CN105601835A - Vinyl acetate/butyl acrylate/acrylic acid ternary soap-free emulsion and preparation method thereof - Google Patents
Vinyl acetate/butyl acrylate/acrylic acid ternary soap-free emulsion and preparation method thereof Download PDFInfo
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- CN105601835A CN105601835A CN201510791989.7A CN201510791989A CN105601835A CN 105601835 A CN105601835 A CN 105601835A CN 201510791989 A CN201510791989 A CN 201510791989A CN 105601835 A CN105601835 A CN 105601835A
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Abstract
The invention provides a vinyl acetate/butyl acrylate/acrylic acid ternary soap-free emulsion; a ternary soap-free emulsion is prepared by adding acrylic acid functional monomers, and the ternary soap-free emulsion is polymerized by using an anion-nonionic reactive copolymerization system; the product is milky white in color, has blue light, has good water resistance, compactness, stability and cohesiveness, has no toxicity and no corrosion, avoids the influence of an emulsifier on the environment, and solves the problem of bad stability of a traditional binary soap-free vinyl acetate-acrylic emulsion; and the raw materials are easy to obtain, the cost is low, and the preparation method is simple and convenient.
Description
Technical field
The present invention relates to a kind of ethylene acetate/acrylic acid butyl ester/acrylic acid ternary soap-free emulsion, the preparation method of soap-free emulsion is also provided simultaneously, have qualitative energy good, film-forming quality is good, and tensile strength is high, belongs to macromolecule gluing agent material technical field.
Background technology
Conventional emulsion polymerization be monomer under emulsifying agent effect and mechanical agitation, in water, be dispersed into the polymerisation that emulsion state carries out. Emulsion polymerization systems viscosity is low, easily heat radiation; There is high reaction rate; With the water as medium temperature control that readily conducts heat; Device therefor technique is simple, flexible to operation. But also there are many deficiencies in emulsion polymerisation. The post processing trouble that obtains solid polymer, cost is higher; All there is certain impact in emulsifying agent residue very obstinate and the compactness on glued membrane, resistance to water, adhesive force and gloss etc.; Emulsifying agent can cause environmental pollution, and price is more expensive conventionally, uses emulsifying agent can increase product cost.
Emulsifier-free emulsion polymerization emulsifier-free emulsion polymerization is the new technology growing up on conventional emulsion polymerization basis, refers to and in course of reaction, does not add the adolescence completely or only add the micro-emulsifying agent emulsion polymerization process of (being less than critical micelle concentration CMC). Emulsifier-free emulsion polymerization is due to the effect such as avoided the isolation of emulsifying agent under existing, absorb water, ooze out, can obtain single dispersion, the clean latex particle in surface, eliminated the pollution of emulsifying agent to environment, the stability of soap-free polymerization emulsion forms charged layer by comonomer on emulsion particle surface and realizes simultaneously. The today receiving much concern at environment, emulsifier-free emulsion polymerization comes into one's own day by day, has been widely used in the research of colloidal particle character. Emulsifier-free emulsion polymerization main method has: " initator fragment is sent out ", " water-soluble monomer copolymerization method " and " ionic comonomer copolymerization method " etc.
Acrylate and vinyl acetate emulsion adhesive belongs to an application class emulsion-type adhesive very widely, it has higher transparency and superior ageing-resistant performance, conventionally, usedly carry out binary emulsifier-free emulsion polymerization without soap acrylate and vinyl acetate emulsion taking vinylacetate and butyl acrylate as monomer, because the reactivity ratio of two kinds of monomers differs larger, gained is without stability and the non-constant of water resistance of soap acrylate and vinyl acetate emulsion; Therefore for solving binary without the bad problem of soap acrylate and vinyl acetate emulsion stability.
Summary of the invention
The invention provides a kind of ethylene acetate/acrylic acid butyl ester/acrylic acid ternary soap-free emulsion, solved traditional binary without the bad problem of soap acrylate and vinyl acetate emulsion stability.
Content of the present invention is that the good ternary of the various aspects of performance such as a kind of environmental protection of preparation, stability, caking property is without soap acrylate and vinyl acetate emulsion.
A kind of ethylene acetate/acrylic acid butyl ester/acrylic acid ternary soap-free emulsion provided by the present invention, it is characterized in that mainly by following raw materials by weight portion than making:
Vinyl acetate 12 ~ 16, butyl acrylate 4 ~ 8, acrylic acid 0.5 ~ 1.5, nonionic comonomer 0.084 ~ 0.21, anionic comonomer 0.042 ~ 0.126, initator 10.168 ~ 10.252.
The preparation method of a kind of ethylene acetate/acrylic acid butyl ester/acrylic acid ternary soap-free emulsion provided by the present invention, comprises the following steps:
1) in nonionic comonomer, anionic comonomer, add the deionized water of 30 ~ 40 parts, after evenly mixing, heating constantly stirring in the water bath with thermostatic control of 76 ~ 84 DEG C, obtains mixing comonomer;
2) vinyl acetate, butyl acrylate, acrylic acid are mixed in proportion to obtain to mix monomer, splash in mixing comonomer prepared by step 1) 1/6 of mix monomer total amount, after 30 minutes, drip again the initator of 1/2 total amount; Described initator be by ammonium persulfate and deionized water by (0.168 ~ 0.252): 10 ratio of quality and the number of copies is mixed with;
3) in step 2) mix the mix monomer and the initator that in comonomer, continue slowly to drip remainder, treat that titration is complete, bath temperature is raise 4.5 DEG C, constant temperature two hours;
4) cool to room temperature, 7 ~ 8, filter rewinding with 1mol/L sodium hydroxide solution adjusting emulsion pH.
Good effect of the present invention is:By adding acrylate functional monomer to prepare ternary without soap acrylate and vinyl acetate emulsion, utilize the reactive copolymerization system of anion-nonionic type to carry out ternary emulsifier-free emulsion polymerization; Product color is milky, has blue light; Have good resistance to water, compactness, stability, caking property, nontoxic non-corrosiveness, has avoided the impact of emulsifying agent on environment, and raw material are easy to get, cost, and preparation method is easy.
Detailed description of the invention
Embodiment 1:
1) nonionic comonomer methyl allyl alcohol polyoxyethylene ether 0.084g and anionic comonomer methylpropene sodium sulfonate 0.042g evenly heated it and constantly stirred after mixing by 30g deionized water in the water bath with thermostatic control of 76 DEG C, obtaining mixing comonomer;
2) polymerization single polymerization monomer vinyl acetate 12g, butyl acrylate 8g, acrylic acid are evenly mixed to get to mix monomer by 0.5g, splash in mixing comonomer prepared by step 1) 1/6 of mix monomer total amount, after 30 minutes, drip again the initator of 1/2 total amount; Described initator is to be mixed with by the ratio of quality and the number of copies of 0.168:10 by ammonium persulfate and deionized water;
3) in step 2) mix the mix monomer and the initator that in comonomer, continue slowly to drip remainder, treat that titration is complete, bath temperature is raise 4.5 DEG C, constant temperature two hours;
4) cool to room temperature, 7 ~ 8, filter rewinding with 1mol/L sodium hydroxide solution adjusting emulsion pH.
The ternary making is 21.6% without soap acrylate and vinyl acetate emulsion solid content, and gel fraction is 3.58%, and average grain diameter is 1.05 μ m.
Advantage major embodiment of the present invention has gone out: ternary is milky without the color and luster of soap acrylate and vinyl acetate emulsion, has blue light; Ternary can be good without pH stability, Calcium ion stability, the dilution stability equistability of soap acrylate and vinyl acetate emulsion; Ternary is good without resistance to water, compactness and the adhesive property of soap acrylate and vinyl acetate emulsion.
Embodiment 2:
1) nonionic comonomer methyl allyl alcohol polyoxyethylene ether 0.116g and anionic comonomer methylpropene sodium sulfonate 0.21g evenly heated it and constantly stirred after mixing by 30g deionized water in the water bath with thermostatic control of 84 DEG C, obtaining mixing comonomer;
2) polymerization single polymerization monomer vinyl acetate 13g, butyl acrylate 7g, acrylic acid are evenly mixed to get to mix monomer by 0.75g, splash in mixing comonomer prepared by step 1) 1/6 of mix monomer total amount, after 30 minutes, drip again the initator of 1/2 total amount; Described initator is to be mixed with by the ratio of quality and the number of copies of 0.105:10 by ammonium persulfate and deionized water;
3) in step 2) mix the mix monomer and the initator that in comonomer, continue slowly to drip remainder, treat that titration is complete, bath temperature is raise 4.5 DEG C, constant temperature two hours;
4) cool to room temperature, 7 ~ 8, filter rewinding with 1mol/L sodium hydroxide solution adjusting emulsion pH.
The ternary making is 18.83% without soap acrylate and vinyl acetate emulsion solid content, and gel fraction is 0.36%, and average grain diameter is 0.89 μ m.
Advantage major embodiment of the present invention has gone out: ternary is milky without the color and luster of soap acrylate and vinyl acetate emulsion, has blue light; Ternary can be good without pH stability, Calcium ion stability, the dilution stability equistability of soap acrylate and vinyl acetate emulsion; Ternary is good without resistance to water, compactness and the adhesive property of soap acrylate and vinyl acetate emulsion.
Embodiment 3:
1) nonionic comonomer methyl allyl alcohol polyoxyethylene ether 0.147g and anionic comonomer methylpropene sodium sulfonate 0.063g evenly heated it and constantly stirred after mixing by 30g deionized water in the water bath with thermostatic control of 82 DEG C, obtaining mixing comonomer;
2) polymerization single polymerization monomer vinyl acetate 14g, butyl acrylate 6g, acrylic acid are evenly mixed to get to mix monomer by 1g, splash in mixing comonomer prepared by step 1) 1/6 of mix monomer total amount, after 30 minutes, drip again the initator of 1/2 total amount; Described initator is to be mixed with by the ratio of quality and the number of copies of 0.252:10 by ammonium persulfate and deionized water;
3) in step 2) mix the mix monomer and the initator that in comonomer, continue slowly to drip remainder, treat that titration is complete, bath temperature is raise 4.5 DEG C, constant temperature two hours;
4) cool to room temperature, 7 ~ 8, filter rewinding with 1mol/L sodium hydroxide solution adjusting emulsion pH.
The ternary making is 19.90% without soap acrylate and vinyl acetate emulsion solid content, and gel fraction is 0.25%, and average grain diameter is 0.31 μ m.
Advantage major embodiment of the present invention has gone out: ternary is milky without the color and luster of soap acrylate and vinyl acetate emulsion, has blue light; Ternary can be good without pH stability, Calcium ion stability, the dilution stability equistability of soap acrylate and vinyl acetate emulsion; Ternary is good without resistance to water, compactness and the adhesive property of soap acrylate and vinyl acetate emulsion.
Embodiment 4:
1) nonionic comonomer methyl allyl alcohol polyoxyethylene ether 0.179g and anionic comonomer methylpropene sodium sulfonate 0.126g evenly heated it and constantly stirred after mixing by 30g deionized water in the water bath with thermostatic control of 80 DEG C, obtaining mixing comonomer;
2) polymerization single polymerization monomer vinyl acetate 15g, butyl acrylate 5g, acrylic acid are evenly mixed to get to mix monomer by 1.25g, splash in mixing comonomer prepared by step 1) 1/6 of mix monomer total amount, after 30 minutes, drip again the initator of 1/2 total amount; Described initator is to be mixed with by the ratio of quality and the number of copies of 0.189:10 by ammonium persulfate and deionized water;
3) in step 2) mix the mix monomer and the initator that in comonomer, continue slowly to drip remainder, treat that titration is complete, bath temperature is raise 4.5 DEG C, constant temperature two hours;
4) cool to room temperature, 7 ~ 8, filter rewinding with 1mol/L sodium hydroxide solution adjusting emulsion pH.
The ternary making is 18.09 without soap acrylate and vinyl acetate emulsion solid content, and gel fraction is 0.01%, and average grain diameter is 0.32 μ m.
Advantage major embodiment of the present invention has gone out: ternary is milky without the color and luster of soap acrylate and vinyl acetate emulsion, has blue light; Ternary can be good without pH stability, Calcium ion stability, the dilution stability equistability of soap acrylate and vinyl acetate emulsion; Ternary is good without resistance to water, compactness and the adhesive property of soap acrylate and vinyl acetate emulsion.
Embodiment 5:
1) nonionic comonomer methyl allyl alcohol polyoxyethylene ether 0.21g and anionic comonomer methylpropene sodium sulfonate 0.084g evenly heated it and constantly stirred after mixing by 30g deionized water in the water bath with thermostatic control of 78 DEG C, obtaining mixing comonomer;
2) polymerization single polymerization monomer vinyl acetate 16g, butyl acrylate 4g, acrylic acid are evenly mixed to get to mix monomer by 1.5g, splash in mixing comonomer prepared by step 1) 1/6 of mix monomer total amount, after 30 minutes, drip again the initator of 1/2 total amount; Described initator is to be mixed with by the ratio of quality and the number of copies of 0.231:10 by ammonium persulfate and deionized water;
3) in step 2) mix the mix monomer and the initator that in comonomer, continue slowly to drip remainder, treat that titration is complete, bath temperature is raise 4.5 DEG C, constant temperature two hours;
4) cool to room temperature, 7 ~ 8, filter rewinding with 1mol/L sodium hydroxide solution adjusting emulsion pH.
The ternary making is 18.27% without soap acrylate and vinyl acetate emulsion solid content, and gel fraction is 0.3%, and average grain diameter is 0.60 μ m.
Advantage major embodiment of the present invention has gone out: ternary is milky without the color and luster of soap acrylate and vinyl acetate emulsion, has blue light; Ternary can be good without pH stability, Calcium ion stability, the dilution stability equistability of soap acrylate and vinyl acetate emulsion; Ternary is good without resistance to water, compactness and the adhesive property of soap acrylate and vinyl acetate emulsion.
Claims (2)
1. ethylene acetate/acrylic acid butyl ester/acrylic acid ternary soap-free emulsion, it is characterized in that mainly by following raw materials by weight portion than making:
Vinyl acetate 12 ~ 16, butyl acrylate 4 ~ 8, acrylic acid 0.5 ~ 1.5, nonionic comonomer 0.084 ~ 0.21, anionic comonomer 0.042 ~ 0.126, initator 10.168 ~ 10.252.
2. the preparation method of a kind of ethylene acetate/acrylic acid butyl ester/acrylic acid ternary soap-free emulsion claimed in claim 1, comprises the following steps:
1) in nonionic comonomer, anionic comonomer, add the deionized water of 30 ~ 40 parts, after evenly mixing, heating constantly stirring in the water bath with thermostatic control of 76 ~ 84 DEG C, obtains mixing comonomer;
2) vinyl acetate, butyl acrylate, acrylic acid are mixed in proportion to obtain to mix monomer, splash in mixing comonomer prepared by step 1) 1/6 of mix monomer total amount, after 30 minutes, drip again the initator of 1/2 total amount; Described initator be by ammonium persulfate and deionized water by (0.168 ~ 0.252): 10 ratio of quality and the number of copies is mixed with;
3) in step 2) mix the mix monomer and the initator that in comonomer, continue slowly to drip remainder, treat that titration is complete, bath temperature is raise 4.5 DEG C, constant temperature two hours;
4) cool to room temperature, 7 ~ 8, filter rewinding with 1mol/L sodium hydroxide solution adjusting emulsion pH.
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| CN201510791989.7A CN105601835A (en) | 2015-11-18 | 2015-11-18 | Vinyl acetate/butyl acrylate/acrylic acid ternary soap-free emulsion and preparation method thereof |
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| CN201510791989.7A CN105601835A (en) | 2015-11-18 | 2015-11-18 | Vinyl acetate/butyl acrylate/acrylic acid ternary soap-free emulsion and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724416A (en) * | 2019-09-25 | 2020-01-24 | 湖北工业大学 | Preparation method of modified hydroxyl ester-based polymer emulsion |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032950A (en) * | 1987-11-02 | 1989-05-17 | 阜新矿务局局直综合公司 | Three new series of acrylate latices |
| US5928783A (en) * | 1998-03-09 | 1999-07-27 | National Starch And Chemical Investment Holding Corporation | Pressure sensitive adhesive compositions |
| CN101717467A (en) * | 2009-11-18 | 2010-06-02 | 北京高盟化工有限公司 | Aqueous acrylic emulsion, aqueous adhesive for pearlized film composite materials and preparation method thereof |
| US20110014465A1 (en) * | 2009-07-16 | 2011-01-20 | Lg Chem, Ltd. | Acrylic Pressure Sensitive Adhesive And Method Of Preparing The Same |
| CN103059211A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工集团公司 | Vinyl acetate-acrylate copolymer emulsion, its synthesis method and application |
| CN103408691A (en) * | 2013-08-06 | 2013-11-27 | 中科院广州化学有限公司 | Acrylate pressure-sensitive adhesive emulsion and preparation method and application thereof |
| CN104558379A (en) * | 2013-10-15 | 2015-04-29 | 青岛三秀新科技复合面料有限公司 | Preparation technology of polyacrylic ester adhesive |
-
2015
- 2015-11-18 CN CN201510791989.7A patent/CN105601835A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032950A (en) * | 1987-11-02 | 1989-05-17 | 阜新矿务局局直综合公司 | Three new series of acrylate latices |
| US5928783A (en) * | 1998-03-09 | 1999-07-27 | National Starch And Chemical Investment Holding Corporation | Pressure sensitive adhesive compositions |
| US20110014465A1 (en) * | 2009-07-16 | 2011-01-20 | Lg Chem, Ltd. | Acrylic Pressure Sensitive Adhesive And Method Of Preparing The Same |
| CN101717467A (en) * | 2009-11-18 | 2010-06-02 | 北京高盟化工有限公司 | Aqueous acrylic emulsion, aqueous adhesive for pearlized film composite materials and preparation method thereof |
| CN103059211A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工集团公司 | Vinyl acetate-acrylate copolymer emulsion, its synthesis method and application |
| CN103408691A (en) * | 2013-08-06 | 2013-11-27 | 中科院广州化学有限公司 | Acrylate pressure-sensitive adhesive emulsion and preparation method and application thereof |
| CN104558379A (en) * | 2013-10-15 | 2015-04-29 | 青岛三秀新科技复合面料有限公司 | Preparation technology of polyacrylic ester adhesive |
Non-Patent Citations (2)
| Title |
|---|
| 郑志荣，等: "新型聚醋酸乙烯酯乳液的制备", 《浙江纺织服装职业技术学院学报》 * |
| 郑志荣,等: "无皂改性醋酸乙烯酯乳液的制备", 《涂料工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724416A (en) * | 2019-09-25 | 2020-01-24 | 湖北工业大学 | Preparation method of modified hydroxyl ester-based polymer emulsion |
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Application publication date: 20160525 |