CN102020735A - Purification method of polyvinyl alcohol - Google Patents
Purification method of polyvinyl alcohol Download PDFInfo
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- CN102020735A CN102020735A CN2009101908855A CN200910190885A CN102020735A CN 102020735 A CN102020735 A CN 102020735A CN 2009101908855 A CN2009101908855 A CN 2009101908855A CN 200910190885 A CN200910190885 A CN 200910190885A CN 102020735 A CN102020735 A CN 102020735A
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Abstract
The invention relates to a purification method of polyvinyl alcohol obtained by alkali catalysis on polyvinyl acetate. In the method, a solution in which polyvinyl alcohol is undissolved or difficult to be dissolved while residues of polyvinyl alcohol are soluble is taken as a solvent, and purification on polyvinyl alcohol is carried out. The invention requires no modification on the traditional mature and complete industrialized PVA preparation process, thus being beneficial to implementation of industrialization, and ash content of the polyvinyl alcohol purified by the method in the invention is close to or less than 0.1%; and the solvent required in the process for preparing polyvinyl alcohol from polyvinyl acetate by hydrolysis or the product obtained by the process is taken as a solvent for purification treatment of polyvinyl alcohol, the produced waste liquor can be merged into the original waste liquor recovery and purification system, the cost is effectively reduced, and the separation of the polyvinyl alcohol after being purified is convenient.
Description
Technical field
The present invention relates to a kind of purification process of polyvinyl alcohol, be specially adapted to the purification process of the polyvinyl alcohol that alkaline process catalysis polyvinyl acetate (PVA) makes.
Background technology
Because polyvinyl alcohol (to call PVA in the following text) is nontoxic, has well water-soluble and better biocompatibility, a lot of special purposes are arranged in fields such as medicine and lives, domestic and international all very big (the UhrichK E of demand to polyvinyl alcohol, Canizarro S M, et al.Polymeric systems for control drug release[J] .ChemRev, 1999,99:3181-3198).Polyvinyl alcohol mainly obtains by acid system or alkali process hydrolysis polyvinyl acetate (PVA).Wherein, the acid system hydrolysis is owing to exist a lot of shortcomings, and, corrosive equipment slow as speed of response, product are painted easily etc., less employing in industrial production; With sodium hydroxide NaOH is but that the method that the alkali process hydrolysis polyvinyl acetate (PVA) of catalyzer prepares polyvinyl alcohol has advantages such as technology is simple, the production of process safety continuous high-efficient, is widely used in the industrial production.Yet, traditional base catalysis technology, because the existence of factors such as the kind of catalyzer and unavoidable side reaction, can contain a certain amount of sodium-acetate and a spot of catalyst n aOH in the finished product polyvinyl alcohol, this part residue makes product polyvinyl alcohol purity drop, influences the performance and the use range of polyvinyl alcohol.Improve polyvinyl alcohol purity and can effectively improve the polyvinyl alcohol quality, expand the range of application of polyvinyl alcohol.
At present, the method for inorganic content, raising polyvinyl alcohol purity mainly contains following several in the reduction PVA product:
1, with ammoniacal liquor is ashless minute polyvinyl alcohol of catalyzer (Steffenssen Otto, Johnsen Henry, Johnsen Reidar, Processfor the production of polyvinyl alcohol[P], DE948087,1956) preparation.Because the alkalescence of ammonia is very weak, be difficult to the catalytic hydrolysis polyvinyl acetate (PVA).Therefore, the ammonia process hydrolysis can only be used for the polyvinyl ester than facile hydrolysis, as poly-Monochloro Acetic Acid vinyl acetate, poly-dichloro acetic acid vinyl acetate and polyvinyl formate etc., can not be used for the catalysis polyvinyl acetate (PVA), does not possess industrialized meaning.
2, with the organic bases be catalyzer (Griffith Bowen, Alcoholysis of polyvinyl esters[P], US2464290,1949) preparation high purity white polyvinyl alcohol.Usually organic bases has higher toxicity and explosion hazard, and preparation is complicated, has bigger potential safety hazard, has therefore limited the industrial applications of this method.
3, adopt potassium hydroxide KOH catalysis (Li Shengji work, Feng Baosheng translates, vinylon [M], Beijing: textile industry press, p249,1986).Because the catalytic efficiency of KOH is higher than NaOH, and by product Potassium ethanoate (CH
3COOK) solubleness in methyl alcohol is than sodium-acetate (CH
3COONa) solubleness in methyl alcohol is big, therefore, uses KOH should help removing acetate from the PVA that makes, thereby obtains the polyvinyl alcohol of higher degree.But in fact since the molecular weight that the consumption of KOH can not infinitely reduce and the molecular weight of KOH is greater than NaOH (wait under the residual condition of alkali mol ratio acetate, use KOH to make the catalyzer ash content and want high), use KOH to substitute NaOH merely and can not prepare the very high polyvinyl alcohol product of purity very effectively.
4, ion-exchange remove inorganic salt in the polyvinyl alcohol (Paul Halbig, Paul Wicht, Preparation ofpolyvinyl alcohol[P], US2940948,1960; Hayes Richard A, Removal of base residuesfrom poly (vinyl alcohol) reaction-slurries[P], US5425879,1995).This method can prepare highly purified PVA product very effectively under the condition that does not change preparation technology in early stage, but when carrying out ion-exchange, must dissolve PVA (or being partly dissolved) in water earlier, after waiting to remove metal ion, also dissolved PVA will be precipitated out again, energy consumption is very high, complex process, cost increases significantly, and therefore certain difficulty is arranged in industrial application.
In addition, the above method need be made bigger adjustment to relatively ripe perfect preparation of industrialization PVA technology usually, has very big difficulty in actual applications.
Summary of the invention
The object of the present invention is to provide a kind of technology simple, can effectively remove the wherein purification process of the polyvinyl alcohol of residual inorganics.It need not change the preparation technology of polyvinyl alcohol, and just can reach the effect that reduces the polyvinyl alcohol ash content by prepared polyvinyl alcohol being carried out aftertreatment.
The object of the present invention is achieved like this: a kind of purification process of polyvinyl alcohol, the polyvinyl alcohol that makes for alkaline process catalysis polyvinyl acetate (PVA) particularly, reduce the purification process of its ash content, its adopt polyvinyl alcohol insoluble therein or be difficult for molten and in the polyvinyl alcohol residue therein solubleness big as solvent, polyvinyl alcohol is carried out purification process.
Above-mentioned solvent is selected solvent or the product that is adopted in the poly-ethanol of polyvinyl acetate (PVA) hydrolysis preparation for use.
Above-mentioned solvent is selected at least a in methyl alcohol, water, the ethyl acetate for use; Especially the mixed solvent of selecting the first alcohol and water is good.
The temperature of above-mentioned purification process is 30 ℃～60 ℃, and usually conduct got final product in 10～60 minutes.
The treatment capacity of above-mentioned polyvinyl alcohol is: polyvinyl alcohol parts by weight and solvent volume portion rate are 10～50 parts: 50～90 parts.
Specifically, a kind of purification process of polyvinyl alcohol, it is under 30 ℃～60 ℃ temperature, and 10～50 weight account polyethylenes alcohol and 50～90 parts by volume solvent are stirred, and makes that residue is dissolved in the solvent in the polyvinyl alcohol; Divide the solvent of the molten residue of leaving away then, more separating obtained polyvinyl alcohol is carried out drying and get final product; Wherein solvent is at least a in methyl alcohol, water, the ethyl acetate.
Above-mentioned polyvinyl alcohol is a particulate polyethylene alcohol, is good with process pulverizing and undried granule of polyvinyl alcohol especially.
If adopt the first alcohol and water as solvent, both mixed volumes ratio be 5: 1 for good.
The present invention has following advantage:
1, the present invention is the purification process that the polyvinyl alcohol that alkaline process catalysis polyvinyl acetate (PVA) makes is carried out, and it does not need that what traditional comparatively ripe perfect preparation of industrialization PVA technology done adjusts, and is very beneficial for industrialized enforcement; And be near 0.1% or lower through the ash content of the polyvinyl alcohol of the method for the invention purifying.
2. adopt methyl alcohol, water, ethyl acetate or their mixture as solvent, these solvents also are that the polyvinyl acetate (PVA) hydrolysis prepares solvent required in the polyvinyl alcohol technology or product, therefore, adopt the waste liquid that the present invention produced to incorporate former waste liquid recovery, purification system into, effectively reduce cost;
3. adopt methyl alcohol, water, ethyl acetate or their mixture as mixed solvent, can guarantee dissolving, when removing in the polyvinyl alcohol residual inorganics, dissolve polyvinyl alcohol not helps the separation of polyvinyl alcohol behind the purifying.
Description of drawings
Fig. 1 is an infrared spectra spectrogram before and after embodiment 4 gained polyvinyl alcohol are handled by the inventive method;
Fig. 2 is an XRD spectra before and after embodiment 4 gained polyvinyl alcohol are handled by the inventive method.
Embodiment:
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
On the whole, a kind of purification process of polyvinyl alcohol, it comprises the steps: under 30 ℃～60 ℃ temperature, and 10～50 weight account polyethylenes alcohol and 50～90 parts by volume solvent were stirred 10～60 minutes, and the inorganics that contains in the polyvinyl alcohol is dissolved in the solvent; Divide to leave away then to be dissolved with the solvent of inorganic salt, again polyvinyl alcohol is carried out drying and get final product; Wherein solvent is at least a in methyl alcohol, water, the ethyl acetate.
Embodiment 1: 25 parts of granule of polyvinyl alcohol (polymerization degree is 2400, and alcoholysis degree is 99%) are distributed in 75 parts the methyl alcohol, stir 20min down, filter to isolate polyvinyl alcohol then at 50 ℃, 60 ℃ of oven dry down, high purity polyethylene alcohol.Measure processing front and back polyvinyl alcohol ash content respectively according to national standard (GB 12010.7-89), the result shows that the ash content of polyvinyl alcohol (polymerization degree is 2400, and alcoholysis degree is 99%) drops to 0.064% by 0.27% before handling.
Embodiment 2: (polymerization degree is 2400 with 30 parts of granule of polyvinyl alcohol, alcoholysis degree is 99%) be distributed to the mixing solutions (methyl alcohol: water=5: 1 of 70 parts first alcohol and water, in volume ratio) in, stir 30min down at 40 ℃, filter to isolate polyvinyl alcohol then, 60 ℃ of oven dry down get high purity polyethylene alcohol.Measure processing front and back polyvinyl alcohol ash content respectively according to national standard (GB 12010.7-89), the result shows that the ash content of polyvinyl alcohol (polymerization degree is 2400, and alcoholysis degree is 99%) drops to 0.043% by 0.27% before handling.
Embodiment 3: 30 parts of polyvinyl alcohol (polymerization degree is 1700, and alcoholysis degree is 88%) are distributed in 70 parts the ethyl acetate, stir 10min down, filter to isolate polyvinyl alcohol then at 60 ℃, 60 ℃ of oven dry down, high purity polyethylene alcohol.Measure processing front and back polyvinyl alcohol ash content respectively according to national standard (GB 12010.7-89), the result shows that the ash content of polyvinyl alcohol (polymerization degree is 1700, and alcoholysis degree is 88%) drops to 0.013% by 0.19% before handling.
Certainly, in this example, also can carry out purification process as solvent to polyvinyl alcohol by water.
Embodiment 4: (polymerization degree is 1700 with 20 parts of granule of polyvinyl alcohol, alcoholysis degree is 99%) be distributed to 80 parts methyl alcohol and the mixing solutions of ethyl acetate (methyl alcohol: ethyl acetate=9: 1, in volume ratio) in, stir 60min down at 30 ℃, filter to isolate polyvinyl alcohol then, 60 ℃ of oven dry down get high purity polyethylene alcohol.Measure processing front and back polyvinyl alcohol ash content respectively according to national standard (GB12010.7-89), the result shows that the ash content of polyvinyl alcohol (polymerization degree is 1700, and alcoholysis degree is 99%) drops to 0.12% by 0.4% before handling.
Referring to Fig. 1 and Fig. 2, find in Fig. 1 that further undressed polyvinyl alcohol is at 1570cm
-1There is assorted peak at the place, and polyvinyl alcohol does not after treatment have this assorted peak, shows that the purity through handling PVA is improved; Find that in Fig. 2 the XRD curve of polyvinyl alcohol almost overlaps before and after handling, and shows by the present invention program polyvinyl alcohol is carried out structure and the crystal property that purification process can not influence polyvinyl alcohol.
Claims (8)
1. the purification process of a polyvinyl alcohol is characterized in that: its adopts polyvinyl alcohol insoluble therein or be difficult for molten and residue in the polyvinyl alcohol is easily molten therein as solvent, and polyvinyl alcohol is carried out purification process.
2. the purification process of polyvinyl alcohol as claimed in claim 1, it is characterized in that: described polyvinyl alcohol is the polyvinyl alcohol that alkaline process catalysis polyvinyl acetate (PVA) makes, when it was carried out purification process, solvent selected for use the polyvinyl acetate (PVA) hydrolysis to prepare solvent or the product that is adopted in the polyvinyl alcohol technology.
3. the purification process of polyvinyl alcohol as claimed in claim 1, it is characterized in that: described polyvinyl alcohol is the polyvinyl alcohol that alkaline process catalysis polyvinyl acetate (PVA) makes, when it was carried out purification process, described solvent was selected at least a in methyl alcohol, water, the ethyl acetate for use.
4. the purification process of polyvinyl alcohol as claimed in claim 3 is characterized in that: the mixed solvent of described solvent selection first alcohol and water.
5. as the purification process of each described polyvinyl alcohol of claim 1 to 4, it is characterized in that: the purification process amount of described polyvinyl alcohol is that polyvinyl alcohol parts by weight and solvent volume portion rate are 10～50: 50～90; Treatment temp is 30 ℃～60 ℃, 10～60 minutes treatment times.
6. as the purification process of each described polyvinyl alcohol of claim 1 to 4, it is characterized in that: it is under 30 ℃～60 ℃ temperature, 10～50 weight account polyethylenes alcohol and 50～90 parts by volume solvent are stirred, the residue in the polyvinyl alcohol is dissolved in the solvent; Divide to leave away then to be dissolved with the solvent of residue, more separating obtained polyvinyl alcohol is carried out drying and get final product; Wherein solvent is at least a in methyl alcohol, water, the ethyl acetate.
7. the purification process of polyvinyl alcohol as claimed in claim 6, it is characterized in that: described polyvinyl alcohol is a particulate polyethylene alcohol; When described solvent was the mixture of first alcohol and water, both volume ratios were 5: 1; The drying temperature of described separating obtained polyvinyl alcohol is 60 ℃.
8. the purification process of polyvinyl alcohol as claimed in claim 7 is characterized in that: described polyvinyl alcohol is for through pulverizing and undried granule of polyvinyl alcohol.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617865A (en) * | 2012-03-22 | 2012-08-01 | 盛世泰科生物医药技术(苏州)有限公司 | Method for refining polyvinyl alcohol as pharmaceutic adjuvant for slow release control agent |
| CN102863567A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol through low-alkali method |
| CN103554314A (en) * | 2013-11-08 | 2014-02-05 | 安徽皖维集团有限责任公司 | Production method of high-purity polyvinyl alcohol |
| CN103709296A (en) * | 2013-12-30 | 2014-04-09 | 上海微谱化工技术服务有限公司 | Method for extracting pure ethylene-ethylene vinyl-acetate copolymer |
| CN105837710A (en) * | 2016-03-31 | 2016-08-10 | 温州小伦包衣技术有限公司 | Preparation method for medicinal polyvinyl alcohol, and medicinal polyvinyl alcohol and application thereof |
| CN106279480A (en) * | 2015-06-09 | 2017-01-04 | 中国石油化工集团公司 | The production method of a kind of polyvinyl alcohol and device |
| CN110028602A (en) * | 2019-04-28 | 2019-07-19 | 安徽皖维高新材料股份有限公司 | A method of reducing impurity content in commercial polyethylene alcohol |
| CN110590975A (en) * | 2018-06-12 | 2019-12-20 | 武汉武药科技有限公司 | Medicinal polyvinyl alcohol and preparation method thereof |
| CN114409831A (en) * | 2022-01-02 | 2022-04-29 | 浙江尚能实业股份有限公司 | Method for purifying polyvinyl alcohol resin for diffusion source production |
| CN115873148A (en) * | 2022-12-21 | 2023-03-31 | 浙江瓯伦包衣技术有限公司 | Purification method and application of polyvinyl alcohol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092463A (en) * | 2006-12-18 | 2007-12-26 | 四川大学 | Method for preparing polyvinyl alcohol with low ash |
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2009
- 2009-09-17 CN CN200910190885.5A patent/CN102020735B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092463A (en) * | 2006-12-18 | 2007-12-26 | 四川大学 | Method for preparing polyvinyl alcohol with low ash |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863567A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol through low-alkali method |
| CN102863567B (en) * | 2011-07-07 | 2014-12-24 | 中国石油化工集团公司 | Preparation method of polyvinyl alcohol through low-alkali method |
| CN102617865A (en) * | 2012-03-22 | 2012-08-01 | 盛世泰科生物医药技术(苏州)有限公司 | Method for refining polyvinyl alcohol as pharmaceutic adjuvant for slow release control agent |
| CN103554314A (en) * | 2013-11-08 | 2014-02-05 | 安徽皖维集团有限责任公司 | Production method of high-purity polyvinyl alcohol |
| CN103554314B (en) * | 2013-11-08 | 2015-12-02 | 安徽皖维集团有限责任公司 | Production method of high-purity polyvinyl alcohol |
| CN103709296A (en) * | 2013-12-30 | 2014-04-09 | 上海微谱化工技术服务有限公司 | Method for extracting pure ethylene-ethylene vinyl-acetate copolymer |
| CN103709296B (en) * | 2013-12-30 | 2016-07-20 | 上海微谱化工技术服务有限公司 | The method extracting pure ethylene-ethylene vinyl-acetate copolymer |
| CN106279480A (en) * | 2015-06-09 | 2017-01-04 | 中国石油化工集团公司 | The production method of a kind of polyvinyl alcohol and device |
| CN106279480B (en) * | 2015-06-09 | 2018-09-18 | 中国石油化工集团公司 | A kind of production method and device of polyvinyl alcohol |
| CN105837710A (en) * | 2016-03-31 | 2016-08-10 | 温州小伦包衣技术有限公司 | Preparation method for medicinal polyvinyl alcohol, and medicinal polyvinyl alcohol and application thereof |
| CN110590975A (en) * | 2018-06-12 | 2019-12-20 | 武汉武药科技有限公司 | Medicinal polyvinyl alcohol and preparation method thereof |
| CN110028602A (en) * | 2019-04-28 | 2019-07-19 | 安徽皖维高新材料股份有限公司 | A method of reducing impurity content in commercial polyethylene alcohol |
| CN110028602B (en) * | 2019-04-28 | 2021-09-10 | 安徽皖维高新材料股份有限公司 | Method for reducing impurity content in industrial polyvinyl alcohol |
| CN114409831A (en) * | 2022-01-02 | 2022-04-29 | 浙江尚能实业股份有限公司 | Method for purifying polyvinyl alcohol resin for diffusion source production |
| CN115873148A (en) * | 2022-12-21 | 2023-03-31 | 浙江瓯伦包衣技术有限公司 | Purification method and application of polyvinyl alcohol |
| CN115873148B (en) * | 2022-12-21 | 2023-09-29 | 浙江瓯伦包衣技术有限公司 | Purification method and application of polyvinyl alcohol |
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