CN1330090A - Process for preparing polyvinyl alcohol with low alcoholysis level - Google Patents
Process for preparing polyvinyl alcohol with low alcoholysis level Download PDFInfo
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- CN1330090A CN1330090A CN 01115186 CN01115186A CN1330090A CN 1330090 A CN1330090 A CN 1330090A CN 01115186 CN01115186 CN 01115186 CN 01115186 A CN01115186 A CN 01115186A CN 1330090 A CN1330090 A CN 1330090A
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- polyvinyl alcohol
- alcoholysis
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- methyl alcohol
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Abstract
A process for preparing low-alcoholysis polyvinyl alcohol includes such steps as mixing the solvent additive (ester, ether, ketone, or hydrocarbon) with methanol proportionally to obtain mixed solvent, dissolving polyvinyl acetate in it, heating to 45-50 deg.C, adding sodium hydroxide for alcoholysis, adding reaction arrester, and adding flocculant to obtain the low-alcoholysis (50-90%) polyvinyl alcohol.
Description
The present invention relates to the production technology of high molecular polymer polyvinyl alcohol with low alcoholysis level, a kind of production technique of producing polyvinyl alcohol with low alcoholysis level with the solvent subscription of more clearly saying so.
Polyvinyl alcohol with low alcoholysis level is widely used in aspects such as PVC polymerization, rubber latex polymerization, emulsifying technology, electronic industry and mould material manufacturing owing to have higher surface activity and lower surface tension, needs a large amount of imports, and the import price costliness.Tracing it to its cause, though be that the producer of domestic production polyvinyl alcohol is a lot, all is the single variety of higher alcoholysis degree.The low alcoholysis level kind of alcoholysis degree between 55～85% domesticly still can not be produced at present.In order to produce polyvinyl alcohol with low alcoholysis level, adopt dry technology of carrying out simultaneously in kneader abroad with alcoholysis.Produce the polyvinyl alcohol product of different alcoholysis degrees by control rate of drying and alcoholysis speed.Because the methanol solution of polyvinyl alcohol with low alcoholysis level belongs to highly viscous fluid, thus in the production process of low alcoholysis level product the power consumption height, single device throughput is little.
Purpose of the present invention, be to overcome above-mentioned shortcoming and defect, provide that a kind of power consumption is low, single device throughput is bigger, can satisfy domestic demand to polyvinyl alcohol with low alcoholysis level, substitute import, and can increase substantially the production technique of the polyvinyl alcohol with low alcoholysis level of business economic benefit again.
What in order to achieve the above object, the present invention adopted is solvent subscription technology.The wet method alcoholysis is adopted in the production of polyvinyl alcohol in early days.Just in the methanol solution of Vinyl Acetate Copolymer, add sodium hydroxide solution and carry out alcoholysis reaction.The characteristics of this method are that speed of response is fast, equipment volume is little, throughput is high, and process is that serialization is carried out.Shortcoming is that side reaction speed is fast, sodium acetate content height in the product.Adopt the dry method alcoholysis process in the recent period.Its reaction mass is not moisture substantially.Because the alcoholysis catalysts alkali dissolution is in methyl alcohol, the alkali mol ratio of employing is very low, has only 1/10th of wet method alcoholysis, and the purity of producing product is very high.Solvent subscription of the present invention is on the basis of former process using methyl alcohol as solvent, increases solvent additive, so that the solubleness of Vinyl Acetate Copolymer and polyvinyl alcohol meets the requirement of reaction process.Select for use earlier and dissolve each other with methyl alcohol and solvent additive and methyl alcohol that solvent parameter is less form mixed solvent, then Vinyl Acetate Copolymer is dissolved in the mixed solvent, its concentration is 20～30%, be warming up to 45～50 ℃, ratio adding sodium hydroxide solution in alkali mol ratio 0.05～0.12 carries out alcoholysis again, generate polyvinyl alcohol with low alcoholysis level, add the condensation agent again it is separated out.The solvent additive of selecting for use of dissolving each other with methyl alcohol is hydro carbons or ester time-like, when the quality proportioning of they and methyl alcohol is a kind of in 4: 6,3: 7,2: 8,1: 9 four kinds of proportioning, can obtain the polyvinyl alcohol with low alcoholysis level product, and is effective.The alcoholysis degree of its product is respectively 50～60%, 60～70%, 70～80% and 80～90%.Solvent additive also can be selected ethers or ketone for use.After generating polyvinyl alcohol with low alcoholysis level, should add reaction terminating agent in good time, in time stop alcoholysis reaction, add the condensation agent then it is separated out.After polyvinyl alcohol with low alcoholysis level formed product, remaining catalyzer and impurity still can change alcoholysis degree on some amount, and promptly therefore the poor stability of product will add terminator in good time control.
Solvent additive should have following characteristics: can dissolve each other with methyl alcohol; Can dissolve polyvinyl alcohol, and can change the solubility parameter of solvent after adding; Easily separate with methyl alcohol; Price is low, and toxicity is little, and addition is few.Above-mentioned hydro carbons, ester class, ethers or ketone such as ethanol, toluene, acetone etc. meet the requirements.Widened the gap between the solvent parameter of the solvent parameter of solvent and polyvinyl alcohol with low alcoholysis level by the solvent parameter that reduces mixed solvent.When the Vinyl Acetate Copolymer alcoholysis to a certain degree the time, become insolubles and separate out.Otherwise polyvinyl alcohol with low alcoholysis level solvent constant is close with the methanol solvent constant, and polyvinyl alcohol then can't be separated out in alcoholysis process.
The speed of response of alcoholysis can be by the alkali mol ratio control that adds.Adding alkali mol ratio is 0.05～0.12 sodium hydroxide solution, has speed of response, higher production efficiency faster.This is a kind of catalyst formulation preferably.The concentration of 45～50 ℃ temperature of reaction, Vinyl Acetate Copolymer 20～30%, alkali mol ratio 0.05～0.12nd, The optimum reaction conditions, satisfactory for result.
Isolate in the solvent behind the product and contain a certain amount of catalyzer, terminator, condensation agent and salt.If this solution circulated is used, need partial elements is wherein separated, the simplest method is to carry out rectifying separation by packing tower.
Task of the present invention comes to this and finishes.
The invention provides a kind of production technique of better simply polyvinyl alcohol with low alcoholysis level newly.It has higher production efficiency, and lower power consumption is arranged, and it can satisfy domestic demand to polyvinyl alcohol with low alcoholysis level, substitutes import, can increase substantially the economic benefit of manufacturing enterprise again.It can be widely used in and produce in the production that alcoholysis degree is 50～90% polyvinyl alcohol with low alcoholysis level.
Below in conjunction with embodiment the present invention is done further explanation.But flesh and blood of the present invention is not limited to embodiment.
Embodiment 1, a kind of production technique of polyvinyl alcohol with low alcoholysis level.It is to select for use the ester class to form mixed solvent as solvent additive and methyl alcohol, and the quality proportioning of methyl alcohol and ester class is 6: 4 in the mixed solvent.Then Vinyl Acetate Copolymer is dissolved in the mixed solvent, its concentration is 20～30%, is warming up to 45～50 ℃.Ratio adding catalyzer sodium hydroxide solution in alkali mol ratio 0.05～0.12 carries out alcoholysis again.The back adds reaction terminating agent and stops alcoholysis reaction, adds the condensation agent again and separates out polyvinyl alcohol with low alcoholysis level.The alcoholysis degree of the product of producing is 50～60%.
Embodiment 2, a kind of production technique of polyvinyl alcohol with low alcoholysis level.Select for use hydro carbons as solvent additive.The quality proportioning of methyl alcohol and hydro carbons is 6: 4 in the mixed solvent.All the other processing condition are with embodiment 1.The alcoholysis degree of product is 50～60%.
Embodiment 3, a kind of production technique of polyvinyl alcohol with low alcoholysis level.Select for use the ester class as solvent additive.The quality proportioning of methyl alcohol and ester class is 7: 3 in the mixed solvent.All the other processing condition are with embodiment 1.The alcoholysis degree of product is 60～70%.
Embodiment 4, a kind of production technique of polyvinyl alcohol with low alcoholysis level.Select for use hydro carbons as solvent additive.The mass ratio of methyl alcohol and hydro carbons is 7: 3 in the mixed solvent.All the other processing condition are with embodiment 1.The alcoholysis degree of product is 60～70%.
Embodiment 5, a kind of production technique of polyvinyl alcohol with low alcoholysis level.Select for use the ester class as solvent additive.The mass ratio of methyl alcohol and ester class is 8: 2 in the mixed solvent.All the other processing condition are with embodiment 1.The alcoholysis degree of product is 70～80%.
Embodiment 6, a kind of production technique of polyvinyl alcohol with low alcoholysis level.Select for use hydro carbons as solvent additive.The mass ratio of methyl alcohol and hydro carbons is 8: 2 in the mixed solvent.All the other processing condition are with embodiment 1.The alcoholysis degree of product is 70～80%.
Embodiment 7, a kind of production technique of polyvinyl alcohol with low alcoholysis level.Select for use the ester class as solvent additive.The mass ratio of methyl alcohol and ester class is 9: 1 in the mixed solvent.All the other processing condition are with embodiment 1.The alcoholysis degree of product is 80～90%.
Embodiment 8, a kind of production technique of polyvinyl alcohol with low alcoholysis level.Select for use hydro carbons as solvent additive.The mass ratio of methyl alcohol and hydro carbons is 9: 1 in the mixed solvent.All the other processing condition are with embodiment 1.The alcoholysis degree of product is 80～90%.
Claims (4)
1, a kind of production technique of polyvinyl alcohol with low alcoholysis level, it dissolves by Vinyl Acetate Copolymer is added in the methyl alcohol, add the catalyzer sodium hydroxide solution again and carry out technological process compositions such as alcoholysis reaction, it is characterized in that it is to select for use earlier to dissolve each other with methyl alcohol and solvent additive and methyl alcohol that solvent parameter is less form mixed solvent, then Vinyl Acetate Copolymer is dissolved in the mixed solvent, its concentration is 20～30%, is warming up to 45～50 ℃.Ratio adding sodium hydroxide solution in alkali mol ratio 0.05～0.12 carries out alcoholysis again, generates polyvinyl alcohol with low alcoholysis level and adds the condensation agent it is separated out.
2, according to the production technique of the described polyvinyl alcohol with low alcoholysis level of claim 1, it is characterized in that the said solvent additive of dissolving each other with methyl alcohol that select for use is hydro carbons or ester class etc., the quality proportioning of they and methyl alcohol is a kind of in 4: 6,3: 7,2: 8,1: 9 four kinds of proportioning.
3,, it is characterized in that the said solvent additive of dissolving each other with methyl alcohol that select for use is ethers or ketone according to the production technique of the described polyvinyl alcohol with low alcoholysis level of claim 1.
4, according to the production technique of the described polyvinyl alcohol with low alcoholysis level of any claim in the claim 1～3, should add reaction terminating agent after it is characterized in that generating polyvinyl alcohol with low alcoholysis level in good time, in time stop alcoholysis reaction, add the condensation agent then it is separated out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011151862A CN1164629C (en) | 2001-08-01 | 2001-08-01 | Process for preparing polyvinyl alcohol with low alcoholysis level |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011151862A CN1164629C (en) | 2001-08-01 | 2001-08-01 | Process for preparing polyvinyl alcohol with low alcoholysis level |
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| CN1330090A true CN1330090A (en) | 2002-01-09 |
| CN1164629C CN1164629C (en) | 2004-09-01 |
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| CNB011151862A Expired - Fee Related CN1164629C (en) | 2001-08-01 | 2001-08-01 | Process for preparing polyvinyl alcohol with low alcoholysis level |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626903A (en) * | 2013-12-10 | 2014-03-12 | 济南开发区星火科学技术研究院 | Production method of polyvinyl alcohol with low polymerization degree and low alcoholysis degree |
| CN106008772A (en) * | 2016-07-12 | 2016-10-12 | 中国石油化工股份有限公司 | Method for safely controlling polymerization reaction of vinyl acetate-methanol mixed liquid |
| CN111072824A (en) * | 2019-12-30 | 2020-04-28 | 内蒙古蒙维科技有限公司 | Preparation method of polyvinyl alcohol with low ash content and low alcoholysis degree |
| CN111763275A (en) * | 2020-07-23 | 2020-10-13 | 安徽皖维高新材料股份有限公司 | Method for prolonging production period of polyvinyl alcohol with low alcoholysis degree |
| CN113004443A (en) * | 2021-03-09 | 2021-06-22 | 内蒙古双欣环保材料股份有限公司 | Rapid gelation method of polyvinyl alcohol and preparation method of polyvinyl alcohol with low alcoholysis degree |
| CN115418144A (en) * | 2022-08-19 | 2022-12-02 | 复旦大学 | Antifogging coating material of polyvinyl alcohol with ultra-low alcoholysis degree and preparation method thereof |
-
2001
- 2001-08-01 CN CNB011151862A patent/CN1164629C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626903A (en) * | 2013-12-10 | 2014-03-12 | 济南开发区星火科学技术研究院 | Production method of polyvinyl alcohol with low polymerization degree and low alcoholysis degree |
| CN106008772A (en) * | 2016-07-12 | 2016-10-12 | 中国石油化工股份有限公司 | Method for safely controlling polymerization reaction of vinyl acetate-methanol mixed liquid |
| CN106008772B (en) * | 2016-07-12 | 2018-06-19 | 中国石油化工股份有限公司 | The method of controlling security of vinyl acetate-methyl alcohol mixed liquor polymerisation |
| CN111072824A (en) * | 2019-12-30 | 2020-04-28 | 内蒙古蒙维科技有限公司 | Preparation method of polyvinyl alcohol with low ash content and low alcoholysis degree |
| CN111763275A (en) * | 2020-07-23 | 2020-10-13 | 安徽皖维高新材料股份有限公司 | Method for prolonging production period of polyvinyl alcohol with low alcoholysis degree |
| CN111763275B (en) * | 2020-07-23 | 2023-03-28 | 安徽皖维高新材料股份有限公司 | Method for prolonging production period of polyvinyl alcohol with low alcoholysis degree |
| CN113004443A (en) * | 2021-03-09 | 2021-06-22 | 内蒙古双欣环保材料股份有限公司 | Rapid gelation method of polyvinyl alcohol and preparation method of polyvinyl alcohol with low alcoholysis degree |
| CN115418144A (en) * | 2022-08-19 | 2022-12-02 | 复旦大学 | Antifogging coating material of polyvinyl alcohol with ultra-low alcoholysis degree and preparation method thereof |
| CN115418144B (en) * | 2022-08-19 | 2023-10-31 | 复旦大学 | Ultra-low alcoholysis degree polyvinyl alcohol anti-fog coating material and manufacturing method thereof |
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| Publication number | Publication date |
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| CN1164629C (en) | 2004-09-01 |
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Assignee: Shandong Tuobo Plastic Products Co., Ltd. Assignor: Qingdao University of Science & Technology Contract fulfillment period: 2009.9.10 to 2014.9.10 contract change Contract record no.: 2009370000497 Denomination of invention: Process for preparing polyvinyl alcohol with low alcoholysis level Granted publication date: 20040901 License type: Exclusive license Record date: 2009.11.6 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.9.10 TO 2014.9.10; CHANGE OF CONTRACT Name of requester: SHANDONG TUOBO PLASTIC PRODUCTS CO.,LTD. Effective date: 20091106 |
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Assignee: Shandong Tuobo Plastic Products Co., Ltd. Assignor: Qingdao University of Science & Technology Contract fulfillment period: 2009.9.10 to 2014.9.10 contract change Contract record no.: 2009370000501 Denomination of invention: Process for preparing polyvinyl alcohol with low alcoholysis level Granted publication date: 20040901 License type: Exclusive license Record date: 20091118 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.9.10 TO 2014.9.10; CHANGE OF CONTRACT Name of requester: SHANDONG TUOBO PLASTIC PRODUCTS CO.,LTD. Effective date: 20091118 |
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Granted publication date: 20040901 |