CN111662400A - Method for preparing polyvinyl alcohol with high polymerization degree through solution polymerization - Google Patents
Method for preparing polyvinyl alcohol with high polymerization degree through solution polymerization Download PDFInfo
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- CN111662400A CN111662400A CN202010640073.2A CN202010640073A CN111662400A CN 111662400 A CN111662400 A CN 111662400A CN 202010640073 A CN202010640073 A CN 202010640073A CN 111662400 A CN111662400 A CN 111662400A
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 68
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 53
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 52
- 238000010528 free radical solution polymerization reaction Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 34
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 34
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 7
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical group CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical group 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004148 unit process Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 38
- 239000000243 solution Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 4
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229940075582 sorbic acid Drugs 0.000 description 4
- 235000010199 sorbic acid Nutrition 0.000 description 4
- 239000004334 sorbic acid Substances 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 medical supplies Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F118/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F118/02—Esters of monocarboxylic acids
- C08F118/04—Vinyl esters
- C08F118/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing polyvinyl alcohol with high polymerization degree by solution polymerization, which takes tertiary butanol as a solvent to obtain polyvinyl acetate by the solution polymerization method, and then obtains a target product by alcoholysis. The polyvinyl alcohol obtained by the invention has high polymerization degree and narrow molecular weight distribution, and has the advantages of simple synthesis process, low reaction temperature, short polymerization time, high product purity, easy industrial production and the like.
Description
Technical Field
The invention relates to a preparation method of polyvinyl alcohol, in particular to a method for preparing polyvinyl alcohol with high polymerization degree through solution polymerization.
Background
Polyvinyl alcohol (PVA) is a water-soluble polymer, and has been widely used in additives, adhesives, emulsifiers, films, butyral resins, cosmetics, medical supplies, ceramic adhesives, and the like, due to its water solubility and excellent strength characteristics and film-forming ability. The properties and use of PVA are related to its degree of polymerization. The high-strength and high-modulus fiber prepared from the polyvinyl alcohol with high polymerization degree can reduce the defects at the tail end of a molecular chain, improve the stretching multiple, shorten the production process flow and reduce the production cost. In addition, the polyvinyl alcohol with high polymerization degree can be used for producing various products such as PVA films, PVA plates and the like.
At present, the polyvinyl alcohol with high polymerization degree is mostly prepared by adopting suspension polymerization and emulsion polymerization methods. In patent CN 103172774A, an emulsion polymerization mode and an oxidation-reduction low-temperature initiation system are adopted, a polyvinyl acetate emulsion is prepared by polymerization for 2-8 hours at 0-40 ℃, and alcoholysis is carried out on the polyvinyl acetate emulsion after freezing demulsification to prepare polyvinyl alcohol with high polymerization degree and narrow dispersion. In patent CN 101177467a, emulsion polymerization of vinyl acetate is performed by redox initiation system and composite emulsifier, and alcoholysis of polyvinyl acetate is performed in alkali methanol solution by low alkali method to obtain polyvinyl alcohol with high polymerization degree and high alcoholysis degree. CN 106749802A adopts suspension polymerization method, mixing polymerization monomer, initiator and organic solvent in a static mixer to obtain mixed solution, mixing the mixed solution with desalted water, carrying out polymerization reaction under anaerobic closed condition to obtain polyvinyl acetate, and then saponifying to obtain polyvinyl alcohol.
However, the methods of emulsion polymerization and suspension polymerization have the problems of high operation difficulty, poor polymerization stability, complex post-treatment, large wastewater treatment capacity and the like. And impurities such as residual emulsifier, dispersant and the like are left in the obtained polyvinyl alcohol, so that the product performance is influenced, and the application is limited.
Solution polymerization is easy to mix and transfer heat, easy to control temperature and less in gel effect, so that local overheating can be avoided, and other raw materials such as an emulsifier, a dispersing agent and the like are not required to be added, so that the polyvinyl alcohol produced industrially at present is mainly subjected to solution polymerization. However, it is difficult to obtain a high degree of polymerization for materials such as high-strength high-modulus fibers from polyvinyl alcohol obtained by solution polymerization.
Disclosure of Invention
Based on the defects of the existing preparation method of polyvinyl alcohol with high polymerization degree, the invention provides a method for preparing polyvinyl alcohol with high polymerization degree through solution polymerization, aiming at preparing polyvinyl alcohol with high polymerization degree through a solution polymerization method by using a solvent with low chain transfer constant, providing improvement for industrialization of preparing polyvinyl alcohol with high polymerization degree through solution polymerization, and providing raw materials for preparing products such as polyvinyl alcohol fiber with high strength and high modulus.
In order to realize the purpose of the invention, the following technical scheme is adopted:
a method for preparing polyvinyl alcohol with high polymerization degree by solution polymerization is characterized in that: comprises three unit processes of polymerization, monomer removal and alcoholysis; the polymerization is carried out by taking tert-butyl alcohol as a solvent and adding an initiator, and vinyl acetate is polymerized by a solution polymerization method.
Further, the mass percentage of the vinyl acetate to the tertiary butanol is 70% to 90%: 30 to 10 percent.
Furthermore, the addition amount of the initiator accounts for 0.004-0.01% of the mass of the vinyl acetate monomer.
Further, the polymerization temperature is 40-65 ℃ and the polymerization time is 1-4 h.
Further, the initiator is a peroxide initiator, such as tert-Butyl Peroxypivalate (BPV) or di-n-propyl peroxydicarbonate (NPP).
Further, the monomer removal is to continuously introduce methanol into the polyvinyl acetate solution obtained through polymerization under vacuum, and to distill at 50-60 ℃ until unreacted vinyl acetate in the solution is removed, so as to obtain an alcohol solution of polyvinyl acetate.
Further, the alcoholysis is carried out by adding a methanol solution of NaOH into an alcoholic solution of polyvinyl acetate obtained by removing monomers, and carrying out alcoholysis for 0.1-1 h at 30-60 ℃; after alcoholysis is finished, crushing, filtering, washing and vacuum drying the obtained product to obtain the target product polyvinyl alcohol with high polymerization degree.
Further, the molar ratio of NaOH to polyvinyl acetate was 0.02: 1.
The polymerization degree of the polyvinyl alcohol obtained by the method is 4000-7000, and the molecular weight distribution is 1.5-2.0.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes tertiary butanol as solvent, prepares polyvinyl alcohol with high polymerization degree by solution polymerization method, the polymerization degree of the obtained polyvinyl alcohol can reach more than 4000, the molecular weight distribution is less than 2.0, and the invention has the advantages of simple synthesis process, low reaction temperature, short polymerization time, high product purity, easy industrial production and the like.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
This example prepares polyvinyl alcohol with a high degree of polymerization as follows:
step 1, adding 400mL of vinyl acetate and 85.1mL of tert-butyl alcohol into a 1000mL four-necked flask provided with a stirrer, a reflux condenser, a thermometer and a nitrogen protection device, heating to 50 ℃, then adding 2.82mL of methanol solution containing 1.0% by mass of NPP, and reacting for 1 h. After the reaction, 0.03g of sorbic acid was added, and the mixture was cooled to room temperature after stopping heating to obtain a polyvinyl acetate solution.
And 2, continuously introducing methanol into the polyvinyl acetate solution obtained by polymerization under vacuum, and distilling at 60 ℃ until unreacted vinyl acetate in the solution is removed to obtain an alcohol solution of polyvinyl acetate.
Step 3, adding a methanol solution of NaOH with the mass concentration of 45g/L (the molar ratio of NaOH to polyvinyl acetate is 0.02:1) into the polyvinyl acetate alcohol solution obtained in the step 2, and carrying out alcoholysis at 38 ℃ for 1 h; after alcoholysis is finished, the obtained product is crushed, filtered by a Buchner funnel, washed by methanol and dried in vacuum to constant weight, and the target product polyvinyl alcohol with high polymerization degree is obtained.
Example 2
This example prepares polyvinyl alcohol with a high degree of polymerization as follows:
step 1, adding 400mL of vinyl acetate and 72.3mL of tert-butyl alcohol into a 1000mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen protection device, heating to 50 ℃, then adding 3.13mL of a methanol solution containing 1.2 mass% of BPV, and reacting for 2 h. After the reaction, 0.05g of sorbic acid was added, and the mixture was cooled to room temperature after stopping heating to obtain a polyvinyl acetate solution.
And 2, continuously introducing methanol into the polyvinyl acetate solution obtained by polymerization under vacuum, and distilling at 60 ℃ until unreacted vinyl acetate in the solution is removed to obtain an alcohol solution of polyvinyl acetate.
Step 3, adding a methanol solution of NaOH with the mass concentration of 45g/L (the molar ratio of NaOH to polyvinyl acetate is 0.02:1) into the polyvinyl acetate alcohol solution obtained in the step 2, and carrying out alcoholysis at 38 ℃ for 1 h; after alcoholysis is finished, the obtained product is crushed, filtered by a Buchner funnel, washed by methanol and dried in vacuum to constant weight, and the target product polyvinyl alcohol with high polymerization degree is obtained.
Example 3
This example prepares polyvinyl alcohol with a high degree of polymerization as follows:
step 1, adding 400mL of vinyl acetate and 89.6mL of tert-butyl alcohol into a 1000mL four-necked flask provided with a stirrer, a reflux condenser, a thermometer and a nitrogen protection device, heating to 46 ℃, then adding 1.89mL of a methanol solution containing 1.0% by mass of NPP, and reacting for 3 hours. After the reaction, 0.02g of sorbic acid was added, and the mixture was cooled to room temperature after stopping heating to obtain a polyvinyl acetate solution.
And 2, continuously introducing methanol into the polyvinyl acetate solution obtained by polymerization under vacuum, and distilling at 60 ℃ until unreacted vinyl acetate in the solution is removed to obtain an alcohol solution of polyvinyl acetate.
Step 3, adding a methanol solution of NaOH with the mass concentration of 45g/L (the molar ratio of NaOH to polyvinyl acetate is 0.02:1) into the polyvinyl acetate alcohol solution obtained in the step 2, and carrying out alcoholysis at 38 ℃ for 1 h; after alcoholysis is finished, the obtained product is crushed, filtered by a Buchner funnel, washed by methanol and dried in vacuum to constant weight, and the target product polyvinyl alcohol with high polymerization degree is obtained.
Example 4
This example prepares polyvinyl alcohol with a high degree of polymerization as follows:
step 1, adding 400mL of vinyl acetate and 89.6mL of tert-butyl alcohol into a 1000mL four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen protection device, heating to 46 ℃, then adding 1.57mL of a methanol solution containing 1.2% by mass of BPV, and reacting for 4 hours. After the reaction, 0.02g of sorbic acid was added, and the mixture was cooled to room temperature after stopping heating to obtain a polyvinyl acetate solution.
And 2, continuously introducing methanol into the polyvinyl acetate solution obtained by polymerization under vacuum, and distilling at 60 ℃ until unreacted vinyl acetate in the solution is removed to obtain an alcohol solution of polyvinyl acetate.
Step 3, adding a methanol solution of NaOH with the mass concentration of 45g/L (the molar ratio of NaOH to polyvinyl acetate is 0.02:1) into the polyvinyl acetate alcohol solution obtained in the step 2, and carrying out alcoholysis at 38 ℃ for 1 h; after alcoholysis is finished, the obtained product is crushed, filtered by a Buchner funnel, washed by methanol and dried in vacuum to constant weight, and the target product polyvinyl alcohol with high polymerization degree is obtained.
Comparative example
This comparative example prepared polyvinyl alcohol in the same manner as in example 3 except that 89.6mL of t-butanol in step 1 was replaced with an equal amount of methanol.
The performance test method of the products obtained in the above examples and comparative examples is as follows:
1. polymerization rate: the vinyl acetate content was titrated with bromoacetic acid, and the polyvinyl acetate content was measured by weighing, and the polymerization rate of vinyl acetate in the polymerization reaction of each example and comparative example was determined.
2. Polymerization degree: the polymerization degree of the polyvinyl alcohol prepared in each example and comparative example was measured by the viscosity method.
3. Molecular weight distribution: the molecular weight distributions of the polyvinyl alcohols obtained in the respective examples and comparative examples were measured by gel permeation chromatography.
The results are shown in Table 1.
TABLE 1 test results of samples of various examples of the present invention
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Rate of polymerization | 18％ | 15％ | 12％ | 9％ | 21％ |
| Degree of polymerization | 5250 | 4460 | 6480 | 6920 | 2430 |
| Molecular weight distribution | 1.5 | 1.5 | 1.7 | 1.8 | 2.0 |
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing polyvinyl alcohol with high polymerization degree by solution polymerization, which is characterized in that: comprises three unit processes of polymerization, monomer removal and alcoholysis; the polymerization is carried out by taking tert-butyl alcohol as a solvent and adding an initiator, and vinyl acetate is polymerized by a solution polymerization method.
2. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 1, wherein: the mass percentage of the vinyl acetate to the tertiary butanol is 70-90%: 30 to 10 percent.
3. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 1, wherein: the addition amount of the initiator accounts for 0.004-0.01% of the mass of the vinyl acetate monomer.
4. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 1, wherein: the polymerization temperature is 40-65 ℃ and the polymerization time is 1-4 h.
5. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 1, wherein: the initiator is a peroxide initiator.
6. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 5, wherein: the peroxide initiator is tert-Butyl Peroxypivalate (BPV) or di-n-propyl peroxydicarbonate (NPP).
7. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 1, wherein: and in the step of removing the monomers, continuously introducing methanol into the polyvinyl acetate solution obtained by polymerization under vacuum, and distilling at 50-60 ℃ until unreacted vinyl acetate in the solution is removed to obtain an alcohol solution of the polyvinyl acetate.
8. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 1, wherein: the alcoholysis is carried out by adding a methanol solution of NaOH into an alcoholic solution of polyvinyl acetate obtained by removing monomers, and carrying out alcoholysis for 0.1-1 h at 30-60 ℃; after alcoholysis is finished, crushing, filtering, washing and vacuum drying the obtained product to obtain the target product polyvinyl alcohol with high polymerization degree.
9. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to claim 8, wherein: the molar ratio of NaOH to polyvinyl acetate was 0.02: 1.
10. The method for producing a polyvinyl alcohol having a high degree of polymerization by solution polymerization according to any one of claims 1 to 9, wherein: the polymerization degree of the obtained polyvinyl alcohol is 4000-7000, and the molecular weight distribution is 1.5-2.0.
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| CN202010640073.2A CN111662400A (en) | 2020-07-06 | 2020-07-06 | Method for preparing polyvinyl alcohol with high polymerization degree through solution polymerization |
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| CN202010640073.2A CN111662400A (en) | 2020-07-06 | 2020-07-06 | Method for preparing polyvinyl alcohol with high polymerization degree through solution polymerization |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115991802A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | A kind of production method of low methanol polyvinyl alcohol |
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| CN1566165A (en) * | 2003-07-09 | 2005-01-19 | 中国石油化工集团公司 | Polyvinyl alcohol with high degree of polymerization and its preparing process |
| CN106146721A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工集团公司 | The EVOH preparation method that a kind of conversion ratio is high |
| CN106749802A (en) * | 2017-02-23 | 2017-05-31 | 重庆云天化瀚恩新材料开发有限公司 | The preparation method and preparation system of a kind of high polymerization degree narrow ditribution polyvinyl alcohol |
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2020
- 2020-07-06 CN CN202010640073.2A patent/CN111662400A/en active Pending
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|---|---|---|---|---|
| CN1566165A (en) * | 2003-07-09 | 2005-01-19 | 中国石油化工集团公司 | Polyvinyl alcohol with high degree of polymerization and its preparing process |
| CN106146721A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工集团公司 | The EVOH preparation method that a kind of conversion ratio is high |
| CN106749802A (en) * | 2017-02-23 | 2017-05-31 | 重庆云天化瀚恩新材料开发有限公司 | The preparation method and preparation system of a kind of high polymerization degree narrow ditribution polyvinyl alcohol |
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Cited By (1)
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|---|---|---|---|---|
| CN115991802A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | A kind of production method of low methanol polyvinyl alcohol |
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