CN1055366A - A saponification manufactured high soap purification-ness acetate-acetate ethylene copolymer - Google Patents
A saponification manufactured high soap purification-ness acetate-acetate ethylene copolymer Download PDFInfo
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- CN1055366A CN1055366A CN 91107038 CN91107038A CN1055366A CN 1055366 A CN1055366 A CN 1055366A CN 91107038 CN91107038 CN 91107038 CN 91107038 A CN91107038 A CN 91107038A CN 1055366 A CN1055366 A CN 1055366A
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- saponification
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Abstract
The invention relates to alkali is that catalyzer carries out ethene-acetate ethylene copolymer saponified method with the gap method in lower aliphatic alcohols, it is characterized in that ethene-acetate ethylene copolymer is directly obtained the high soap purification-ness acetate-acetate ethylene copolymer of saponification deg more than 99% (mole) through a saponification in pure alkali soap system.
Description
The present invention relates to the manufacture method of a kind of high soap purification-ness acetate-acetate ethylene copolymer (hereinafter to be referred as EVOH), particularly to relate to ethylene-vinyl acetate copolymer (hereinafter to be referred as EVA) in the lower aliphatic alcoholic solution be catalyzer with alkali obtains the method that saponification deg is higher than 99% EVOH resin through a saponification.
EVOH resin, particularly ethylene content are the 20-50%(mole) saponification deg be higher than 99% EVOH resin, have high gas barrier properties and good working properties, it is widely used in food, in the oxygen barrier Freshkeeping Packagings such as medicine.
The EVOH resin generally is to be obtained by the saponified method by corresponding EVA resin.The method for saponification of EVA mainly contains continuous saponification and gap saponification two big classes at present.Introduced the tower continuous saponification method of EVA among U.S. Pat 4611029 and the Japanese Patent JP85141702.This continuous saponification method is to producing larger industrialized unit per year, the equal very economical of its norm quota of consumption and cost, but the device less to the annual output scale because its equipment complexity, invest bigger, so be non-remunerative economically.The gap saponification of EVA normally adds basic catalyst in the alcoholic solution of EVA, carry out under heating condition.Because the base catalysis saponification reaction of EVA is a balanced reaction, can constantly carry out in order to make saponification reaction, reaction by product ritalin constantly must be removed from system.Therefore, be higher than 99% EVOH resin in order to obtain saponification deg, generally need through secondary saponification process, be about to for the first time the saponified product carries out the saponification second time under stronger reaction conditions.Japanese Patent JP7641789, introduced among JP7627279 and the Japanese Patent JP87143954 elder generation with EVA in the methanol solution of sodium hydroxide 40 ℃ the reaction 3 hours, isolate saponification resultant then, its is dropped in the aqueous solution of sodium hydroxide under higher temperature, carry out the secondary saponification, obtain the method that saponification deg is higher than 99% EVOH resin.In having introduced in riser reactor always earlier with the methanol solution of granular EVA resin among Japanese Patent JP8396603 and the JP83138703 at sodium hydroxide by the bottom of pipe to the top 40 ℃ of circulations 6 hours down, and then the alkali methanol solution in the former saponification system is cemented out with the methanol solution of fresh alkali, and, obtain saponification deg and be 98.6% granular EVOH resin 60 ℃ of down circulations 10 hours.Though its equipment of gap saponification method of EVA is simple, for the saponification deg that reaches more than 99% need carry out twice saponification, thereby its technological process is longer, and operation is more.
The objective of the invention is to alcohol is saponifying agent, is catalyzer with alkali, EVA is directly obtained saponification deg through a saponification be higher than 99% EVOH resin.
The present invention realizes like this.At first the lower aliphatic alcoholic solution of EVA is joined nitrogen ingress pipe is housed, in the reactor of condenser and reliever, at room temperature stir and add catalyzer simultaneously.With this system be warming up to gradually have in the system alcohol steam go out reaction system through condenser condenses, keep suitable methyl alcohol to distillate speed.Because methanol vapor can constantly be taken saponification by product ritalin out of, thereby saponification reaction is constantly carried out to the direction that generates EVOH.Constantly add the methanol solution of fresh methanol and alkali in the saponification reaction process, the methanol solution additional amount sum of methyl alcohol and alkali should be suitable substantially with the distilled quantity of methyl alcohol, and ratio between two was selected between 0.5: 1 to 1: 1.When reaction finishes, in reaction system, add an amount of Glacial acetic acid, the wherein remaining alkali that neutralizes, the pH value that makes system is 7.And then EVOH resin isolation in the system come out, and washing, drying.Can obtain saponification deg like this and be higher than 99% EVOH resin.
In the saponification reaction process, in system, blast rare gas element and vacuumize and to help reacting the expeling of by product ritalin, thereby make saponification reaction can under lower temperature, carry out obtaining the EVOH resin of high saponification deg fully.
The present invention can also be applicable to ethene that except being applicable to ethylene-vinyl acetate copolymer vinyl acetate between to for plastic is main body and a small amount of and its multipolymer of being made up of the possible monomer of copolymerization.These monomers can be alkene such as propylene, iso-butylene; Vinylformic acid, unsaturated acid or their esters such as methylacrylic acid; Maleic Acid, Anhydrous, maleic acid ester and vinylchlorid etc.
Be applicable to EVA of the present invention, therein ethylene content is the 5-45%(mole), particularly ethylene content is the 20-40%(mole) ethylene-vinyl acetate copolymer be suitable for method of the present invention most.
The concentration that is applicable to EVA methanol solution of the present invention is 20-50%(weight).If excessive concentration then stirs difficulty, saponification reaction is difficult to evenly carry out.On the contrary, if concentration is low excessively, then inadvisable economically.
Be applicable to that saponification reaction catalyzer of the present invention is a sodium hydroxide, potassium hydroxide, basic metal etc. are wherein with the sodium hydroxide best results.
Being applicable to that the unitary mol ratio of vinyl acetate between to for plastic is 0.5: 10 to 5: 10 among the add-on of saponification reaction catalyzer of the present invention and the EVA, was the best with 1.5: 10 to 4: 10 wherein.
Being applicable to that saponification reaction temperature of the present invention is 40 ℃ to 90 ℃, is optimal reaction temperature with 50 ℃ to 70 ℃ wherein.
Be applicable to that reaction system pressure of the present invention can be 760 mmhg to 100 mmhg (absolute pressure), wherein with 560 mmhg to 260 mmhg best results.
The example that exemplifies below will the present invention is further illustrated." % " all refers to weight percentage if during no particular restriction in the following example.
Example 1:
With ethylene content is the 31%(mole) ethylene-vinyl acetate copolymer be dissolved in the methyl alcohol for 100 parts, be mixed with 24.9% EVA methanol solution, this solution input is equipped with agitator, condenser, in the round bottom reactor of nitrogen conduit and thermometer, and then add as 89 parts of 10% sodium hydrate methanol solutions of catalyzer, feed nitrogen, at room temperature stirred 10 minutes, with the heat-up rate of 1 ℃ of per minute the temperature of reaction system is risen to 70 ℃, have methanol vapor through condenser condenses after to flow out reaction system in the system this moment.Keeping the speed of distillating of methyl alcohol is 1～2 of per second.Distillate speed for keeping such methyl alcohol, system needs to heat up gradually, and in 6 hours, system temperature rises to 90 ℃ by 70 ℃.In entire reaction course, divide to add 400 milliliters of fresh methanol four times, and after reaction is carried out 2.5 hours, add 50 milliliter 10% sodium hydrate methanol solution.System viscosity is little in entire reaction course, can very successfully stir.When reaction finishes, add in an amount of Glacial acetic acid and system in remaining alkali, the pH value that makes system is 7.Add about 1700 ml distilled waters then in system, and keep simultaneously stirring fast, EVOH separates out with the small particles form precipitation in the system.With water washing EVOH particle 3～4 times, and under vacuum thorough drying.The saponification deg of gained EVOH is the 99.86%(mole).
Reference examples 1:
Saponification reaction process and EVOH aftertreatment be with example 1, but the saponification reaction time be 1 hour, temperature of reaction system is 70 ℃.The saponification deg of analyzing gained EVOH is the 97.2%(mole).
Reference examples 2:
The aftertreatment of saponification reaction process and EVOH is with example 1, but the saponification reaction time is 3 hours.The saponification deg of gained EVOH resin is the 98.7%(mole).
Example 2:
With ethylene content is the 31%(mole) ethylene-vinyl acetate copolymer be dissolved in the methyl alcohol for 100 parts, be mixed with 24.9% EVA methanol solution.This solution input is equipped with agitator, condenser, nitrogen conduit in many necks round bottom reactor of thermometer and reliever, and then adds as 162 parts of 10% sodium hydrate methanol solutions of catalyzer, feeds nitrogen, at room temperature stirs 10 minutes.Heat-up rate with 1 ℃ of per minute is warming up to 60 ℃, and open reliever this moment, makes that pressure is 300 mmhg (absolute pressures) in the system.Methanol vapor begins by flow out reaction system in the saponification system after condenser condenses, and keeping the speed of distillating of methyl alcohol is 1～4 of per second.System temperature slowly rose to 65 ℃ by 60 ℃ in five hours, and to keep saponification reaction device internal pressure simultaneously be 300 mmhg (absolute pressures).In entire reaction course, divide to add 800 ml methanol four times, and after reaction proceeds to 2 hours, add 70 milliliter of 10% sodium hydrate methanol solution.When reaction finishes, add in an amount of Glacial acetic acid and system in remaining alkali, the pH value that makes saponification system is 7.And then in system, add 1700 ml distilled waters, and keep simultaneously stirring fast, EVOH separates out with the small particles form precipitation.With water washing EVOH particle 3～4 times, thorough drying under vacuum then.The saponification deg of gained EVOH resin is the 99.64%(mole).
Reference examples 1:
The saponification reaction process is with example 2.Stopped reaction after saponification reaction is carried out 2 hours.The saponification deg of gained EVOH resin is the 98.60%(mole).
Reference examples 2:
The saponification reaction process is with example 2.Stopped reaction after saponification reaction is carried out 3 hours, the saponification deg of gained EVOH resin is the 99.2%(mole).
Claims (9)
1, is catalyzer carries out ethylene-vinyl acetate copolymer in lower aliphatic alcohols method for saponification with gap method alkali, it is characterized in that directly obtaining high soap purification-ness acetate-acetate ethylene copolymer that saponification deg is higher than 99% (mole) with a saponification process.
2,, it is characterized in that in the saponification reaction process lower aliphatic alcohols in the saponification system is constantly by volatilization in the system and condense, and regularly add fresh lower aliphatic alcohols simultaneously by the described method of claim 1.
3, by claim 1 and 2 described methods, it is characterized in that the additional amount of fresh lower aliphatic alcohols should be suitable substantially with distilled lower aliphatic alcohols amount, the ratio of the former with the latter should be in 0.5: 1 to 1: 1 scope.
4, by claim 1 and 2 described methods, it is characterized in that carrying out adding basic catalyst in the process in saponification reaction.
5, by claim 1 and 2 described methods, it is characterized in that lower aliphatic alcohols is a methyl alcohol, ethanol, Virahol is best saponifying agent with methyl alcohol wherein.
6, by the described method of claim 1, it is characterized in that the basic catalyst that is adopted can be a sodium hydroxide, potassium hydroxide, basic metal etc. wherein are optimum catalyst with sodium hydroxide.
7, by claim 1 and 6 described methods, it is characterized in that the unitary mol ratio of vinyl acetate between to for plastic is 0.5: 10 to 5: 10 in the add-on of alkali and the ethylene-vinyl acetate copolymer, be the best wherein with 1.5: 10 to 4: 10.
8, by claim 1 and 2 described methods, the temperature that it is characterized in that saponification reaction is 40 ℃ to 90 ℃, is the best with 50 ℃ to 70 ℃ wherein.
9, by the described method of claim 1, the ethylene content that it is characterized in that being suitable for ethylene-vinyl acetate copolymer of the present invention is the 5-45%(mole), wherein with ethylene content at the 20-40%(mole) the most suitable the present invention of ethylene-vinyl acetate copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107038 CN1055366A (en) | 1991-05-14 | 1991-05-14 | A saponification manufactured high soap purification-ness acetate-acetate ethylene copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107038 CN1055366A (en) | 1991-05-14 | 1991-05-14 | A saponification manufactured high soap purification-ness acetate-acetate ethylene copolymer |
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| CN1055366A true CN1055366A (en) | 1991-10-16 |
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| CN 91107038 Pending CN1055366A (en) | 1991-05-14 | 1991-05-14 | A saponification manufactured high soap purification-ness acetate-acetate ethylene copolymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098728A (en) * | 2013-04-11 | 2014-10-15 | 中国石油化工集团公司 | Alcoholysis method of ethylene-vinyl acetate copolymer |
| CN110316690A (en) * | 2019-06-11 | 2019-10-11 | 惠科股份有限公司 | Flexible device buffer layer and preparation method thereof and flexible device |
| CN114181333A (en) * | 2020-09-15 | 2022-03-15 | 中国石油化工股份有限公司 | Method and device for preparing ethylene-vinyl acetate copolymer |
-
1991
- 1991-05-14 CN CN 91107038 patent/CN1055366A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104098728A (en) * | 2013-04-11 | 2014-10-15 | 中国石油化工集团公司 | Alcoholysis method of ethylene-vinyl acetate copolymer |
| CN110316690A (en) * | 2019-06-11 | 2019-10-11 | 惠科股份有限公司 | Flexible device buffer layer and preparation method thereof and flexible device |
| CN114181333A (en) * | 2020-09-15 | 2022-03-15 | 中国石油化工股份有限公司 | Method and device for preparing ethylene-vinyl acetate copolymer |
| CN114181333B (en) * | 2020-09-15 | 2024-01-26 | 中国石油化工股份有限公司 | Method and device for preparing ethylene-vinyl acetate copolymer |
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