CN100400551C - Improved polyvinyl alcohol-beta-cyanoethyl ether preparing method - Google Patents
Improved polyvinyl alcohol-beta-cyanoethyl ether preparing method Download PDFInfo
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- CN100400551C CN100400551C CNB031350801A CN03135080A CN100400551C CN 100400551 C CN100400551 C CN 100400551C CN B031350801 A CNB031350801 A CN B031350801A CN 03135080 A CN03135080 A CN 03135080A CN 100400551 C CN100400551 C CN 100400551C
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Abstract
The present invention relates to an improved manufacturing method of polyvinyl alcohol-beta-cyanoethyl ether which is prepared by the synthesis reaction between polyvinyl alcohol and acrylonitrile under the action of a catalyst with strong basicity, and the purification treatment of coarse product. The polymerization degree of the polyvinyl alcohol is 600 to 2000; because the polyvinyl alcohol with the large polymerization degree is adopted as a raw material, the prepared polyvinyl alcohol-beta-cyanoethyl ether has high substitution value, high purity and high yield.
Description
Technical field
The present invention relates to a kind of manufacture method of in the presence of strong alkali catalyst, making polyvinyl alcohol-β-cyanoethyl ether by polyvinyl alcohol and vinyl cyanide.
Technical background
Polyvinyl alcohol-β-this organic dielectric materials of cyanoethyl ether has high-k, can strengthen the adhesive power to glass, improves brightness, reduces luminescent screen and plays photovoltage, has a extensive future.Russian patent SU509607 " preparation method who contains the cyanoethyl ether polymer of vinyl alcohol ring " has set forth the multipolymer of vinyl alcohol and the ethene dibasic alcohol that contains 40%-60% (molecule) ethene dibasic alcohol ring in the presence of strong alkali catalyst, method with acrylonitrile reactor generation polyvinyl alcohol-β-cyanoethyl ether, be reflected to mix under the ebullient temperature and carry out, until the color of solution change into from yellow orange till, precipitated cyanoethyl product, redeposition final vacuum drying repeatedly in acetone soln.The deficiency that this method exists is to adopt the single step reaction method, and the polyvinyl alcohol-β of acquisition-cyanoethyl ether purity is not high, and substitution value is low, and the performance of product does not reach index.
Summary of the invention
Invention is just in order to overcome above-mentioned deficiency, provide a kind of on the aforesaid method basis method of improved manufacturing polyvinyl alcohol-β-cyanoethyl ether, product purity height by this method acquisition, substitution value is big, performance index are qualified, main innovate point is that the polyvinyl alcohol of selective polymerization degree between 600-2000 make raw material, and the polymerization degree of raw material is too low or too high, and the product color of producing is very yellow, unfavorable to improving illumination effect, in addition, building-up reactions is divided two stages, promptly adopts two step reaction methods, first section temperature of reaction is controlled at 50-70 ℃, reacted 30-70 minute, second section temperature of reaction is lower than first section 2-15 ℃, reacts 60-120 minute.Specifically be achieved like this, improved polyvinyl alcohol-β-cyanoethyl ether manufacture method, building-up reactions under the strong alkali catalyst effect makes with thick purification of product by polyvinyl alcohol and vinyl cyanide, and the polymerization degree that it is characterized in that polyvinyl alcohol is between 600-2000.Only possess the higher polymerization degree, can guarantee the purity of product behind the cyanoethylation, the polymerization degree of best polyvinyl alcohol of the present invention is 1200-1800.The building-up reactions that the present invention adopts is formed by two sections, and first section temperature of reaction is controlled at 50-70 ℃, reacts 30-70 minute, and second section temperature of reaction is lower than first section 2-10 ℃, reacts 60-120 minute.In order effectively to guarantee carrying out smoothly of positive reaction, suppress side reaction to bottom line.The present invention adopts two step reaction methods, and beginning is carried out under comparatively high temps, suitably reduces temperature of reaction then, and not only substitution value is big and purity is high for the product of producing like this.In the synthetic method of the present invention, the optimum temps of first section reaction is 60-66 ℃, and optimum reacting time is 35-60 minute, and second section optimum temps is 55-62 ℃, and optimum reacting time is 70-100 minute.
In the building-up reactions of the present invention, what catalyzer was selected for use is alkali metal hydroxide, in the industrialization from cost consideration, especially be best with sodium hydroxide, the height of naoh concentration is also influential to reaction, excessive concentration or mistake are low all can to impact product color and yield, and the naoh concentration that the present invention adopts is controlled at about 3-6% (weight).
In order not only to guarantee product yield but also do not increase vinyl cyanide and the recovery of oxygen sodium oxide and neutralizing treatment amount, the weight proportion relation of raw material is in the two step reaction methods of the present invention: vinyl cyanide: polyvinyl alcohol=15-10: 1, sodium hydroxide: polyvinyl alcohol=0.08-0.12: 1, wherein especially with vinyl cyanide: polyvinyl alcohol=14-11: 1 is the best.
After second period reaction times arrives, with in the acid and the alkaline catalysts termination reaction in the system, reclaims excessive vinyl cyanide, the recovery of vinyl cyanide is to add deionized water, with the distillating method recovery, separate out polyvinyl alcohol-β-thick product of cyanoethyl ether simultaneously.
In reaction process, be difficult in the product removing owing to exist side reaction, the by product of generation to be mingled in, for the good polyvinyl alcohol-β of obtained performance-cyanoethyl ether product, also must carry out purification process to polyvinyl alcohol-β-thick product of cyanoethyl ether.The purification process that the present invention adopts is the acetone soln precipitating of 25-30%, and precipitating carries out twice repeatedly, and temperature is controlled at 90-95 ℃.
Product after purified carries out vacuum-drying at last, and to remove moisture content, vacuum degree control is more than 755mmHg, and temperature is 80-90 ℃, removes fully until moisture content.
The polyvinyl alcohol of the polymerization degree is a raw material owing to adopt greatly in the present invention, and building-up reactions divided for two steps finished, and the polyvinyl alcohol-β that makes-cyanoethyl ether substitution value is big, purity and productive rate height, the purification process of the heavy precipitating of acetone, it is light that product color is subtracted greatly, guaranteed the quality of product.
Embodiment
Embodiment 1, in flask, successively add the polymerization degree and be 1 part of 1750 polyvinyl alcohol, 12 parts of fine propylene nitriles, 2.5 the catalyzer oxygen sodium oxide of part 4%, under agitation holding temperature is about 64 ℃, carried out cyanoethylation reaction 40 minutes, cool to 60 ℃, carry out second-stage reaction, after 90 minutes, the alkaline catalysts that adds in the acetic acid neutralization reaction system stops building-up reactions, then add appropriate amount of deionized water, excessive vinyl cyanide is reclaimed in distillation, and polyvinyl alcohol-β-thick product of cyanoethyl ether is then come out by precipitating.
Thick product polyvinyl alcohol-β-purification process of cyanoethyl ether is to use the acetone precipitating, and process is:
(1) deionized water wash;
(2) with the acetone soln dissolved product of 25-30%, add deionized water and stir, controlled temperature is precipitating between 90-95 ℃, twice repeatedly;
(3) vacuum-drying.Is about 760mmHg with the product after purified in vacuum tightness, and temperature is carried out vacuum-drying under about 80-90 ℃, no longer present to the product steam bubble then drying finish.
Embodiment 2, in flask, successively add the polymerization degree and be 1 part of 1500 polyvinyl alcohol, 11 parts of fine propylene nitriles, 2 part 5% catalyzer oxygen potassium oxide, under agitation holding temperature is about 58 ℃, carried out cyanoethylation reaction 70 minutes, cool to 55 ℃, carry out second-stage reaction, after 110 minutes, the alkaline catalysts that adds in the acetic acid neutralization reaction system stops building-up reactions, then add appropriate amount of deionized water, excessive vinyl cyanide is reclaimed in distillation, and polyvinyl alcohol-β-thick product of cyanoethyl ether is then come out by precipitating.
The purification process of thick product polyvinyl alcohol-β-cyanoethyl ether is with embodiment 1.
Embodiment 3, in flask, successively add the polymerization degree and be 1 part of 1650 polyvinyl alcohol, 14 parts of fine propylene nitriles, 2 part 4.5% catalyzer oxygen sodium oxide, under agitation holding temperature is about 68 ℃, carried out cyanoethylation reaction 50 minutes, cool to 62 ℃, carry out second-stage reaction, after 80 minutes, the alkaline catalysts that adds in the acetic acid neutralization reaction system stops building-up reactions, then add appropriate amount of deionized water, excessive vinyl cyanide is reclaimed in distillation, and polyvinyl alcohol-β-thick product of cyanoethyl ether is then come out by precipitating.
The purification process of thick product polyvinyl alcohol-β-cyanoethyl ether is with embodiment 1.
Claims (10)
1. improved polyvinyl alcohol-β-cyanoethyl ether manufacture method, building-up reactions under the strong alkali catalyst effect makes with thick purification of product at polyvinyl alcohol between the 600-2000 and vinyl cyanide by the polymerization degree, it is characterized in that building-up reactions forms by two sections, first section temperature of reaction is controlled at 50-70 ℃, reacted 30-70 minute, second section temperature of reaction is lower than first section 2-10 ℃, reacts 60-120 minute.
2. manufacture method according to claim 1, the polymerization degree that it is characterized in that polyvinyl alcohol is 1200-1800.
3. manufacture method according to claim 1 and 2, the temperature of reaction that it is characterized in that first section of building-up reactions is 60-66 ℃, and the reaction times is 35-60 minute, and second section temperature of reaction is 55-62 ℃, and the reaction times is 70-100 minute.
4. manufacture method according to claim 1 and 2 is characterized in that strong alkali catalyst is an alkali metal hydroxide.
5. manufacture method according to claim 4 is characterized in that alkali metal hydroxide is a sodium hydroxide.
6. manufacture method according to claim 3 is characterized in that the raw material weight proportioning of building-up reactions is: vinyl cyanide: polyvinyl alcohol=15-10: 1, and sodium hydroxide: polyvinyl alcohol=0.08-0.12: 1.
7. manufacture method according to claim 6 is characterized in that vinyl cyanide in the raw material weight proportioning: polyvinyl alcohol=14-11: 1.
8. manufacture method according to claim 1 and 2, it is characterized in that building-up reactions is with in the acid and the alkaline catalysts termination reaction in the system, add deionized water again, excessive vinyl cyanide is reclaimed in distillation, separates out polyvinyl alcohol-β-thick product of cyanoethyl ether simultaneously.
9. manufacture method according to claim 8, the purifying that it is characterized in that polyvinyl alcohol-β-thick product of cyanoethyl ether are to adopt the acetone soln precipitating.
10. manufacture method according to claim 9 is characterized in that precipitating is 25-30% with the concentration of acetone, and precipitating carries out twice repeatedly, and temperature is controlled at 90-95 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB031350801A CN100400551C (en) | 2003-09-27 | 2003-09-27 | Improved polyvinyl alcohol-beta-cyanoethyl ether preparing method |
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| CNB031350801A CN100400551C (en) | 2003-09-27 | 2003-09-27 | Improved polyvinyl alcohol-beta-cyanoethyl ether preparing method |
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| CN1528799A CN1528799A (en) | 2004-09-15 |
| CN100400551C true CN100400551C (en) | 2008-07-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11066490B2 (en) | 2016-12-27 | 2021-07-20 | Lg Chem, Ltd. | Cyanoethyl group-containing polymer and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344511B (en) * | 2010-08-05 | 2013-07-03 | 卢树杰 | Modified synthesis method for high-viscosity film forming resin with dielectric property |
| US20120258348A1 (en) * | 2011-04-05 | 2012-10-11 | Kazuhisa Hayakawa | Binder for Separator of Non-Aqueous Electrolyte Battery Comprising 2-Cyanoethyl Group-Containing Polymer and Separator and Battery Using the Same |
| CN102942645B (en) * | 2012-10-22 | 2014-09-24 | 广州市杰迅电子材料有限公司 | Preparation method and application of modified polyvinyl alcohol resin |
| CN105153336B (en) * | 2015-10-14 | 2017-12-08 | 天津一森材料科技有限公司 | A kind of polyvinyl acetate cyanoethyl etherate and its synthetic method |
| KR102405288B1 (en) | 2019-01-22 | 2022-06-07 | 주식회사 엘지화학 | Vinyl alcohol based copolymer, method for preparing the same and gas barrier film comprising the same |
| CN117175141B (en) * | 2023-07-31 | 2024-03-19 | 中国科学院大连化学物理研究所 | Lithium battery diaphragm and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU509607A1 (en) * | 1971-06-11 | 1976-04-05 | Предприятие П/Я Р-6875 | The method of obtaining cyanoethyl ether polymer containing units of vinyl alcohol |
| JPS62259389A (en) * | 1986-05-02 | 1987-11-11 | 株式会社 興人 | Sianoethyl compound and device employing the same |
-
2003
- 2003-09-27 CN CNB031350801A patent/CN100400551C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU509607A1 (en) * | 1971-06-11 | 1976-04-05 | Предприятие П/Я Р-6875 | The method of obtaining cyanoethyl ether polymer containing units of vinyl alcohol |
| JPS62259389A (en) * | 1986-05-02 | 1987-11-11 | 株式会社 興人 | Sianoethyl compound and device employing the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11066490B2 (en) | 2016-12-27 | 2021-07-20 | Lg Chem, Ltd. | Cyanoethyl group-containing polymer and preparation method thereof |
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