CN102030856A - Method for devolatilizing vinyl methyl ether/maleic anhydride copolymer - Google Patents
Method for devolatilizing vinyl methyl ether/maleic anhydride copolymer Download PDFInfo
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- CN102030856A CN102030856A CN2009101722610A CN200910172261A CN102030856A CN 102030856 A CN102030856 A CN 102030856A CN 2009101722610 A CN2009101722610 A CN 2009101722610A CN 200910172261 A CN200910172261 A CN 200910172261A CN 102030856 A CN102030856 A CN 102030856A
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- maleic anhydride
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- methoxy ethylene
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Abstract
The invention discloses a method for devolatilizing vinyl methyl ether/maleic anhydride copolymer, which comprises the following steps of: 1, washing wet or dry powder vinyl methyl ether/maleic anhydride copolymer by using alcohol; 2, filtering the washed copolymer and the alcohol; and 3, evaporating an alcohol-containing wet material from the filtered copolymer and the alcohol in vacuum at the temperature of between 50 and 150 DEG C to remove the alcohol. By the devolatilizing process, an inappropriate solvent or other impurities in polymer can be efficiently removed, so that a product is suitable for medicine, mouth care and food; the product, namely alkyl vinyl ether/maleic anhydride copolymer powder actually does not contain any inappropriate solvent or the other impurities; and the molar ratio of the copolymer is 1:1, and the special viscosity is between 0.2 and over 10.
Description
Technical field
The present invention relates to a kind of devolatilization method of multipolymer, especially a kind of devolatilization method of methoxy ethylene/copolymer-maleic anhydride.
Background technology
Existing invention discloses the technology of alkyl vinyl ether/maleic anhydride suspension copolymer, and two kinds of monomers participating in polyreaction can obtain insoluble multipolymer in aliphatics or aromatic hydrocarbons in organic system.
English Patent 906,230 have described methoxy ethylene and maleic anhydride carry out suspension polymerization in benzene solvent research, U.S. Patent No. 5,385,995 and 6,624,271 have described methoxy ethylene and copolymer-maleic anhydride carry out copolyreaction respectively in blended fat/hydrocarbon solvent and ethyl acetate situation.
United States Patent (USP) 5,047,490 and 6,184,325 have discussed the technology of synthesis of alkyl vinyl ether/maleic anhydride multipolymer under solvent-free state, but this technology actual be a suspension polymerization process, wherein alkyl vinyl ether is excessive more, therefore holds solvent and two kinds of functions of reaction partner.
United States Patent (USP) 5,959 has been described intermittence, the no-solvent process of preparation C1-C4 alkyl vinyl ether/maleic anhydride high molecular alternating copolymer powder in 053 and 5,939,506.
Chinese patent CN 1443202A has introduced a kind of under solvent-free state, with continuously feeding, the continuous successive polymerization reaction process of the C1-C4 alkyl vinyl ether/maleic anhydride multipolymer that carries out of discharge method, the feature of this method is that monomer A VE, maleic anhydride and three principal reaction partners of initiator are to add in the reactor respectively.
Residual solvent and impurity are more in the powder that a total shortcoming of the disclosed suspension polymerization of above-mentioned prior art is a polymkeric substance, the allowed band that has surpassed cosmetic industry, pharmaceutical sector and food service industry is especially worked as the situation that the such carcinogenic substance of benzene is used for the copolyreaction solvent.
Solvent-free technology is used in the production practice of recently increasing alkyl vinyl ether/maleic anhydride multipolymer.In such technology, to add in the reaction with bigger ratio as monomeric alkyl vinyl ether, so that allow this material have both the effect of polymerization solvent simultaneously.The content of " solvent " is limited in the powder-product of the prepared of even now, can not accept smell and the sense of taste is unhappy but still comprised some impurities that should not exist or residual monomer and caused.
Summary of the invention
Technical problem to be solved by this invention provides a kind of polymkeric substance devolatilization method and prepares the alkyl vinyl ether/maleic anhydride multipolymer and obtain high-quality powder-product, wherein do not contain solvent, residual monomer or other impurity that should not exist in this powder-product, reach the requirement that this polymkeric substance can be used for medicine, mouth care and food uses.
In order to solve the problems of the technologies described above, the present invention discloses a kind of devolatilization method of methoxy ethylene/copolymer-maleic anhydride, and this devolatilization method may further comprise the steps: step 1, will wet or dry powder under methoxy ethylene/copolymer-maleic anhydride wash with alcohol; Step 2, with washed multipolymer with alcohol suspension filter; Step 3, multipolymer after the filtration treatment and alcohol are removed alcohol at the wet stock that evaporation under the vacuum condition and in 50 ℃ of-150 ℃ of temperature ranges contains alcohol.
Further, described alcohol is ethanol or Virahol.
Further, described multipolymer is 1: 0.2～1: 20 to the usage ratio of alcohol by weight scope, and preferred proportion is 1: 1～1: 10.
Further, the wash temperature of described alcohol is 10 ℃～80 ℃, preferred 20 ℃～80 ℃.
Further, it is 1 minute～5 hours that described alcohol washs perdurability, preferred 10 minutes～1 hour.
Further, the temperature range in the step 3 is preferred 0 ℃～130 ℃.
Further, described three step operating method are the operate continuously mode.
Further, described three step operating method are the batch operation mode.
Further, after step 1 alcohol washing multipolymer, water is with the suspension washing of alcohol with multipolymer again.
Beneficial effect of the present invention is:
Thereby process for devolatilization of the present invention can be accomplished to remove efficiently solvent or other impurity that should not exist and accomplish that product is applicable to medicine, mouth care and food uses from polymkeric substance; Its products therefrom alkyl vinyl ether/maleic anhydride copolymer powder is actual can accomplish not contain solvent or other impurity that should not exist, and its mol ratio is 1: 1, special viscosity from 0.2 to surpassing 10.
Embodiment
Below in conjunction with embodiment technical solution of the present invention is described in further detail.
Embodiment:
With the reactor of 60L with nitrogen replacement after; the methoxy ethylene that adds 32L; add the 5.5kg maleic anhydride in the another one container, 6.3kg ethyl acetate and 7.5kg didecyl acyl peroxide obtain the maleic anhydride/initiator solution of a clear after the mixing.Temperature of reaction kettle is risen to 70 ℃ and carry out strong stirring.After temperature rose to 70 ℃, beginning was interior with the 4 hours even maleic anhydride/initiator homogeneous phase liquid that adds toward reactor.4 hours afterreaction stills continue to keep 70 ℃ 2 hours, cool off reactor then.The multipolymer that generates obtains the flowing powder of white after drying, and does not contain remaining maleic anhydride monomer and impurity.The special viscosity of multipolymer reaches more than 5.The copolymer powder that obtains contains very strong ethyl acetate and methoxy ethylene smell, then with the ethanol of 10kg 30 ℃ of washings 30 minutes down, then with polymkeric substance and alcoholic acid mixing suspension through filtering the back with 120 ℃ of dryings 4 hours.The polymkeric substance that obtains is scentless free flowing powder, detects through fourier-transform infrared chromatographic instrument (FTIR), shows that the chemical structure of maleic anhydride part in the multipolymer and the powder before the devolatilization processing are on all four.
The principle of work and the characteristics of technical solution of the present invention are as described below:
1, the present invention is by washing multipolymer wet feed or dried powder with alcohol, then under vacuum condition, evaporation contains alcohol in 50 ℃～150 ℃ temperature ranges wet stock removes the process for devolatilization of alcohol.The alcohol that is suitable for comprises food grade or pharmaceutical grade ethanol or Virahol.The amount of washing required pure and mild polymkeric substance in principle can be from 1: 0.2～1: 20 than the specification of quality that depends on the finished product, preferred 1: 1～1: 20.The temperature range of washing is 10 ℃～80 ℃, and preferred 20 ℃～50 ℃, washing time is 1 minute～5 hours, preferred 10 minutes～1 hour.After washing process finishes, polymkeric substance is placed in the vacuum environment, carries out drying with 50 ℃-150 ℃, preferred range is 80 ℃-130 ℃.
2, known studies show that, alcohols material such as ethanol or Virahol can react with half family of maleic anhydride in the alkyl vinyl ether/maleic anhydride multipolymer, generate toxilic acid/alkyl half fat derivative.If carry out but wash in the short relatively time, its derivatization reaction can be controlled in the minimum scope.In addition, because by washing, can slough the impurity that causes bad color, smell and the sense of taste in the product, therefore the powder-product of handling can enough higher temperature carry out drying and polymer quality not had influence.This not only can improve the speed of dry materials, but also a part can be separated with alcohol with the material generation reversed reaction that half fat derivatization reaction takes place fat in washing process, comes back to the state of anhydrous multipolymer.
3, under some special situation, multipolymer can also carry out repeatedly such devolatilization operation, thereby obtains the very high polymkeric substance of purity.For example, multipolymer can be carried out dry this material of alcohol washing final vacuum with above-mentioned way, and then once wash and drying process, the multipolymer of handling like this can accomplish that reality does not contain any residual solvent or impurity.Directly to wash multipolymer be not an effective way to water, because a lot of dissolvent residuals in the multipolymer or impurity are water-fast, what only water washed out with them is very difficult.It is emphasized that treated high purity multipolymer allows to carry out drying with higher temperature, such high temperature can come back to original multipolymer state with alkyl half fat or diacid generation reversed reaction simultaneously.
4, the present invention can adopt the mode of intermittent type or continous way to handle.This process for devolatilization goes for any alkyl vinyl ether/maleic anhydride copolymer powder, but is best suited for the multipolymer with the suspension polymerization process preparation.Also be applicable to any special viscosity from 0.2 to the multipolymer that surpasses 10.
Protection domain of the present invention is not limited to the described scope of above-mentioned embodiment, and every technology distortion of being done according to the technical solution of the present invention principle all falls into protection scope of the present invention.
Claims (9)
1. the devolatilization method of a methoxy ethylene/copolymer-maleic anhydride is characterized in that, this devolatilization method may further comprise the steps: step 1, will wet or dry powder under methoxy ethylene/copolymer-maleic anhydride wash with alcohol; Step 2, with washed multipolymer with alcohol suspension filter; Step 3, multipolymer after the filtration treatment and alcohol are removed alcohol at the wet stock that evaporation under the vacuum condition and in 50 ℃ of-150 ℃ of temperature ranges contains alcohol.
2. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1, it is characterized in that: described alcohol is ethanol or Virahol.
3. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1 is characterized in that: described multipolymer is 1: 0.2～1: 20 to the usage ratio of alcohol by weight scope, and preferred proportion is 1: 1～1: 10.
4. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1, it is characterized in that: the wash temperature of described alcohol is 10 ℃～80 ℃, preferred 20 ℃～80 ℃.
5. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1 is characterized in that: described alcohol washing perdurability is 1 minute～5 hours, preferred 10 minutes～1 hour.
6. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1 is characterized in that: preferred 0 ℃～130 ℃ of the temperature range in the step 3.
7. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1, it is characterized in that: described three step operating method are the operate continuously mode.
8. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1, it is characterized in that: described three step operating method are the batch operation mode.
9. the devolatilization method of methoxy ethylene/copolymer-maleic anhydride according to claim 1 is characterized in that: after step 1 alcohol washing multipolymer, water is with the suspension washing of alcohol with multipolymer again.
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| CN2009101722610A CN102030856B (en) | 2009-09-25 | 2009-09-25 | Method for devolatilizing vinyl methyl ether/maleic anhydride copolymer |
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| CN2009101722610A CN102030856B (en) | 2009-09-25 | 2009-09-25 | Method for devolatilizing vinyl methyl ether/maleic anhydride copolymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020151009A1 (en) * | 2019-01-25 | 2020-07-30 | Boai Nky Medical Holdings Ltd. | Ultra-pure methyl vinyl ether-co-maleic anhydride copolymers and methods for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5223567A (en) * | 1992-03-16 | 1993-06-29 | Isp Investments Inc. | Process for production of an ethanol solution of the ethyl or butyl half-ester of a copolymer of maleic anhydride and methyl vinyl ether |
| US6214956B1 (en) * | 1997-10-02 | 2001-04-10 | Isp Investments Inc. | Solvent-free copolymers of maleic anhydride and alkyl vinyl ethers having a specific viscosity of 0.5 to 5 and method of making |
| JP2000191705A (en) * | 1998-12-25 | 2000-07-11 | Daicel Chem Ind Ltd | Method for producing methylvinyl ether-maleic anhydride copolymer |
| ATE306505T1 (en) * | 2000-06-15 | 2005-10-15 | Isp Investments Inc | CONTINUOUS SOLVENT-FREE PROCESS FOR PRODUCING COPOLYMERS OF MALEIC ANHYDRIDE AND C1-4? ALKYL VINYL ETHER |
| DE10163449A1 (en) * | 2000-07-28 | 2002-07-11 | Daicel Chem | Process for the preparation of a copolymer of alkyl vinyl ether and maleic anhydride and a copolymer of alkyl vinyl ether and maleic anhydride |
| JP2004292501A (en) * | 2003-03-25 | 2004-10-21 | Daicel Chem Ind Ltd | Method for producing maleic anhydride-alkyl vinyl ether copolymer |
| CN101456932A (en) * | 2008-12-25 | 2009-06-17 | 锦西化工研究院 | Method for preparing maleic anhydride-alkyl vinyl ether co-polymer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020151009A1 (en) * | 2019-01-25 | 2020-07-30 | Boai Nky Medical Holdings Ltd. | Ultra-pure methyl vinyl ether-co-maleic anhydride copolymers and methods for preparing same |
| CN113383023A (en) * | 2019-01-25 | 2021-09-10 | 博爱新开源医疗科技集团股份有限公司 | Ultrapure methyl vinyl ether-co-maleic anhydride copolymer and preparation method thereof |
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Address after: The town of Thanh Hoa Boai County in Henan province 454450 No. 9 Zhongshan Road Patentee after: The medical fraternity xinkaiyuan Technology Group Limited by Share Ltd Address before: The town of Thanh Hoa Boai County in Henan province 454450 No. 9 Zhongshan Road Patentee before: Boai New Kaiyuan Pharmaceutical Co., Ltd. |
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Effective date of registration: 20220309 Address after: 454450 No. 1888, Cultural Road (eastern section), Poai County, Jiaozuo, Henan Patentee after: Boai Xinkaiyuan Pharmaceutical Co.,Ltd. Address before: The town of Thanh Hoa Boai County in Henan province 454450 No. 9 Zhongshan Road Patentee before: BOAI NKY MEDICAL HOLDINGS Ltd. |