CN106349417B - The method for removing volatile component in vinyl-vinyl acetate copolymer solution - Google Patents

The method for removing volatile component in vinyl-vinyl acetate copolymer solution Download PDF

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CN106349417B
CN106349417B CN201510420313.7A CN201510420313A CN106349417B CN 106349417 B CN106349417 B CN 106349417B CN 201510420313 A CN201510420313 A CN 201510420313A CN 106349417 B CN106349417 B CN 106349417B
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water
solution
vinyl
copolymer
vinyl acetate
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CN106349417A (en
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刘小萌
刘金伟
陈博
于鲁强
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses a kind of methods of solvent in removing vinyl-vinyl acetate copolymer solution, comprising the following steps: 1) by solution copolymerization, obtains vinyl-vinyl acetate copolymer solution;2) water of the solution of the copolymer and certain temperature is mixed to get mixed liquor, is passed through vapor and is sufficiently mixed with the mixed liquor, obtain the mixed gas comprising water and solvent, and the mixture comprising micelle and water;3) mixture of the micelle and water is separated by solid-liquid separation, obtains dry vinyl-vinyl acetate copolymer.Method in through the invention makes the volatile component in micelle reach high standard removing, to reduce the volatile component content in polymer billet, creates advantage for the post-production of polymer billet.

Description

The method for removing volatile component in vinyl-vinyl acetate copolymer solution
Technical field
The present invention relates to polymerization reaction fields, and in particular to a kind of removing vinyl-vinyl acetate copolymer solution evaporation The method of property component.The invention further relates to the equipment of volatile component in removing vinyl-vinyl acetate copolymer solution.
Background technique
Vinyl-vinyl acetate copolymer (EVA) is a kind of very high random copolymer of the degree of branching, by non-polar ethylene Monomer (E) is copolymerized with highly polar vinyl acetate monomer (VAc), is one of most important ethylene derivative copolymer.EVA With excellent low temperature resistant and environmental stress cracking resistance, while there is good optical property, nontoxic, is widely used in Packaging film, agricultural film, wire and cable, shoemaking, injection extrude the fields such as product, solar energy.
United States Patent (USP) US 4485225 and European patent EP 136559 are described for ethylene and vinyl acetate, Radical initiator and in the presence of carry out copolymerization process.This reaction is gas-liquid two-phase copolyreaction, and vinyl monomer exists In gas phase, vinyl acetate, initiator and solution are present in liquid phase.After reaction, ethane-acetic acid ethyenyl ester solution is obtained.
In practical applications, ethane-acetic acid ethyenyl ester solution obtains ethylene-vinyl alcohol copolymer after being saponified, can also To be directly applied in industrial production in the form of a solution, but in most cases, need to carry out the removing and recycling of solvent, from And obtain ethane-acetic acid ethyenyl ester micelle or blob of viscose.
Currently, the method in industrial production for removing solvent in polymer solution, it usually needs more kettle joint operations, work It is skill long flow path, complicated for operation, it is at high cost, and the removal efficiency of solvent is not high.And it is produced for vinyl-vinyl acetate copolymer The method and technique of volatile component removing are also rarely reported in the process.
Summary of the invention
It is an object of the invention to aiming at the shortcomings in the prior art, provide a kind of removing ethylene-vinyl acetate c The method of volatile component in object solution makes volatile component (solvent and possibility in vinyl-vinyl acetate copolymer solution Existing a small amount of unreacted monomer) it can be removed by simple process flow, the copolymer after making obtained drying The content of middle volatile component is very small, and such as less than 0.02%.The present invention also provides the equipment used in the above method.
According to an aspect of the invention, there is provided volatility in a kind of removing vinyl-vinyl acetate copolymer solution The method of component, comprising the following steps:
1) by solution copolymerization, vinyl-vinyl acetate copolymer solution is obtained;
2) solution of the copolymer and the water of certain temperature are mixed to get in container mixed liquor, are passed through into container Vapor, the vapor are mixed with the mixed liquor, then obtain the mixed gas comprising water and solvent, and include copolymerization The mixture of object micelle and water;
3) mixture of the micelle and water is separated by solid-liquid separation, obtains dry vinyl-vinyl acetate copolymer.
Method according to the present invention, vapor therein are capable of providing heat and conveying power, promote the temperature of system Degree rises, solvent evaporation and promotion mixed gas are discharged, and such as promotes solvent composition to strip and is discharged, micelle is precipitated;In turn, lead to The method crossed in the present invention makes the volatile component in micelle reach high standard removing, to reduce the volatilization in polymer billet Property constituent content, create advantage for the post-production of polymer billet.
A specific embodiment according to the method for the present invention, the water of certain temperature refer to that the temperature of water should be not less than 60 DEG C. For the water of the certain temperature, temperature raising is conducive to save vapor, and as the temperature rises, heating energy consumption increases, The heat resistant requirements of equipment are improved.It is preferred that the temperature of water is not less than 80 DEG C, more preferably 80-90 DEG C in the water of certain temperature.
Another specific embodiment according to the method for the present invention, the volume of the solution of the water and copolymer of the certain temperature Than be greater than 1:1, adequately contacted to guarantee that the micelle to be formed has with the water of the certain temperature, and guarantee micelle precipitation after not It will form large-scale micelle, wind agitating paddle and block discharge pipe.However, if the dosage of the water of certain temperature is excessive, it will substantially Degree increases the energy consumption of heating and follow-up separation process, leads to the above-mentioned of production cost.It is preferred that the water and copolymer of certain temperature The volume ratio of solution is greater than 1:1 to 5:1, more preferable 1.5:1-4:1.
Another specific embodiment according to the method for the present invention, solvent used in the solution copolymerization are fatty alcohol, It is preferred that carbon atom is not more than 4 fatty alcohol, at least one of more preferable methanol, ethyl alcohol, propyl alcohol and butanol.The copolymer is molten The solid content in copolymer solution that solid content in liquid can obtain for conventional polymerisation in solution, details are not described herein again.
In a specific embodiment, in the step 2), the copolymer solution spurts into the water of certain temperature In, obtain mixed liquor.By the way of injection, the drop for spraying formation can control the size of micelle, thus further advantageous In avoiding the formation of micelle.Form the removal that big micelle is unfavorable for wherein volatile component.
According to the present invention, the vapor can (1) for spray into condensing field in solution heat is provided, reach stripping Temperature;(2) latent heat of vaporization is provided for the evaporation of volatile component;(3) conveying is provided as the volatile component of gas to evaporate Power promotes its discharge.It is preferred that control vapor flow, so that the temperature being passed through in the container after vapor is controlled in 85-100 DEG C, in this way, both ensure that operation temperature was higher than the boiling point of volatile matter, be conducive to volatile matter gasification, while reducing disappearing for steam Consumption saves energy consumption.It is preferred that control the solution of the copolymer residence time be 10-60 minutes, preferably 30-40 minutes, Be conducive to micelle to be adequately precipitated in water.In a specific embodiment, the container is coacervation device.
In another specific embodiment according to the method for the present invention, the mixed gas and/or the mixture, can also it wrap Containing unreacted monomer, the unreacted monomer is separated from the mixed gas and/or the mixture, is returned To the step 1), copolyreaction is carried out, to realize recycling for unreacted monomer, discharge is avoided to pollute, and Reduce cost and material consumption.
Another specific embodiment according to the method for the present invention, by the mixed gas solvent and water separate, Obtained solvent and water is back to step 1) and 2) respectively.At the same time it can also which the water separated in step 3) is back to step It is rapid 2).By aforesaid operations, realization recycles solvent and water, avoids discharge from polluting, and reduce cost and object Consumption.
It is molten can to remove vinyl-vinyl acetate copolymer by simple technique for the method provided according to the present invention Solvent in liquid makes volatile matter remaining in polymer obtain high standard removing, to reduce the volatilization in polymer billet Property component.In a specific example, the content of the volatile component in polymer billet can be decreased below 0.02%. Meanwhile the method provided according to the present invention, solvent, unreacted monomer and water can be continued cycling through into utilization, reduce energy consumption And material consumption, to also reduce production cost.
According to another aspect of the present invention, it additionally provides in a kind of removing vinyl-vinyl acetate copolymer solution The equipment of volatile component, comprising: coacervation device, interior to be equipped with rabbling mechanism, middle part, which is equipped with, to be respectively used to introduce copolymer The first import and the second import of solution and the water of certain temperature, bottom are equipped with for introducing the third import of vapor and drawing The first outlet of mixture out containing micelle and water, top are equipped with the second outlet for drawing the mixed gas containing solvent and water; The equipment for separating liquid from solid being connected with the coacervation device is filled from the mixture that first outlet is drawn into the separation of solid and liquid It sets, obtains dry copolymer micelle.
Equipment according to the present invention, the position of preferably described first import are higher than the position of the second import.It is preferred that institute The liquid level position in coacervation device is stated between the position of the first import and the position of the second import.By above-mentioned setting, have Conducive to being blended for the copolymer solution flowed into from the first import and the water of certain temperature, avoid the first entrance solution and water too fast Contact forms micelle, blocks the first import.
The pressure of another specific embodiment according to the present invention, first entrance is greater than in the coacervation device Pressure, to be conducive to push copolymer solution to flow to coacervation device by pressure difference;And first entrance can copolymer it is molten Spray regime is presented in liquid, and the drop of formation can control the size of micelle, avoids the formation of micelle, winds agitating paddle.In the present invention Method can be carried out continuously, can also intermittently carry out.
Equipment according to the present invention, the vinyl-vinyl acetate copolymer solution obtained by solution copolymerization pass through First import introduces the coacervation device, mixes in the coacervation device with the water of the certain temperature introduced from the second import, It is preferred that the copolymer solution is in spray regime.Vapor is introduced into coacervation device from the third import of coacervation device bottom, is led to Two for crossing control vapor, control the temperature in coacervation device, and the operation temperature of the preferably described coacervation device is controlled in 85- 100℃.In this way, both ensure that operation temperature was higher than the boiling point of volatile matter, be conducive to volatile matter gasification, while reducing steam Consumption saves energy consumption.Residence time of the copolymer solution in coacervation device controls 10-60 minutes, preferably 30-40 Minute, be conducive to micelle and be fully precipitated.
Equipment according to the present invention, the vapor introduced from the third import of the bottom of coacervation device is by second in coacervation device The mixed liquor heat temperature raising of alkene-vinyl acetate copolymer solution and the water of certain temperature strips solvent composition therein, glue Size separation goes out, and the mixed gas containing solvent and vapor is by the second outlet discharge at the top of coacervation device, containing micelle and water Mixture is drawn by being located at the first outlet of the coacervation device bottom.
One specific embodiment of equipment according to the present invention, the specific example of the equipment for separating liquid from solid may include Dehydration and vibration sieve, screw expansion dryer and baking oven etc..
The method and apparatus of solvent in the removing vinyl-vinyl acetate copolymer solution provided according to the present invention, can The volatile component in copolymer solution is removed by a kind of simple technique and equipment, the copolymer after making obtained drying The content of middle volatile component is very small, and such as less than 0.02%.
Detailed description of the invention
Fig. 1 is the flow chart of volatile component in present invention removing vinyl-vinyl acetate copolymer solution.
Specific embodiment
The present invention is described further with reference to the accompanying drawings and examples, but is not caused to the scope of the present invention Any restrictions
With reference to attached drawing 1, vinyl-vinyl acetate copolymer solution 1 and hot water 2 are separately added into coacervation device 4, into cohesion The steam 3 of device 4 is heated heating, while the volatile component in ethane-acetic acid ethyenyl ester solution 2 is stripped out.It is de- Except the glue grain 6 of volatile component separates hot water and wet polymer micelle 7 by dehydration and vibration sieve 10.Wet polymer micelle 7 Wet polymer micelle 8 is obtained by screw extruding dewaterer 12;It is further dehydrated using screw expansion dryer 13;It is most laggard Enter drying in baking oven 14, dry vinyl-vinyl acetate copolymer micelle 11 can be obtained.The steaming that coacervation device 4 is isolated Gas 5 passes through with the water that dehydration and vibration sieve 10 is separated and separates, solvent, unreacted monomer and water are able to by condensation (not shown) is recycled.
Embodiment 1
Removing is the flow chart of volatile component in the vinyl-vinyl acetate copolymer solution of solvent referring to attached using methanol Fig. 1.
80 DEG C of hot water are passed through in coacervation device with water pump;Using methanol as solvent, ethylene-acetate that solid content is about 30% Ethylene ester solution is passed through in coacervation device;The volume ratio of hot water and ethane-acetic acid ethyenyl ester solution is 3:1;Steam is passed through solidifying Poly- device, by the control of steam flow, maintaining the operation temperature of coacervation device is 85 DEG C;In ethane-acetic acid ethyenyl ester solution Volatile component be stripped out.The residence time for controlling ethane-acetic acid ethyenyl ester solution casting device is 30 minutes, is guaranteed Micelle is adequately precipitated in water.The glue grain for removing volatile component is sieved by dehydration and vibration by hot water and wet polymer micelle It separates, the volatile component content in micelle is about 0.3% at this time.Wet polymer micelle is de- by the dehydration of screw extruding dewaterer It waves;Devolatilization is further dehydrated using screw expansion dryer;Drying in baking oven is finally entered, dry ethylene-can be obtained Vinyl acetate copolymer micelle, the volatile component content in micelle is less than 0.02% at this time.
Embodiment 2
Removing using the tert-butyl alcohol as the flow chart of volatile component in the vinyl-vinyl acetate copolymer solution of solvent referring to Attached drawing 1.90 DEG C of hot water are passed through in coacervation device with water pump;Using the tert-butyl alcohol as solvent, ethylene-acetate that solid content is about 30% Ethylene ester solution is passed through in coacervation device;The volume ratio of hot water and ethane-acetic acid ethyenyl ester solution is 2:1;Steam is passed through solidifying Poly- device, by the control of steam flow, maintaining the operation temperature of coacervation device is 95 DEG C;In ethane-acetic acid ethyenyl ester solution Volatile component be stripped out.The residence time for controlling ethane-acetic acid ethyenyl ester solution casting device is 40 minutes, is guaranteed Micelle is adequately precipitated in water.The glue grain for removing volatile component is sieved by dehydration and vibration by hot water and wet polymer micelle It separates, the volatile component content in micelle is about 0.5% at this time.Wet polymer micelle is de- by the dehydration of screw extruding dewaterer It waves;Devolatilization is further dehydrated using screw expansion dryer;Drying in baking oven is finally entered, dry ethylene-can be obtained Vinyl acetate copolymer micelle, the volatile component content in micelle is less than 0.02% at this time.
By the above content it is known that the method and apparatus provided according to the present invention, can fully remove polymer latex Volatile component in grain, and it is simple process, easy to operate, and production cost is low.According to the present invention, it provides a kind of for second The minimizing technology of volatile component in alkene-vinyl acetate copolymer solution.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair It is bright to can be extended to other all methods and applications with the same function.

Claims (9)

1. a kind of method of volatile component in removing vinyl-vinyl acetate copolymer solution, comprising the following steps:
1) by solution copolymerization, vinyl-vinyl acetate copolymer solution is obtained;
2) copolymer solution and the water of certain temperature are mixed to get in container mixed liquor, water steaming is passed through into container Gas, the vapor are mixed with the mixed liquor, then obtain the mixed gas comprising water and solvent, and include copolymer glue The mixture of grain and water;
3) mixture of the micelle and water is separated by solid-liquid separation, obtains dry vinyl-vinyl acetate copolymer;
The volume ratio of the solution of the water and copolymer of the certain temperature is greater than 1:1 to 5:1;
The water of the certain temperature refers to that the temperature of water should be not less than 80 DEG C;
Vapor flow is controlled, so that the temperature being passed through after vapor in container is controlled at 85-100 DEG C;
Controlling residence time of the solution of the copolymer in container is 30-40 minutes;
The method uses following equipment, comprising:
Coacervation device, interior to be equipped with rabbling mechanism, middle part is equipped with the water for being respectively used to introduce copolymer solution and certain temperature The first import and the second import, bottom be equipped with for introduce vapor third import and draw the mixing containing micelle and water The first outlet of object, top are equipped with the second outlet for drawing the mixed gas containing solvent and water;
The equipment for separating liquid from solid being connected with the coacervation device divides from the mixture that first outlet is drawn into the solid-liquid From device, dry vinyl-vinyl acetate copolymer is obtained;
The position of first import is higher than the position of the second import;
Liquid level position in the coacervation device is between the position of the first import and the position of the second import;Described first into The pressure of mouth is higher than the pressure in the coacervation device.
2. the method according to claim 1, wherein the volume of the solution of the water and copolymer of the certain temperature Than for 1.5:1 to 4:1.
3. the method according to claim 1, wherein the water of the certain temperature refers to that the temperature of water should be 80- 90℃。
4. the method according to claim 1, wherein solvent used in the solution copolymerization is fatty alcohol.
5. the method according to claim 1, wherein solvent used in the solution copolymerization be carbon atom not Fatty alcohol greater than 4.
6. the method according to claim 1, wherein solvent used in the solution copolymerization is methanol, second At least one of alcohol, propyl alcohol and butanol.
7. the method according to claim 1, wherein the solution of the copolymer is spurted into step 2) In the water of the certain temperature, mixed liquor is mixed to get with the water of certain temperature.
8. method according to any one of claims 1-7, which is characterized in that the mixed gas and/or described mixed Closing in object includes unreacted monomer, and the unreacted monomer is separated from the mixed gas and/or the mixture Out, it is back to the step 1), carries out copolyreaction.
9. method according to any one of claims 1-7, which is characterized in that by the mixed gas solvent and Water is separated, and obtained solvent and water is back to step 1) and 2) respectively;And/or the water separated in step 3) is returned To step 2).
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Publication number Priority date Publication date Assignee Title
CN102549025A (en) * 2009-10-07 2012-07-04 日本合成化学工业株式会社 Process for producing ethylene/vinyl alcohol copolymer
CN103626910A (en) * 2013-11-29 2014-03-12 西南化工研究设计院有限公司 Solid ethylene-vinyl acetate copolymer and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN102549025A (en) * 2009-10-07 2012-07-04 日本合成化学工业株式会社 Process for producing ethylene/vinyl alcohol copolymer
CN103626910A (en) * 2013-11-29 2014-03-12 西南化工研究设计院有限公司 Solid ethylene-vinyl acetate copolymer and preparation method thereof

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Title
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