CN116003668A - Preparation method of high-viscosity polyvinyl alcohol - Google Patents
Preparation method of high-viscosity polyvinyl alcohol Download PDFInfo
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- CN116003668A CN116003668A CN202111225684.1A CN202111225684A CN116003668A CN 116003668 A CN116003668 A CN 116003668A CN 202111225684 A CN202111225684 A CN 202111225684A CN 116003668 A CN116003668 A CN 116003668A
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- Prior art keywords
- polyvinyl alcohol
- preparation
- ether
- polymerization step
- linking agent
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 25
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical group C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- -1 papermaking Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of polyvinyl alcohol, and particularly relates to a preparation method of polyvinyl alcohol. The method comprises the steps of polymerization and alcoholysis, wherein monomers are adopted in the polymerization step, the monomers comprise vinyl acetate, and the polymerization step also comprises ether and amine crosslinking agents containing two or more carbon-carbon double bonds. The polyvinyl alcohol prepared by the method has high viscosity and can meet the performance requirement of a lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of polyvinyl alcohol, and particularly relates to a preparation method of high-viscosity polyvinyl alcohol.
Background
The polyvinyl alcohol has- (CH) 2 CHOH) n-structured substance having a head-to-tail structure and a head-to-head structure ("regularity of polyvinyl alcohol chemical structure", zhou, etc., chemical world, 1 st phase of 1966, page 9 left column 1 st line 1 to 2 nd line, publication date 1966 12 month 31).
The polyvinyl alcohol contains hydroxyl with stronger activity, can perform esterification, etherification and acetalation reactions, can generate various derivatives, has wide application, is a main raw material for producing vinylon, can be used as an emulsifying agent, an adhesive and a fiber processing agent, and has application fields related to textile, papermaking, chemical industry, food and medical use (various applications of the polyvinyl alcohol, shi Yaxiang, synthetic fibers, 4 th 1982, 1 st section and 1 st to 10 lines on a 57 th left column, and 31 th 1982 public days).
In recent years, with the rapid development of the electronic industry and the improvement of environmental protection requirements, lithium ion batteries are receiving more and more attention and research ("EVOH-so_3li/PET/PVA electrospun lithium ion battery separator research", blue-key, halbine university's filing treatises, 2016, abstract 1 st-3, open day 2016, 8 and 31 days), and polyvinyl alcohol is also gradually applied as a binder in lithium ion batteries.
However, the conventional polyvinyl alcohol has low viscosity, and the viscosity of a 4% aqueous solution is only 20-100 mPa.s, so that the performance requirement of a lithium ion battery cannot be met.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing high-viscosity polyvinyl alcohol, which has high viscosity, and the viscosity of 4% aqueous solution can reach 500-800mpa·s, so that the performance requirement of lithium ion battery can be satisfied.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention aims to protect a preparation method of the polyvinyl alcohol, which comprises a polymerization step and an alcoholysis step, wherein monomers adopted in the polymerization step comprise vinyl acetate, and the monomers adopted in the polymerization step also comprise ether and amine crosslinking agents containing two or more carbon-carbon double bonds.
The crosslinking agent is a compound capable of converting a linear polymer into a three-dimensional network structure ("chemical industry dictionary", chemical industry dictionary editorial department, beijing: chemical industry press, 1 st printing in 1 st year 2003, 1154 th page, publication date, 1 st month, 31 th year 2003).
Further, the ether cross-linking agent is pentaerythritol triallyl ether.
Further, the amine cross-linking agent is N, N-methylene bisacrylamide.
Further, the monomers used in the polymerization step include acrylic acid, methacrylic acid, maleic acid, crotonic acid, or itaconic acid.
Further, the mass ratio of the vinyl acetate, the cross-linking agent and the acrylic acid is as follows: 88.4-95.5 percent, 3.8-11.4 percent and 0.2-0.7 percent.
The invention also aims to protect the application of the polyvinyl alcohol in lithium ion batteries.
The invention also relates to the use of a protective crosslinker for increasing the viscosity of polyvinyl alcohol.
Further, the crosslinking agent is an ether and amine crosslinking agent containing two or more carbon-carbon double bonds.
The invention has the beneficial effects that:
the invention adopts a special cross-linking structure to improve the viscosity of the polyvinyl alcohol, thereby meeting the performance requirement of the lithium ion battery.
The invention does not need to change the existing working procedures, and is convenient for popularization and application of industrial production.
Detailed Description
The examples are presented for better illustration of the present invention, but are not intended to limit the scope of the present invention to the examples. Those skilled in the art will appreciate that various modifications and adaptations of the embodiments described above are possible in light of the above teachings and are intended to be within the scope of the invention.
Example 1
The polyvinyl alcohol is prepared by the following steps:
respectively adding vinyl acetate, acrylic acid, pentaerythritol triallyl ether and methanol into a three-neck glass flask according to the mass ratio of 74.5:3:0.5:22, then adding initiator tert-butyl neodecanoate peroxide with the mass of 0.2% of the vinyl acetate, and reacting for 5 hours at the temperature of 60 ℃ to obtain a vinyl acetate copolymer;
then rectifying and purifying the polymerization solution at 75 ℃ to obtain a vinyl acetate copolymer with the purity of 99.0%;
preparing a methanol solution with the mass concentration of 30.0% from a copolymer of vinyl acetate with the purity of 99.0%, then mixing the methanol solution with a sodium methoxide-methanol solution with the mass concentration of 30% (the mixing ratio is that the molar ratio of sodium methoxide contained in the sodium methoxide-methanol solution to the vinyl acetate copolymer contained in the methanol solution is 20:100), and carrying out alcoholysis at the temperature of 40 ℃ for 0.6 hours; obtaining a polyvinyl alcohol product; finally, the polyvinyl alcohol product is washed by absolute ethanol solution for a plurality of times and dried for 6 hours at the temperature of 85 ℃ to obtain white powdery particles.
Example 2
This embodiment differs from embodiment 1 in that: the cross-linking agent is N, N-methylene bisacrylamide.
Example 3
This embodiment differs from embodiment 1 in that: the modified monomer is methacrylic acid.
Example 4
This embodiment differs from embodiment 1 in that: the modified monomer is itaconic acid.
Example 5
This embodiment differs from embodiment 1 in that: the modified monomer is maleic acid, and the cross-linking agent is N, N-methylene bisacrylamide.
Example 6
This embodiment differs from embodiment 1 in that: the modified monomer is crotonic acid.
Comparative example 1
Comparative example 1 other parameter settings were the same as in example 1 except that the polymerization process used monomers consisting of vinyl acetate and acrylic acid in a mass ratio of 74.5:3.
Viscosity detection
The powders prepared in examples 1, 2, 3, 4, 5, 6 and comparative example 1 were prepared as 4% by mass aqueous solutions, and the viscosities of the aqueous solutions were measured at 20℃using a Brookerfield viscometer, and the results are shown in Table 1.
TABLE 1 Performance test results
| Source | viscosity/(mPa.s) |
| Example 1 | 730 |
| Example 2 | 660 |
| Example 3 | 538 |
| Example 4 | 790 |
| Example 5 | 580 |
| Example 6 | 630 |
| Comparative example 1 | 80 |
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The preparation method of polyvinyl alcohol includes polymerization and alcoholysis steps, and the polymerization step adopts monomers including vinyl acetate, and is characterized by that in the polymerization step the monomers also include ether and amine cross-linking agent containing two or more carbon-carbon double bonds.
2. The method of claim 1, wherein the ether-based cross-linking agent is pentaerythritol triallyl ether.
3. The method of claim 1, wherein the amine cross-linking agent is N, N-methylenebisacrylamide.
4. A process according to any one of claims 1 to 3, wherein the monomers used in the polymerization step further comprise acrylic acid, methacrylic acid, maleic acid, crotonic acid or itaconic acid.
5. The preparation method according to claim 4, wherein the mass ratio of the vinyl acetate, the crosslinking agent and the acrylic acid is: 88.4-95.5 percent, 3.8-11.4 percent and 0.2-0.7 percent.
6. Use of the polyvinyl alcohol prepared by the method of any one of claims 1-5 in lithium ion batteries.
7. The use of a cross-linking agent to increase the viscosity of polyvinyl alcohol.
8. The use according to claim 7, wherein the crosslinking agent is an ether containing two or more carbon-carbon double bonds and an amine crosslinking agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111225684.1A CN116003668A (en) | 2021-10-21 | 2021-10-21 | Preparation method of high-viscosity polyvinyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111225684.1A CN116003668A (en) | 2021-10-21 | 2021-10-21 | Preparation method of high-viscosity polyvinyl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116003668A true CN116003668A (en) | 2023-04-25 |
Family
ID=86028492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111225684.1A Pending CN116003668A (en) | 2021-10-21 | 2021-10-21 | Preparation method of high-viscosity polyvinyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116003668A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB828957A (en) * | 1957-06-26 | 1960-02-24 | British Oxygen Co Ltd | Copolymer emulsions |
| JPH11279986A (en) * | 1998-03-25 | 1999-10-12 | Unitika Chemical Kk | Polyvinyl alcohol-based paper coating agent excellent in high speed coating property |
| CN1319615A (en) * | 2000-03-29 | 2001-10-31 | Basf公司 | Hard capsule containing vinyl ester and polyether polymer, its use and production process |
| JP2008184495A (en) * | 2007-01-29 | 2008-08-14 | Kuraray Co Ltd | Cross-linkable aqueous dispersion and its production method, and adhesive and coating agent |
| CN105636996A (en) * | 2013-10-18 | 2016-06-01 | 日本瓦姆&珀巴尔株式会社 | Method of producing polyvinyl alcohol resin, and polyvinyl alcohol resin obtained thereby |
| US20160319048A1 (en) * | 2013-12-26 | 2016-11-03 | Kuraray Co., Ltd. | Modified polyvinyl alcohol and production method therefor |
| CN108047372A (en) * | 2013-04-19 | 2018-05-18 | 株式会社可乐丽 | Ethenol system copolymer and its manufacturing method |
| CN108659428A (en) * | 2018-05-23 | 2018-10-16 | 宁波宝亭生物科技有限公司 | A kind of preparation method of polyvinyl alcohol hydrogel |
| WO2020007466A1 (en) * | 2018-07-04 | 2020-01-09 | Wacker Chemie Ag | Water-soluble copolymers |
| CN110845747A (en) * | 2019-10-30 | 2020-02-28 | 中国石油化工股份有限公司 | PVA film with good flexibility and manufacturing method thereof |
| CN111072800A (en) * | 2019-12-06 | 2020-04-28 | 天津辛德玛悬浮剂有限公司 | Modified ultra-high molecular weight polyvinyl alcohol and preparation method and application thereof |
| CN112521532A (en) * | 2014-10-17 | 2021-03-19 | 株式会社可乐丽 | Vinyl alcohol polymer and use thereof |
-
2021
- 2021-10-21 CN CN202111225684.1A patent/CN116003668A/en active Pending
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| JPH11279986A (en) * | 1998-03-25 | 1999-10-12 | Unitika Chemical Kk | Polyvinyl alcohol-based paper coating agent excellent in high speed coating property |
| CN1319615A (en) * | 2000-03-29 | 2001-10-31 | Basf公司 | Hard capsule containing vinyl ester and polyether polymer, its use and production process |
| JP2008184495A (en) * | 2007-01-29 | 2008-08-14 | Kuraray Co Ltd | Cross-linkable aqueous dispersion and its production method, and adhesive and coating agent |
| CN108047372A (en) * | 2013-04-19 | 2018-05-18 | 株式会社可乐丽 | Ethenol system copolymer and its manufacturing method |
| CN105636996A (en) * | 2013-10-18 | 2016-06-01 | 日本瓦姆&珀巴尔株式会社 | Method of producing polyvinyl alcohol resin, and polyvinyl alcohol resin obtained thereby |
| US20160319048A1 (en) * | 2013-12-26 | 2016-11-03 | Kuraray Co., Ltd. | Modified polyvinyl alcohol and production method therefor |
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| CN111072800A (en) * | 2019-12-06 | 2020-04-28 | 天津辛德玛悬浮剂有限公司 | Modified ultra-high molecular weight polyvinyl alcohol and preparation method and application thereof |
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