CN103980504B - A kind of method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity - Google Patents
A kind of method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity Download PDFInfo
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- CN103980504B CN103980504B CN201310050872.4A CN201310050872A CN103980504B CN 103980504 B CN103980504 B CN 103980504B CN 201310050872 A CN201310050872 A CN 201310050872A CN 103980504 B CN103980504 B CN 103980504B
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- alcoholic solution
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Abstract
The present invention is a kind of method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity.The present invention is the solution comprising ethylene-vinyl alcohol bipolymer or ethylene-vinyl alcohol vinylacetate terpolymer and aliphatic alcohol compound solvent composition containing ethene and vinyl alcohol construction unit copolymer alcoholic solution, the method is, water or vapor are added in the copolymer alcoholic solution containing ethene and vinyl alcohol construction unit, after being sufficiently mixed, the solution of copolymer/solvent/water is formed.The method of the reduction system viscosity of the present invention is applied to ethene and vinyl alcohol units copolymer alcoholic solution has reached effect following prominent：1）Copolymer alcoholic solution viscosity is can obviously reduce, reduction amplitude may be up to more than 70%, reduce the energy consumption of transportational process；2）In the case of solution viscosity similar in holding, copolymer concentration is further improved to reach by the system for adding suitable quantity of water, so as to further improve production efficiency, and solvent consumption is reduced, reduces cost.
Description
Technical field
It is specific next the present invention relates to a kind of method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity
Say, be related to one kind by adding a certain amount of environmental-friendly medium in containing ethene and vinyl alcohol construction unit copolymer alcoholic solution,
Reaching reduces the method for solution viscosity.
Background technology
Copolymer containing ethene and vinyl alcohol construction unit, such as ethylene-vinyl alcohol copolymer（Abbreviation EVOH）Or ethene-second
Enol-vinyl acetate co-polymer etc., is a kind of collection ethene polymers excellent processability and vinyl alcohol polymer superior in gas
Barrier is in the high molecular material of one.This high molecular material have excellent barrier properties for gases, mechanical strength, retractility,
Wearability, antistatic property, solvent resistance, machinability and the transparency.Therefore, this high molecular material is in packaging material, spinning
The fields such as material, medical material are knitted to be widely used, referring to《Plastics industry》2011,39 phases, 1-4 pages.In grocery trade, this height
Molecular material can be used for making aseptic packaging, hot tank and retort pouch etc..Such as pack dairy produce, meat, canned fruit juice and
In flavouring, EVOH plastic containers can substitute glass and canister completely.In terms of non-food stuff, EVOH sees molten for packing
Agent, chemicals, air conditioner structure part, petrol drum liner, electronic component etc..Therefore, ethene and vinyl alcohol construction unit are copolymerized
The product purity and quality of thing are proposed very high requirement, avoid the occurrence of the phenomenon of bad order, such as flake, coloring.
Copolymer containing ethene and vinyl alcohol construction unit is typically further to be existed by ethene and vinyl acetate co-polymer
Saponification or alcoholysis reaction are carried out in alcohol medium to be made, when saponification degree is relatively low, generates ethylene-vinyl acetate-ethene
Alcohol copolymer, when saponification degree is higher, generates ethylene-vinyl alcohol copolymer.It is total to obtaining ethylene-vinylacetate-vinyl alcohol
Post-processed and solid forming, it is necessary to be transported to other devices after the alcoholic solution of polymers or ethylene-vinyl alcohol copolymer, ginseng
See CN1333300A, CN1341671A, JP11140136A and CN1798642A.
In the conveying of these copolymer alcoholic solutions or last handling process, in order to improve production efficiency, usually increase as much as possible
Polymer content in addition polymerization polymer solution, and reduce the dosage of wherein solvent to the greatest extent.But result of which, it can cause
Polymer solution viscosity increases considerably, thus substantially increases the energy consumption in transportational process is transmitted and reduce post processing effect
Fruit.In order to solve this conflict, only while polymer concentration is improved, and the effect for reaching and reducing solution viscosity is taken into account
.
Prior art CN102212353A discloses one kind and is added in viscous crude with raw materials such as dodecyl benzene sulfonic acid, urea
The thinner being re-dubbed, for reducing the viscosity of viscous crude.But this method for adding thinner is not suitable for containing ethene and second
Enol structure unit copolymer alcoholic solution, because can so make thinner residual in the product, influences product quality.
The content of the invention
It is an object of the invention to improve production efficiency and reduce on the premise of not influencing properties of product containing ethene and
The viscosity of vinyl alcohol construction unit copolymer alcoholic solution, reduces the energy consumption of transportational process；Another object of the present invention is suitable
Under conditions of the viscosity of copolymer alcoholic solution is reduced, copolymer concentration is further improved, further improves production efficiency, and drop
Low solvent consumption, reduces cost.
What method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity of the present invention was realized in：
The ethene and vinyl alcohol construction unit copolymer alcoholic solution of the present invention of containing is total to comprising ethylene-vinyl alcohol binary
The solution that polymers or ethylene-vinyl alcohol-vinylacetate terpolymer are formed with aliphatic alcohol compound solvent respectively, it is described
The method for reducing viscosity is that water or vapor are added in the copolymer alcoholic solution containing ethene and vinyl alcohol construction unit, is filled
After dividing mixing, the solution of copolymer/solvent/water is formed.
In specific implementation,
The mass concentration containing polymer in ethene and vinyl alcohol units copolymer alcoholic solution is 4~60%, preferably 6
~55%, more preferably 7~50%；
Alcohol in the copolymer alcoholic solution can be selected from least one of methanol, ethanol, propyl alcohol, preferably methanol；
The copolymer is 1 with the mass ratio for adding water or vapor：（0.05~5）, preferably 1：（0.1~4.5）,
More preferably 1：（0.3~4）, add that the amount of water is related with polymer concentration, and amount of water is big when polymer concentration is low.
The water or the temperature of vapor can be in the range of 2~160 DEG C, preferably 5~150 DEG C, more preferably 8~
150℃.In general, the temperature of industrial Low pressure steam is 140~150 DEG C.
The mixing of the solution is using one of following two ways：
First, water or vapor are used and mixed in a reservoir with containing ethene and vinyl alcohol units copolymer/alcoholic solution；
Second, water or vapor are used and mixed in copolymer alcoholic solution flow process by static mixer or dynamic
Device is mixed.
It is heretofore described containing ethene and vinyl alcohol construction unit copolymer include ethylene-vinyl alcohol bipolymer with
And ethylene-vinyl alcohol-vinylacetate terpolymer, they are not soluble in water.These contain ethene and vinyl alcohol units copolymer
Solution, further include ethene and vinyl acetate co-polymer and carry out the original after saponification or alcoholysis reaction in alcohol medium under base catalysis
Solution, wherein containing base catalyst residual and accessory substance such as methyl acetate, acetaldehyde etc..
By the method for the present invention, add in copolymer/alcoholic solution containing ethene and vinyl alcohol construction unit more than 50 DEG C
Enter the water of a certain amount of certain temperature, solution is formed, to reduce solution viscosity.
The present invention can obviously reduce copolymer alcoholic solution viscosity up to more than 70%, or in solution viscosity similar in holding
In the case of, copolymer concentration can be improved 5~50% by forming copolymer/solvent/aqueous solution.
Water can be used and mixed in a reservoir with containing ethene and vinyl alcohol construction unit copolymer/alcoholic solution, can also be
Mixed in copolymer alcoholic solution flow process by static mixer or dynamic mixer.Water can also be as a vapor
It is passed through in system.The addition speed of water is related with temperature, and addition is related with polymer concentration.
The method proposed by the present invention for reducing system viscosity is applied to ethene and vinyl alcohol units copolymer alcoholic solution reaches
Effect following prominent：
1）Copolymer alcoholic solution viscosity is can obviously reduce, reduction amplitude may be up to more than 70%, reduce the energy of transportational process
Consumption；
2）In the case of solution viscosity similar in holding, further improved altogether by adding the system of suitable quantity of water to reach
Oligomer concentrations, for example, the copolymer alcoholic solution that concentration is 40%, which adds suitable water viscosity, is reduced to the copolymerization for being 25% with concentration
Thing solution viscosity is suitable, so as to further improve production efficiency, and reduces solvent consumption, reduces cost.
Embodiment
By representative embodiment in detail below, the present invention can be better understood from.
Embodiment 1
Ethylene-vinyl alcohol copolymer is obtained after carrying out saponification or alcoholysis reaction in sodium hydroxide catalyzed lower methanol（Ethene
Content 37mol%）Original solution, copolymer concentration 40%.Solution system viscosity at 42 DEG C is 5400mPas；It is in temperature
In 52 DEG C of above-mentioned solution, 80 DEG C of water is added, the usage ratio of copolymer quality and water is 1:0.4, system viscosity is at 42 DEG C
When be 2200mPas, reduce amplitude be 59%.Copolymer/methanol solution viscosity phase that copolymer concentration with being not added with water is 25%
When copolymer concentration improves 38%.
Embodiment 2
Concentration is 35% ethylene-vinyl alcohol copolymer（Ethylene contents 38mol%）Methanol/ethanol solution（Methanol/ethanol
=16:1）At 41 DEG C, system viscosity is 5700mPas；In the above-mentioned solution that temperature is 65 DEG C, adding 10 DEG C of water makes altogether
The mass ratio of polymers and water is 1:1.7, system viscosity is 1800mPas at 41 DEG C, and viscosity reduces 68%.
Embodiment 3
Concentration is 30% to contain ethene and vinyl alcohol units copolymer（Ethylene contents 38mol%）Methanol/propanol solution（First
Alcohol/propyl alcohol=15:1）At 45 DEG C, system viscosity is 3900mPas；In the above-mentioned solution that temperature is 60 DEG C, 15 DEG C are added
Water makes the mass ratio of copolymer and water be 1:2, system viscosity is 1800mPas at 45 DEG C, and viscosity reduces 54%.
Embodiment 4
Concentration is 42%, and saponification degree is 80% ethylene-vinyl alcohol-vinyl acetate co-polymer（Ethylene contents 37mol%, second
Enol content 50mol%, vinyl acetate content 13mol%）Methanol solution at 47 DEG C system viscosity be 6400mPas；
Temperature is in 55 DEG C of above-mentioned solution, and being passed through 140 DEG C of vapor makes the mass ratio of copolymer and water be 1:1.4, system viscosity exists
It is 1900mPas at 47 DEG C, viscosity reduces 70%.
Embodiment 5
Ethylene-vinyl alcohol copolymer is obtained after carrying out saponification or alcoholysis reaction in sodium hydroxide catalyzed lower methanol（Ethene
Content 37mol%）Original solution, copolymer concentration 45%.Solution system viscosity at 44 DEG C is 6200mPas；It is in temperature
In 55 DEG C of above-mentioned solution, 70 DEG C of water is added, when copolymer and water quality ratio are 1:At 1.3,44 DEG C system viscosity for
1800mPas, viscosity, which is compared, reduces 71%.
Embodiment 6
Ethylene-vinyl alcohol copolymer is obtained after carrying out saponification or alcoholysis reaction in sodium hydroxide catalyzed lower methanol（Ethene
Content 37mol%）Original solution, copolymer concentration 38%.Solution system viscosity at 40 DEG C is 5100mPas；At 80 DEG C
Above-mentioned solution is mixed with 70 DEG C of water by static mixer, and the usage ratio of copolymer quality and water is 1:0.5, system viscosity
It is 1900mPas at 40 DEG C, it is 63% that viscosity, which reduces amplitude,.
Claims (6)
1. a kind of method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity, described contains ethene and ethene
Alcohol construction unit copolymer alcoholic solution is to include ethylene-vinyl alcohol bipolymer or ethylene-vinyl alcohol-vinylacetate ternary
The solution that copolymer is formed with aliphatic alcohol compound solvent respectively, it is characterised in that：
The method of the reduction viscosity is, by the copolymer alcoholic solution containing ethene and vinyl alcohol construction unit and water or vapor
It is sufficiently mixed, forms copolymer/solvent/aqueous solution；
The mass concentration containing copolymer in ethene and vinyl alcohol units copolymer alcoholic solution is 4~60%；
Alcohol in the aliphatic alcohol compound is selected from least one of methanol, ethanol, propyl alcohol；
The copolymer is 1 with the mass ratio for adding water or vapor：(1.3~1.7)；
The water or the temperature of vapor are 2~160 DEG C；
The mixing of the copolymer/solvent/aqueous solution uses following manner：
Water or vapor are used to be mixed in copolymer alcoholic solution flow process by static mixer or dynamic mixer
Close.
2. reducing the method containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity as claimed in claim 1, its feature exists
In：
The mass concentration containing copolymer in ethene and vinyl alcohol units copolymer alcoholic solution is 6~55%.
3. reducing the method containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity as claimed in claim 1, its feature exists
In：
The mass concentration containing copolymer in ethene and vinyl alcohol units copolymer alcoholic solution is 7~50%.
4. reducing the method containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity as claimed in claim 1, its feature exists
In：
The water or the temperature of vapor are 5~150 DEG C.
5. reducing the method containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity as claimed in claim 1, its feature exists
In：
The water or the temperature of vapor are 8~150 DEG C.
6. reducing the method containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity as claimed in claim 5, its feature exists
In：
Alcohol in the aliphatic alcohol compound is selected from methanol；
The mass concentration containing copolymer in ethene and vinyl alcohol units copolymer alcoholic solution is 7~50%.
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| CN201310050872.4A CN103980504B (en) | 2013-02-08 | 2013-02-08 | A kind of method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity |
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| CN201310050872.4A CN103980504B (en) | 2013-02-08 | 2013-02-08 | A kind of method of the reduction containing ethene and vinyl alcohol construction unit copolymer alcoholic solution viscosity |
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| CN105623163A (en) * | 2014-11-06 | 2016-06-01 | 中国石油化工股份有限公司 | Copolymer composition containing ethylene and vinyl alcohol structure unit, and preparation method thereof |
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| JPS4738634Y1 (en) * | 1970-05-23 | 1972-11-22 | ||
| JP3888745B2 (en) * | 1997-09-08 | 2007-03-07 | 日本合成化学工業株式会社 | Process for producing ethylene-vinyl acetate copolymer saponified alcohol / water solution |
| JP4917717B2 (en) * | 2000-08-07 | 2012-04-18 | 株式会社クラレ | Method for treating ethylene-vinyl alcohol copolymer solution |
| JP4953528B2 (en) * | 2000-08-07 | 2012-06-13 | 株式会社クラレ | Process for producing water-containing composition of ethylene-vinyl alcohol copolymer |
| DE10321942A1 (en) * | 2003-05-15 | 2004-12-09 | Wacker Polymer Systems Gmbh & Co. Kg | Process for the preparation of powdery ethylene-vinyl alcohol copolymers |
| EP2487191B1 (en) * | 2009-10-07 | 2016-04-27 | The Nippon Synthetic Chemical Industry Co., Ltd. | Process for producing ethylene/vinyl alcohol copolymer |
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