CN106543331B - A method of preparing EVA elastomer - Google Patents
A method of preparing EVA elastomer Download PDFInfo
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- CN106543331B CN106543331B CN201510590923.1A CN201510590923A CN106543331B CN 106543331 B CN106543331 B CN 106543331B CN 201510590923 A CN201510590923 A CN 201510590923A CN 106543331 B CN106543331 B CN 106543331B
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Abstract
This application discloses a kind of methods for preparing EVA elastomer, comprising: in single reactor, using alcohol compound as solvent, controls ethylene pressure, ethylene is made to liquefy completely, so that ethylene and vinyl acetate be made to carry out the single-phase combined polymerization of liquid-liquid, EVA elastomer is made.According to the present invention, on the basis of existing EVA elastomer solution polymerization process, adjustment ethylene reaction pressure makes ethylene liquefy completely, liquid-liquid is copolymerized to improve comonomer contacting efficiency, improve the solubility of ethylene in the liquid phase, the single-phase copolyreaction of perfect solution greatly improves the diffusion and efficiency of initiation of monomer the copolymerization rate and free radical in comonomer solution；According to different polymerizate application demands, it is deployed by solvent, while significantly improving high glutinous system Copolycondensation rate, high solids content, one-pot technique is selected to also avoid the problems such as manipulation at high cost of more kettle technique raw material process units is complicated, industrial application value with higher.
Description
Technical field
The present invention relates to a kind of methods for preparing high molecular material, and in particular to a method of prepare EVA elastomer.
Background technique
Ethene-vinyl acetate copolymer (EVA) is a kind of very high random copolymer of the degree of branching, by nonpolarity vinyl monomer
(E) it is copolymerized with highly polar vinyl acetate monomer (VAc), is one of most important ethylene derivative copolymer.And polyethylene
(PE) it compares, since molecule segment introduces VAc monomer, greatly reduces polymer crystallinity, make its ageing resistance, impact resistance
Property, compatibility, flexibility significantly increase.EVA performance and copolymerization system VAc content are closely related, low VAc content EVA product, property
It can be similar with LDPE；High VAc content EVA product, performance are infinitely close to rubber elastomer.In polymerization process, E and VAc is controlled
Dosage can produce the different trades mark, miscellaneous EVA product, widen the research field of polyethylene product significantly and using model
It encloses.EVA has excellent low temperature resistant and environmental stress cracking resistance, while having good optical property, nontoxic, extensively
It is general to extrude the fields such as product, solar energy for packaging film, agricultural film, wire and cable, shoemaking, injection.In recent years, both at home and abroad to EVA
Product demand is growing, and exploitation and production EVA product have good development prospect, can bring more considerable economic effect
Benefit.
It is gas-liquid two-phase that the excessively high uncontrollable, reaction system of dicyandiamide solution complexity, ethylene pressure, which exists in the prior art,
The problems such as copolymerization, technique and the device is complicated, cost energy consumption height.
Summary of the invention
It aiming at the shortcomings in the prior art, can be medium this application provides a kind of method for preparing EVA elastomer
By single-phase liquid-liquid combined polymerization under pressure, EVA elastomer is made, the content of VAc is suitable for (40.0-70.0wt%), is shown
Typical elastomeric characteristic, properties of product are excellent, provide a kind of method for simply preparing EVA elastomer.The present invention also mentions
The application of above-mentioned preparation method is supplied.
According to an aspect of the invention, there is provided a kind of method for preparing EVA elastomer, comprising: in single reactor
In, using alcohol compound as solvent, ethylene pressure is controlled, ethylene is made to liquefy completely, so that ethylene and vinyl acetate be made to carry out
EVA elastomer is made in liquid-liquid combined polymerization.
According to a preferred embodiment of the present invention, the ethylene pressure control is in 8.0-20.0MPa.Institute according to the present invention
The method stated, selection alcohol compound are solvent, and the chain transfer constant of solvent is low, are remarkably improved product solid content and product
Mooney viscosity, can substantially reduce the acetaldehyde in system VAc, and EVA elastomer performance is excellent；Dicyandiamide solution is relatively simple,
The lower ethylene that pressurizes liquefies completely, under the conditions of homogeneous copolyreaction, can reasonably adjust solution polymerization system viscosity, be copolymerized in control
While reaction rate, polymerizate VAc content is adjusted, realizes and EVA elastomer molecular weight and molecular weight distribution is regulated and controled, pass through
One-pot can prepare the EVA elastomer product for meeting different needs.
According to the present invention, on the basis of existing EVA elastomer solution polymerization process, adjustment ethylene reaction pressure makes second
Alkene liquefies completely, and liquid-liquid copolymerization improves the solubility of ethylene in the liquid phase, perfect solution to improve comonomer contacting efficiency
Single-phase copolyreaction greatly improves the diffusion and efficiency of initiation of monomer the copolymerization rate and free radical in comonomer solution；According to
Different polymerizate application demands, are deployed by solvent, significantly improve high glutinous system Copolycondensation rate, high solids content it is same
When, select one-pot technique to also avoid the problems such as manipulation at high cost of more kettle technique raw material process units is complicated, it is with higher
Industrial application value.
The temperature of a specific embodiment of the method according to the present invention, the polymerization is controlled at 40-125 DEG C, preferably
55-80℃.Another specific embodiment of the method according to the present invention, the time of the polymerization are 2-10 hours, preferably 3-8
Hour.
Another specific embodiment according to the present invention, the solvent are at least one of the alcohol compound of C1-C6.
C1-C2The chain transfer constant of alcohol is low, is remarkably improved product solid content, while can substantially reduce the acetaldehyde in system VAc,
EVA elastomer performance is excellent.C3-C6Alcohols itself has certain viscosity, and chain transfer constant is relatively low, as solvent, is significantly mentioning
High product solid content, while substantially reduce the acetaldehyde in system VAc, can be the Mooney viscosity of product can be reduced.Choosing
Use C1-C6Alcohols, dicyandiamide solution is relatively simple, pressurizes in ethylene and liquefies completely, under the conditions of homogeneous copolyreaction, can rationally adjust
Whole solution polymerization system viscosity adjusts polymerizate VAc content while controlling Copolycondensation rate, realizes to EVA elasticity
The regulation of body molecular weight and molecualr weight distribution, preparation meet the EVA elastomer product of different needs.It is preferred that vinyl acetate and solvent
Volume ratio be 2/1-1/5.It according to different polymerizate application demands, is deployed by solvent, significantly improving, high glutinous system is total
Poly- reaction rate, high solids content, industrial application value with higher.
Another specific embodiment according to the present invention, the mixing that the solvent is two kinds in the alcohol compound of C1-C6
Object, the volume ratio of described two alcohol compounds are 1/100-100/1.Two different alcohol compounds are selected, are conducive to pair
The viscosity of dicyandiamide solution is regulated and controled, and is conducive to reasonably adjust solution polymerization system viscosity, while controlling Copolycondensation rate,
Adjust polymerizate VAc content.
Another specific embodiment according to the present invention, the initiator of the copolymerization are azo and/or peroxide
Class compound is preferably selected from azodiisobutyronitrile, azobisisoheptonitrile, cumyl hydroperoxide and dibenzoyl peroxide
It is at least one.Wherein, the dosage of the initiator is the 0.4-5.0wt% of vinyl acetate amount.
Another specific embodiment according to the present invention, the technique of the combined polymerization are batch technology.
Method according to the present invention is copolyreaction kettle for the single reactor, interior to be equipped with blender
Structure, upper part are equipped with liquid phase feeding mouth and ethylene feed for solvent, initiator and vinyl acetate charging, its underpart
Equipped with discharge port, it is also connected with the pressure control device for controlling pressure in kettle.Wherein, copolyreaction kettle, for for ethylene and
Vinyl acetate occurs single phase soln copolyreaction and provides reacting environment；And rabbling mechanism, inside copolyreaction kettle
Raw material mixing.In one embodiment of the invention, the rabbling mechanism is located at copolyreaction kettle axis line inside position, by
Sequentially connected driving device, transmission device, agitating shaft and agitating paddle composition.The agitating paddle can be used anchor formula paddle, vane wheel oar,
Ribbon paddle or anchor formula paddle are combined with the compound paddle of vane wheel oar.It is appreciated that having the structure for surveying pressure in the pressure control device, pass through
The ethylene pressure of measurement is regulated and controled, so that the ethylene in kettle liquefies completely.
In one particular embodiment of the present invention, it is longitudinally provided with agitating shaft at copolyreaction kettle center, and stirred
Axis is equipped with blade, and the motor on the upside of autoclave body drives agitating shaft rotation by transmission mechanism.Autoclave body lower end is equipped with end socket simultaneously
In end socket bottom, there are discharge ports.By solvent from liquid phase feeding mouth injection kettle in, lead to nitrogen deoxygenation after be added vinyl acetate and
Ethylene carries out polymerization reaction, using one-pot batch technology.
Based on above-mentioned copolyreaction device, in one embodiment of the invention, using single-phase middle-pressure process preparation EVA elasticity
The method of body includes vinyl acetate, solvent, initiator and ethylene being continuously introduced into copolyreaction kettle, and copolyreaction is produced
Object is continuously exported from aforementioned copolyreaction kettle, carries out the later separation and processing of product.
The present invention can also be added other polymerized monomers while EVA polymerize and be copolymerized.As used in copolymerization
Polymerized monomer can enumerate at least one of alkene such as propylene, n-butene, isobutene, 1- hexene, 1- octene.These polymerized monomers
Additive amount proportion selection do not hinder the present invention realize goal of the invention in the range of.
It should be understood that polymerization inhibitor is usually contained in the monomer such as VAc monomer that are purchased commercially, before being copolymerized
Certainly it to be purified, such as distillation is to remove polymerization inhibitor.
The method provided according to the present invention uses alcohols for solvent (such as C1-C6Alcohols), dicyandiamide solution is relatively simple, in second
Alkene pressurization liquefaction completely, under the conditions of the single-phase copolyreaction of liquid-liquid, improves comonomer contacting efficiency, improves ethylene in the liquid phase
Solubility, greatly improve the diffusion and efficiency of initiation of monomer the copolymerization rate and free radical in comonomer solution；It can be reasonable
Solution polymerization system viscosity is adjusted, realizes and EVA elastomer molecular weight and molecular weight distribution is regulated and controled, in control Copolycondensation rate
While, polymerizate VAc content is adjusted, the EVA elastomer product for meeting different needs can be prepared by one-pot.
According to another aspect of the present invention, it additionally provides the above method and is preparing the application in EVA elastomer.It utilizes
Method provided by the invention, it will be able to which preparing VAC content is suitable for that elastomeric characteristic is obvious, meets the EVA elasticity of different needs
Body.
According to the present invention, use alcohol compound for solvent, the chain transfer constant of solvent is low, and can reduce the Mooney of product
Viscosity significantly improves product solid content, while can substantially reduce the acetaldehyde in system VAc, and EVA elastomer performance is excellent；
Adjustment ethylene reaction pressure makes ethylene liquefy completely, and liquid-liquid copolymerization improves ethylene in liquid phase to improve comonomer contacting efficiency
In solubility, the single-phase copolyreaction of perfect solution greatly improves monomer the copolymerization rate and free radical in comonomer solution
Diffusion and efficiency of initiation；It according to different polymerizate application demands, is deployed by solvent, significantly improving, high glutinous system copolymerization is anti-
While answering rate, high solids content, one-pot technique is selected to also avoid the manipulation at high cost of more kettle technique raw material process units multiple
The problems such as miscellaneous, industrial application value with higher.
Detailed description of the invention
Fig. 1 is ethane-acetic acid ethyenyl ester one-pot copolymerization process schematic device of the invention.
In figure: 1- polymerization reaction kettle；2- stirring motor；3- agitating shaft and agitating paddle；4- liquid phase feeding mouth；5- ethylene feed
Mouthful；6- discharge port.
Specific embodiment
The present invention is further illustrated below by embodiment, but does not constitute any limitation of the invention.
As shown in Figure 1, method according to the present invention prepares the copolyreaction device of EVA elastomer.Using one-pot
Intermittently operated, including copolyreaction kettle 1 and rabbling mechanism；The rabbling mechanism include stirring motor 2, transmission device (in figure not
Show) and agitating shaft and the agitating paddle 3 being fixed on agitating shaft.In reaction kettle work, agitating paddle and part agitating shaft are located at
React liquid level or less.In process of production, copolyreaction kettle is added from liquid phase feeding mouth 4 in solvent, vinyl acetate and initiator
1, it is constant that ethylene is reached into predetermined pressure out of ethylene feed 5 constantly pressurization injection copolyreaction kettle 1, and ethylene is made to liquefy,
Carry out the reaction of ethane-acetic acid ethyenyl ester solution copolymerization.After reaction, reaction mass is discharged from discharge port 6.
Using the VAc content in conventional nuclear-magnetism, elemental analysis and infrared three kinds of methods measurement product EVA in embodiment.
Embodiment 1
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is azodiisobutyronitrile, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and ethylene pressure is
19.0MPa, the reaction time 4 hours.Under this condition, VAc content is 49.7wt% in polymerizate.
Embodiment 2
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is azodiisobutyronitrile, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and ethylene pressure is
17.0MPa, the reaction time 4 hours.Under this condition, VAc content is 51.1wt% in polymerizate.
Embodiment 3
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is azodiisobutyronitrile, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and ethylene pressure is
13.0MPa, the reaction time 4 hours.Under this condition, VAc content is 57.6wt% in polymerizate.
Embodiment 4
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is azodiisobutyronitrile, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and ethylene pressure is
9.0MPa, the reaction time 4 hours.Under this condition, VAc content is 68.3wt% in polymerizate.
Embodiment 5
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is azodiisobutyronitrile, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 55 DEG C, and ethylene pressure is
12.0MPa, the reaction time 4 hours.Under this condition, VAc content is 66.5wt% in polymerizate.
Embodiment 6
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is azodiisobutyronitrile, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 85 DEG C, and ethylene pressure is
12.0MPa, the reaction time 4 hours.Under this condition, VAc content is 63.1wt% in polymerizate.
Embodiment 7
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is benzoyl peroxide, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 70 DEG C, and ethylene pressure is
15.0MPa, the reaction time 3 hours.Under this condition, VAc content is 49.8wt% in polymerizate.
Embodiment 8
In single reaction kettle, use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Draw
Hair agent is benzoyl peroxide, and dosage is the 3.0wt% of vinyl acetate；Polymeric reaction temperature is 70 DEG C, and ethylene pressure is
15.0MPa, the reaction time 8 hours.Under this condition, VAc content is 43.6wt% in polymerizate.
Comparative example 1
With embodiment 1, ethylene reaction pressure is 21.0MPa, other reaction conditions are constant, and copolymerization product VAc content is
27.7wt%, copolymerization product hardness is big, rigidity is stronger, does not show typical elastomeric body characteristics.
Comparative example 2
With embodiment 1, ethylene reaction pressure is 7.0MPa, other reaction conditions are constant, and product VAc content is
73.4wt%, copolymerization product toughness is low, and elastomer apparent property is low.
By embodiment and comparative example data comparison, in the pressure range of reasonable 8.0-20.0MPa, EVA is produced
Object VAc content is moderate, and EVA product form is excellent, shows typical elastomeric body characteristics.When hypertonia,
By the above content it is known that being total to by using single-phase middle pressure solution polymerization process production ethane-acetic acid ethyenyl ester
Polymers, by using C1-C6Alcohols solvent rationally controls reacting ethylene pressure, and changing the copolymerization of polymerization system solution-air is that liquid-liquid is copolymerized
To improve comonomer contacting efficiency, solubility of the ethylene in monomer and solvent is greatly improved, complete single phase soln copolymerization is anti-
It answers, realizes and EVA copolymer molecular weight and molecular weight distribution are regulated and controled, while guaranteeing Copolycondensation rate, when shortening reaction
Between, product solid holdup is greatly improved, preparation meets the EVA elastomer product of different needs, difference VAc content；Meanwhile between one-pot
Skill of knocking off and solvent selection proportion facilitate purification of products and solvent recovery and post-processing, and industrial energy saving consumption reduction is significant.
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 (16)
1. a kind of method for preparing EVA elastomer, comprising: in single reactor, using alcohol compound as solvent, control ethylene
Pressure makes ethylene liquefy completely, so that ethylene and vinyl acetate be made to carry out the single-phase copolymerization of liquid-liquid under the initiation of initiator
It closes, EVA elastomer is made, ethylene pressure is controlled in 8.0-20.0MPa.
2. the method according to claim 1, wherein the temperature of the polymerization is 40-125 DEG C.
3. according to the method described in claim 2, it is characterized in that, the temperature of the polymerization is 55-80 DEG C.
4. method described in any one of -3 according to claim 1, which is characterized in that the time of the polymerization is that 2-10 is small
When.
5. according to the method described in claim 4, it is characterized in that, the time of the polymerization is 3-8 hours.
6. method described in any one of -3 according to claim 1, which is characterized in that the solvent is the alcohols of C1-C6
Close at least one of object.
7. according to the method described in claim 6, it is characterized in that, the volume ratio of vinyl acetate and solvent is 2/1-1/5.
8. method described in any one of -3 according to claim 1, which is characterized in that the solvent is the alcohols of C1-C6
Close two kinds of mixture in object.
9. according to the method described in claim 8, it is characterized in that, the volume ratio of described two alcohol compounds is 1/100-
100/1。
10. method described in any one of -3 according to claim 1, which is characterized in that the initiator be azo and/or
Peroxide compound.
11. according to the method described in claim 10, it is characterized in that, the initiator is selected from azodiisobutyronitrile, azo two
At least one of different heptonitrile, cumyl hydroperoxide and dibenzoyl peroxide.
12. according to the method for claim 11, which is characterized in that the dosage of the initiator is vinyl acetate amount
0.4-5.0wt%.
13. according to the method described in claim 10, it is characterized in that, the technique of the combined polymerization is batch technology.
14. method described in any one of -3 according to claim 1, which is characterized in that for the single reactor, be
Copolyreaction kettle, in be equipped with rabbling mechanism, upper part be equipped with for solvent, initiator and vinyl acetate charging liquid phase into
Material mouth and ethylene feed, its underpart are equipped with discharge port, are also connected with the pressure control device for controlling pressure in kettle.
15. method described in any one of -3 according to claim 1, which is characterized in that during the combined polymerization, be added
Other monomers, the other monomers are selected from least one of propylene, n-butene, isobutene, 1- hexene and 1- octene.
16. any one of -15 the methods are preparing the application in EVA elastomer according to claim 1.
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| CN113105574A (en) * | 2021-04-12 | 2021-07-13 | 江苏斯尔邦石化有限公司 | Ethylene-vinyl acetate copolymer and preparation method and application thereof |
| CN116120496A (en) * | 2021-11-15 | 2023-05-16 | 中国石油化工股份有限公司 | Process for preparing high molecular weight ethylene-vinyl acetate copolymer |
| CN114230700B (en) * | 2022-01-07 | 2022-10-04 | 云南正邦科技有限公司 | Method for preparing high-ethylene-content EVA copolymer through medium and low pressure solution polymerization |
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|---|---|---|---|---|
| US2947735A (en) * | 1957-01-02 | 1960-08-02 | Bayer Ag | Process for the production of copolymers of ethylene |
| US4409187A (en) * | 1980-03-22 | 1983-10-11 | Bayer Aktiengesellschaft | Sealing agent and lubricant for medium-pressure and high-pressure autoclaves |
| US5093450A (en) * | 1988-12-23 | 1992-03-03 | Bayer Aktiengesellschaft | Process for the preparation of ethylene/vinyl acetate copolymers with increased strength, the new ethylene/vinyl acetate copolymers and their use |
| CN1270602A (en) * | 1997-09-18 | 2000-10-18 | 巴斯福股份公司 | Copolymerization of ethylene and vinyl carboxylate |
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2015
- 2015-09-16 CN CN201510590923.1A patent/CN106543331B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2947735A (en) * | 1957-01-02 | 1960-08-02 | Bayer Ag | Process for the production of copolymers of ethylene |
| US4409187A (en) * | 1980-03-22 | 1983-10-11 | Bayer Aktiengesellschaft | Sealing agent and lubricant for medium-pressure and high-pressure autoclaves |
| US5093450A (en) * | 1988-12-23 | 1992-03-03 | Bayer Aktiengesellschaft | Process for the preparation of ethylene/vinyl acetate copolymers with increased strength, the new ethylene/vinyl acetate copolymers and their use |
| CN1270602A (en) * | 1997-09-18 | 2000-10-18 | 巴斯福股份公司 | Copolymerization of ethylene and vinyl carboxylate |
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