012-07-25 | 周杰 | Formula and preparation method of acrylic polymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956824A (en) * | 2021-10-19 | 2022-01-21 | 安徽匠星联创新材料科技有限公司 | Reactive all-solid-containing cationic polyurethane-acrylate copolymer adhesive and synthesis method and application thereof |
| CN113956824B (en) * | 2021-10-19 | 2022-10-25 | 安徽匠星联创新材料科技有限公司 | Reactive full-solid-content cationic polyurethane-acrylate copolymer adhesive and synthesis method and application thereof |
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Application publication date: 20140820 |