CN1187504A - Process for preparing ethylene-vinylacetate-vinyl alcohol ternary atactic copolymer - Google Patents
Process for preparing ethylene-vinylacetate-vinyl alcohol ternary atactic copolymer Download PDFInfo
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- CN1187504A CN1187504A CN97106209A CN97106209A CN1187504A CN 1187504 A CN1187504 A CN 1187504A CN 97106209 A CN97106209 A CN 97106209A CN 97106209 A CN97106209 A CN 97106209A CN 1187504 A CN1187504 A CN 1187504A
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- ethylene
- vinylacetate
- vinyl acetate
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- 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
- C08F8/12—Hydrolysis
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Abstract
A ternary atactic copolymer ethylene-vinyl acetate-ethenol is prepared through granular hydrolysis reaction at 40-75 deg.C, where sodium hydroxide is used as hydrolytic catalyst, the alcohol containing 1-4 C atoms is used as solvent of sodium hydroxide and the aqueous solution of tertiary butyl alcohol is used as swelling agent of ethylene-vinyl acetate copolymer. Its advantages are controllable hydrolysis temp, simple post treatment and recovering and reusing solvent.
Description
The present invention relates to the hydrolysis process of ethylene-vinyl acetate copolymer, particularly hydrolysis prepares the technology of ethylene-vinylacetate-vinyl alcohol ternary random copolymers about ethylene-vinyl acetate copolymer.
The ethylene-vinylacetate-vinyl alcohol ternary random copolymers, it is the macromolecular compound that contains polyethylene, polyvinyl acetate (PVA) and polyvinyl alcohol segments or chain link on the main chain, can be used as compatilizer in Polymer Blending System, also is simultaneously the raw material of preparation another kind of broad spectrum compatilizer ethylene-vinylacetate-vinyl alcohol-toxilic acid vinyl alcohol monoesters random copolymers.The hydrolysis process of ethylene-vinyl acetate copolymer generally can be divided into material copolymerization composition granule shape under solvent action in the past, swelling hydrolysis and be hydrolyzed two kinds in suspension.Introduced the preparation technology of poly-(ethylene-vinyl alcohol) in the U.S. Pat 3925336, this technology is by making catalyzer with sodium hydroxide, make the solvent of sodium hydroxide with methyl alcohol, with the swelling agent of the trimethyl carbinol as ethylene-vinyl acetate copolymer, reaction is hydrolyzed in paraffin suspension.There is following shortcoming in this hydrolysis reaction: on the one hand the hydrolysis degree of hydrolysate cannot be controlled, can only the depth hydrolysis, promptly can only direct hydrolysis become poly-(ethylene-vinyl alcohol); On the other hand, because system is a suspension, so drips of solution is suspended in the non-solvent aftertreatment difficulty.Introduced the technology of hydrolysis preparation poly-(ethylene-vinyl alcohol) in the U.S. Pat 3510463, this raw materials technology ethylene-vinyl acetate copolymer in benzene-methanol solvate with the hydrolysis of particulate state swelling, with sodium methylate as hydrolyst.This hydrolysis reaction exists the hydrolysis degree of hydrolysate to control equally, and the shortcoming of aftertreatment difficulty.
In order to overcome the shortcoming that above-mentioned document exists, the purpose of this invention is to provide a kind of preparation technology of ethylene-vinylacetate-vinyl alcohol ternary random copolymers, make this technology possess the may command hydrolysis degree, simultaneously the aftertreatment technology characteristic of simple of product.
The objective of the invention is to realize: a kind of preparation technology of ethylene-vinylacetate-vinyl alcohol ternary random copolymers by following technical scheme, by the ethylene-vinyl acetate copolymer particle that contains vinyl acetate 10～95% in molar content, with sodium hydroxide as hydrolyst, contain the solvent of 1～4 carbon atom alcohol as sodium hydroxide, sodium hydroxide is 1: 3.75～15 with the weight ratio that contains 1～4 carbon atom alcohol, with the swelling agent of the trimethyl carbinol aqueous solution as ethylene-vinyl acetate, 40～75 ℃ of hydrolysis temperatures, hydrolysis makes under 1～50 hour reaction times condition.
In the technique scheme, in the ethylene-vinyl acetate copolymer in molar content, containing the vinyl acetate preferable range is 14～40%, trimethyl carbinol weight percent concentration is 70～95% in the trimethyl carbinol aqueous solution, contain 1～4 carbon atom alcohol particular methanol, sodium hydroxide is 1: 3.75～8 with the weight ratio preferable range that contains 1～4 carbon atom alcohol, and the temperature preferable range of hydrolysis reaction is 60～70 ℃, and the hydrolysis time preferable range is 6～16 hours.
The present invention is because in the ethylene-vinyl acetate copolymer hydrolytic process, with sodium hydroxide as hydrolyst, contain the solvent of the alcohol of 1～4 carbon atom as sodium hydroxide, with the swelling agent of tertiary butanol aqueous solution as the raw material ethylene-vinyl acetate copolymer, make hydrolysis degree to be controlled effectively, degree of hydrolysis is 2.8～85%, hydrolysate is a particulate state simultaneously, very easily in washing, aftertreatment technology is simplified, the used solvent methanol and the trimethyl carbinol are easy to recycling and recycle, and make the running cost of whole technology and pollution all reduce to very low degree, have obtained effect preferably.
[embodiment 1]
In 400 liter reactors, add 50 kilograms of ethylene-vinyl acetate copolymers, the content of vinyl acetate is 30.1% (mole) in this ethylene-vinyl acetate copolymer, add 110 kilograms of the trimethyl carbinols, 15 kilograms in water, under stirring, middling speed is heated to 60 ℃, stirred 14 hours, particle is swelling to volume at this moment increases about 1 times.With dissolving good sodium hydroxide/methyl alcohol (7.8 kilograms/30 kilograms) in advance, under agitation slowly add, reacted 6 hours down at 60 ℃ then.Behind the stopped reaction reactant is put into filter vat, filtrate is delivered to distillation tower, steams boiling point earlier and be 64 ℃ methyl alcohol, steams the azeotrope that boiling point is 79.9～82.0 ℃ a tertiary butanol and water again.More than methyl alcohol of Hui Shouing and azeotrope can be directly used in the technology of the present invention.Obtain sodium-acetate in the distillation tower bottom, can be used as the by product purification and be product.
Granular ethylene-vinyl acetate is hydrolyzed to ethylene-vinylacetate-vinyl alcohol, is orange, and is translucent.The aqueous hydrochloric acid of putting into PH=3～5 soaked 2 hours, and this moment, the swelling particle shrank gradually, and the solvent that includes etc. is squeezed out.
The molar content that records vinyl acetate in the ethylene-vinylacetate-vinyl alcohol random copolymers with chemical analysis is 24.4%, so degree of hydrolysis is (30.1-24.4)/30.1=18.9%, through infrared spectrogram at 3700～3100em
-1Tangible hydroxyl absorption peak appears in the place.[embodiment 2]
Raw material and reaction process are with embodiment 1, and just swelling and temperature of reaction rise to 64 ℃, and the content of vinyl acetate is 19.2% (mole) in the ethylene-vinylacetate-vinyl alcohol ternary random copolymers of acquisition, and degree of hydrolysis is 36.0%.[embodiment 3]
Raw material and reaction process are with embodiment 1, just swelling temperature and temperature of reaction rise to 70 ℃, the content of vinyl acetate is 7.2% (mole) in the ethylene-vinylacetate-vinyl alcohol ternary random copolymers that obtains, and degree of hydrolysis is 76.1%, at 3700～3100cm
-1The hydroxyl absorption peak at place more obviously and broaden shows that the hydroxyl that has this moment to a certain degree associates.[embodiment 4]
Raw material and reaction process are with embodiment 3, and just the reaction times increased to 11 hours by 6 hours.The content of vinyl acetate is 4.8% (mole) in the ethylene-vinylacetate-vinyl alcohol ternary random copolymers that obtains, and promptly degree of hydrolysis is 84.1%.[embodiment 5]
Reaction process is with embodiment 1, just vinyl acetate content is 41% (mole) in the ethylene-vinyl acetate copolymer, hydrolysis time is 16 hours, the content that obtains vinyl acetate in the ethylene-vinylacetate-vinyl alcohol ternary random copolymers is 31.1% (mole), and promptly degree of hydrolysis is 24.1%.[embodiment 6]
Reaction process is with embodiment 5, just the content of vinyl acetate is 14.0% (mole) in the ethylene-vinyl acetate, hydrolysis time is 1 hour, the content of the vinyl acetate in the ethylene-vinylacetate-vinyl alcohol ternary random copolymers that obtains is 13.35% (mole), and promptly degree of hydrolysis is 4.6%.[embodiment 7]
Raw material and reaction process are with embodiment 1, just the content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 10% (mole), the add-on of sodium hydroxide/methyl alcohol is 2 kilograms/30 kilograms, trimethyl carbinol add-on is 87.5 kilograms, the water add-on is 37.5 kilograms, swelling and temperature of reaction are 40 ℃, hydrolysis time is 50 hours, the content of the vinyl acetate in the ethylene-vinylacetate-vinyl alcohol ternary random copolymers of Huo Deing is 9.72% (mole) at last, and promptly degree of hydrolysis is 2.8%.[embodiment 8]
Raw material and reaction process are with embodiment 1, just the content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 80% (mole), 3.75 kilograms/30 kilograms of the add-ons of sodium hydroxide/methyl alcohol, trimethyl carbinol add-on is 118.75 kilograms, the water add-on is 6.25 kilograms, swelling and temperature of reaction are 65 ℃, hydrolysis time is 6 hours, the content of the vinyl acetate in the ethylene-vinylacetate-vinyl alcohol ternary random copolymers of Huo Deing is 12.96% (mole) at last, and promptly degree of hydrolysis is 83.8%.
Claims (7)
1, a kind of preparation technology of ethylene-vinylacetate-vinyl alcohol ternary random copolymers, by the ethylene-vinyl acetate random copolymerization composition granule that contains vinyl acetate 10～95% in molar content, with sodium hydroxide as hydrolyst, contain the solvent of the alcohol of 1～4 carbon atom as sodium hydroxide, 40～75 ℃ of temperature, under 1～50 hour reaction times condition, hydrolysis makes, it is characterized in that in the hydrolysis reaction that with the swelling agent of the trimethyl carbinol aqueous solution sodium hydroxide is 1: 3.75～15 with the weight ratio that contains 1～4 carbon atom alcohol as ethylene-vinyl acetate.
2,, it is characterized in that in the ethylene-vinyl acetate random copolymers containing vinyl acetate 14～40% in molar content according to the preparation technology of the described ethylene-vinylacetate-vinyl alcohol ternary random copolymers of claim 1.
3,, it is characterized in that 60～70 ℃ of hydrolysising reacting temperatures according to the preparation technology of the described ethylene-vinylacetate-vinyl alcohol ternary random copolymers of claim 1.
4,, it is characterized in that hydrolysis time is 6～16 hours according to the preparation technology of the described ethylene-vinylacetate-vinyl alcohol ternary random copolymers of claim 1.
5,, it is characterized in that trimethyl carbinol weight percent concentration is 70～95% in the trimethyl carbinol aqueous solution according to the preparation technology of the described ethylene-vinylacetate-vinyl alcohol ternary random copolymers of claim 1.
6,, it is characterized in that sodium hydroxide and the weight ratio that contains 1～4 carbon atom alcohol are 1: 3.75～8 according to the preparation technology of the described ethylene-vinylacetate-vinyl alcohol ternary random copolymers of claim 1.
7, according to the preparation technology of the described ethylene-vinylacetate-vinyl alcohol ternary random copolymers of claim 1, it is characterized in that containing 1～4 carbon atom alcohol is methyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97106209 CN1067695C (en) | 1997-01-10 | 1997-01-10 | Process for preparing ethylene-vinylacetate-vinyl alcohol ternary atactic copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97106209 CN1067695C (en) | 1997-01-10 | 1997-01-10 | Process for preparing ethylene-vinylacetate-vinyl alcohol ternary atactic copolymer |
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| CN1187504A true CN1187504A (en) | 1998-07-15 |
| CN1067695C CN1067695C (en) | 2001-06-27 |
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| CN 97106209 Expired - Fee Related CN1067695C (en) | 1997-01-10 | 1997-01-10 | Process for preparing ethylene-vinylacetate-vinyl alcohol ternary atactic copolymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107779007A (en) * | 2017-10-30 | 2018-03-09 | 余姚市顺迪塑料模具厂 | A kind of hypotonic oxygen thermoplastic powder coating |
| CN110028603A (en) * | 2011-06-27 | 2019-07-19 | 瑞立普萨公司 | Method for converting polymeric acid for polyester |
| CN116003661A (en) * | 2022-12-08 | 2023-04-25 | 云南正邦科技有限公司 | Method for preparing EVA copolymer with high ethylene content |
-
1997
- 1997-01-10 CN CN 97106209 patent/CN1067695C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028603A (en) * | 2011-06-27 | 2019-07-19 | 瑞立普萨公司 | Method for converting polymeric acid for polyester |
| CN107779007A (en) * | 2017-10-30 | 2018-03-09 | 余姚市顺迪塑料模具厂 | A kind of hypotonic oxygen thermoplastic powder coating |
| CN107779007B (en) * | 2017-10-30 | 2020-10-20 | 余姚市顺迪塑料模具厂 | Low-oxygen-permeability thermoplastic powder coating |
| CN116003661A (en) * | 2022-12-08 | 2023-04-25 | 云南正邦科技有限公司 | Method for preparing EVA copolymer with high ethylene content |
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| CN1067695C (en) | 2001-06-27 |
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Granted publication date: 20010627 Termination date: 20100210 |