CN116003669A - Polyvinyl alcohol having excellent gel resistance - Google Patents
Polyvinyl alcohol having excellent gel resistance Download PDFInfo
- Publication number
- CN116003669A CN116003669A CN202111225686.0A CN202111225686A CN116003669A CN 116003669 A CN116003669 A CN 116003669A CN 202111225686 A CN202111225686 A CN 202111225686A CN 116003669 A CN116003669 A CN 116003669A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- gel resistance
- washing
- excellent gel
- mass
- Prior art date
- 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.)
- Pending
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 9
- 239000000499 gel Substances 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the technical field of polyvinyl alcohol, and particularly relates to polyvinyl alcohol with excellent gel resistance. The content of free acetate ions in the polyvinyl alcohol is less than 0.07 percent by mass. The polyvinyl alcohol of the invention has excellent gel resistance.
Description
Technical Field
The invention belongs to the technical field of polyvinyl alcohol, and particularly relates to polyvinyl alcohol with excellent gel resistance.
Background
Polyvinyl alcohol (PVA) with molecular formula of (CH) 2 CHOH) n, which is flocculent, powdery or flaky in appearance, is obtained by alcoholysis of polyvinyl acetate, has a planar sawtooth conformation, has regular chemical structure, strong polarity, high crystallinity, chemical stability, high barrier property, oil resistance, film forming property, solvent resistance and unique adhesive property (national polyvinyl alcohol production and market current and development advice, zhang Zhanhong, vinylon communication, volume 2016, no. 36, no. 4, left column 1, section 1-5, publication date 2016)12 months and 31 days; "plasticization modification study of polyvinyl alcohol", ma-Chart, university of east China's Shu-Shi-Ji paper, 2017, page 1, section 1, line 1 to section 2, line 1, publication date 2017, 12, 31).
However, the conventional polyvinyl alcohol has poor gel resistance, and an aqueous solution thereof has a mass concentration of >8%, and after being left for 24 hours, the aqueous solution is gelled to be jelly-like.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a polyvinyl alcohol.
The invention aims to provide polyvinyl alcohol, wherein the content of free acetate ions in the polyvinyl alcohol is less than 0.07 percent in mass percent.
The invention also aims at protecting the production method of the polyvinyl alcohol, which comprises the steps of polymerization, alcoholysis and washing, wherein the washing liquid in the washing step is ethanol with the purity of more than or equal to 99.9 percent.
Preferably, the washing liquid is absolute ethyl alcohol.
The invention also aims at protecting the purification method of the polyvinyl alcohol, which adopts ethanol with the purity of more than or equal to 99.9 percent for washing.
Further, the alcohol is absolute ethanol.
The invention has the beneficial effects that:
the polyvinyl alcohol of the present invention is excellent in gel resistance.
The production method is simple, convenient and fast, and convenient to produce.
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.
In the invention, the method for detecting the content of free acetate ions comprises the following steps: the sample was divided into two parts, and a part of the sample (m 1 ) Placed in a crucible (m) 2 ) In the process, the mixture is put on an electric furnace to be slowly heated until the whole sample is obtainedCharring or volatilizing, weighing (m 3 )；
Taking another portion of the sample (m 4 ) Extracting with Soxhlet extractor for 48 hr, oven drying at 105deg.C for 2 hr, cooling to room temperature in a dryer, and placing in a crucible (m 5 ) Slowly heating in electric furnace until the pattern is carbonized or volatilized, and weighing (m 6 )；
Then according to the formula
Calculating the content of free acetate ions;
wherein m is 3 And m 6 The mass of the crucible and the heated sample is expressed as g; m is m 2 And m 5 The mass of the crucible with constant weight is expressed as g; m is m 1 And m 4 The mass of the sample is given in g.
In the invention, the method for detecting the gel resistance comprises the following steps: 150ml of 10% polyvinyl alcohol aqueous solution is prepared and placed in a 250ml conical flask, the polyvinyl alcohol aqueous solution is stored in a sealed manner at room temperature for 24 hours and then poured out of the conical flask, and if the solution is jelly-like and coagulated, the solution cannot be poured out; if the jelly is not jelly-like and congealed, the jelly can be poured out smoothly.
Example 1
The polyvinyl alcohol is prepared by adopting the following raw materials according to the following steps:
adding vinyl acetate, acrylic acid, pentaerythritol triallyl ether and methanol into a three-necked glass flask according to the mass ratio of 74.5:3:0.5:22, then adding tert-butyl peroxyoctoate serving as an initiator with the mass ratio of 0.02% of the vinyl acetate, and reacting for 5 hours at 60 ℃ to obtain a vinyl acetate copolymer;
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 22.0% from a copolymer of vinyl acetate with the purity of 99.0%, mixing the methanol solution with a sodium methoxide-methanol solution with the mass concentration of 30%, wherein the mixing ratio is that the molar ratio of the copolymer of vinyl acetate to sodium methoxide is 20:100, and then carrying out alcoholysis at 40 ℃ for 0.6 hour;
after the alcoholysis reaction, the solid phase and the liquid phase are completely separated, and the solid phase and the liquid phase are molded and harder. Cutting the polyvinyl alcohol product formed into blocks into small blocks, putting the blocks into a pulverizer for pulverizing, and finally washing the pulverized powdery product with an absolute ethyl alcohol solution for several times, wherein the washing liquid does not contain solid pulverized materials, and can clean metal particles in non-polymerized parts. And drying the washed material in vacuum at 85 ℃ for 6 hours to obtain white powdery particles.
Example 2
This embodiment differs from embodiment 1 in that: the comonomer used was methacrylic acid.
Example 3
This embodiment differs from embodiment 1 in that: the comonomer used was itaconic acid.
Example 4
This embodiment differs from embodiment 1 in that: the comonomer used was crotonic acid.
Example 5
This embodiment differs from embodiment 1 in that: the comonomer used was maleic acid.
Example 6
This embodiment differs from embodiment 1 in that: the comonomer used was N, N-methylenebisacrylamide.
Comparative example 1
The difference between this comparative example and example 1 is that: the crushed powdery product is washed by methanol solution, the surface of the washed product is sticky, the product is partially dissolved in the methanol solution, and the product quality loss is more than 30%.
TABLE 1 Performance test results
| Source | Free sodium acetate/% | Gel resistance test |
| Example 1 | 0.02 | Smoothly pour out |
| Example 2 | 0.05 | Smoothly pour out |
| Example 3 | 0.03 | Smoothly pour out |
| Example 4 | 0.04 | Smoothly pour out |
| Example 5 | 0.02 | Smoothly pour out |
| Example 6 | 0.03 | Smoothly pour out |
| Comparative example 1 | 0.7 | Jelly-like shape can not be poured out |
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 (5)
1. Polyvinyl alcohol characterized by a content of free acetate ions of <0.07% in mass%.
2. The process for producing polyvinyl alcohol according to claim 1 or 2, comprising polymerization, alcoholysis and washing steps, wherein the washing liquid in the washing step is ethanol having a purity of not less than 99.9%.
3. The method according to claim 2, wherein the washing liquid is absolute ethanol.
4. The purification method of the polyvinyl alcohol is characterized in that ethanol with the purity more than or equal to 99.9% is adopted for washing.
5. The method of claim 4, wherein the alcohol is absolute ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111225686.0A CN116003669A (en) | 2021-10-21 | 2021-10-21 | Polyvinyl alcohol having excellent gel resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111225686.0A CN116003669A (en) | 2021-10-21 | 2021-10-21 | Polyvinyl alcohol having excellent gel resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116003669A true CN116003669A (en) | 2023-04-25 |
Family
ID=86035952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111225686.0A Pending CN116003669A (en) | 2021-10-21 | 2021-10-21 | Polyvinyl alcohol having excellent gel resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116003669A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591543A (en) * | 1969-06-09 | 1971-07-06 | Du Pont | Time controlled gelation of polyvinyl alcohol with chromic ion |
| JPH1149915A (en) * | 1997-08-06 | 1999-02-23 | Kuraray Co Ltd | Polyvinyl alcohol composition |
| CN101357956A (en) * | 2008-09-19 | 2009-02-04 | 天津博科林药品包装技术有限公司 | Purification method of polyvinyl alcohol resin |
| CN102695727A (en) * | 2010-03-24 | 2012-09-26 | 日本瓦姆&珀巴尔株式会社 | Polyvinyl alcohol resin and method for producing same |
| CN103140540A (en) * | 2010-09-28 | 2013-06-05 | 东丽株式会社 | Polymer microparticles and process for production thereof |
| CN106854256A (en) * | 2015-12-08 | 2017-06-16 | 中国石化集团四川维尼纶厂 | A kind of melt-processable modified polyvinylalcohol and preparation method thereof |
| CN109988323A (en) * | 2018-01-02 | 2019-07-09 | 山东省科学院能源研究所 | The method of monodisperse polyvinyl alcohol microparticles is quickly prepared under a kind of room temperature |
| CN110903414A (en) * | 2019-10-30 | 2020-03-24 | 中国石油化工股份有限公司 | Method for washing polyvinyl alcohol special for optical material |
| CN112175590A (en) * | 2020-09-30 | 2021-01-05 | 中国石油天然气股份有限公司大港油田分公司 | Modified polyol inhibitor, preparation method thereof and application thereof in water-based drilling fluid |
| CN112592418A (en) * | 2020-12-14 | 2021-04-02 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl alcohol special for optical film |
-
2021
- 2021-10-21 CN CN202111225686.0A patent/CN116003669A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3591543A (en) * | 1969-06-09 | 1971-07-06 | Du Pont | Time controlled gelation of polyvinyl alcohol with chromic ion |
| JPH1149915A (en) * | 1997-08-06 | 1999-02-23 | Kuraray Co Ltd | Polyvinyl alcohol composition |
| CN101357956A (en) * | 2008-09-19 | 2009-02-04 | 天津博科林药品包装技术有限公司 | Purification method of polyvinyl alcohol resin |
| CN102695727A (en) * | 2010-03-24 | 2012-09-26 | 日本瓦姆&珀巴尔株式会社 | Polyvinyl alcohol resin and method for producing same |
| CN103140540A (en) * | 2010-09-28 | 2013-06-05 | 东丽株式会社 | Polymer microparticles and process for production thereof |
| CN106854256A (en) * | 2015-12-08 | 2017-06-16 | 中国石化集团四川维尼纶厂 | A kind of melt-processable modified polyvinylalcohol and preparation method thereof |
| CN109988323A (en) * | 2018-01-02 | 2019-07-09 | 山东省科学院能源研究所 | The method of monodisperse polyvinyl alcohol microparticles is quickly prepared under a kind of room temperature |
| CN110903414A (en) * | 2019-10-30 | 2020-03-24 | 中国石油化工股份有限公司 | Method for washing polyvinyl alcohol special for optical material |
| CN112175590A (en) * | 2020-09-30 | 2021-01-05 | 中国石油天然气股份有限公司大港油田分公司 | Modified polyol inhibitor, preparation method thereof and application thereof in water-based drilling fluid |
| CN112592418A (en) * | 2020-12-14 | 2021-04-02 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl alcohol special for optical film |
Non-Patent Citations (2)
| Title |
|---|
| 向学毅;刘瑾;: "两步法制备高醇解度低醋酸钠含量聚乙烯醇", 安徽科技, no. 12, 20 December 2015 (2015-12-20) * |
| 宋建华;苏育志;李楠;张建华;吕澍;: "聚乙烯醇的制备及其分子链键合方式的测定", 化学教育, no. 12, 18 June 2014 (2014-06-18) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI522373B (en) | Polyvinyl alcohol and purification method thereof | |
| CN106146720B (en) | Alcoholysis method in preparation process of ethylene-vinyl alcohol copolymer | |
| CN104003894B (en) | The preparation method of N-acetyl-β-chloro-ALANINE methyl esters | |
| CN109053389B (en) | Synthetic method of 2,4, 6-tribromophenyl allyl ether | |
| CN116003669A (en) | Polyvinyl alcohol having excellent gel resistance | |
| CN106349197A (en) | Preparing method of emulsifier Span-80 for emulsion explosive | |
| CN115368668B (en) | Modified EVOH resin and preparation method thereof | |
| JP6524074B2 (en) | Process for producing dimethyl polyvinyl phosphonate and polyvinyl phosphonic acid | |
| CN111153887A (en) | Synthesis method of methylene methanedisulfonate | |
| JPH0676451B2 (en) | Method for producing ethylene / vinyl alcohol copolymer | |
| CN107236210B (en) | A kind of glucaric acid zinc coordination polymer is preparing the application in heat stabilizer | |
| CN109400927B (en) | High-transparency flame-retardant polyvinyl alcohol film and preparation method thereof | |
| CA2657206C (en) | Anhydrized copolymer | |
| CN109651541B (en) | Linear chain dialdehyde modified polyvinyl alcohol and preparation method and application thereof | |
| CN103483579B (en) | A kind of method being caused synthesizing branched polymeric amide by end ester group chain branching agent | |
| CN108440693B (en) | High-melt-index resin and preparation method thereof | |
| CN113880971A (en) | Preparation method of yellowing-resistant polyvinyl butyral resin | |
| JP4129177B2 (en) | Purification means | |
| CN110283194B (en) | Preparation method of 1, 7-m-carborane dihydroxyl substituted derivative | |
| CN108976119B (en) | Preparation method and application of plasticizer prepared from mixed anhydride as raw material | |
| CN115536961B (en) | Blow-down pipe with high thermal stability | |
| JP4114040B2 (en) | Method for producing fatty acid ester | |
| CN114835949B (en) | Polypropylene composite nucleating agent based on glucose acetal derivative | |
| CN110590979B (en) | Preparation method of PVB resin powder with high acetal rate | |
| CN109651542B (en) | Modified polyvinyl alcohol dispersant, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |