CN106543344B - A kind of method and its application preparing EVA elastomer - Google Patents
A kind of method and its application preparing EVA elastomer Download PDFInfo
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- CN106543344B CN106543344B CN201510591591.9A CN201510591591A CN106543344B CN 106543344 B CN106543344 B CN 106543344B CN 201510591591 A CN201510591591 A CN 201510591591A CN 106543344 B CN106543344 B CN 106543344B
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Abstract
The invention discloses a kind of methods for preparing EVA elastomer, it include: using alcohol compound as solvent, in single copolyreaction kettle, ethylene and vinyl acetate carry out free radical polymerization under the initiation of initiator, chain initiating stage, chain growth stage and termination step in control polymerization process carry out under the first ethylene pressure, the second ethylene pressure and third ethylene pressure respectively, are all different wherein controlling the first ethylene pressure with the second ethylene pressure and third ethylene pressure.According to the present invention, provide a kind of method for preparing EVA elastomer, pass through the ethylene pressure in control copolyreaction process, it may be implemented to regulate and control elastomer molecular weight and molecular weight distribution, while guaranteeing Copolycondensation rate, the EVA elastomer for meeting different needs is prepared in the content for reasonably adjusting VAc in polymerizate (vinyl acetate).
Description
Technical field
High molecular method is prepared the present invention relates to a kind of, and in particular to a method of prepare EVA elastomer.
Background technique
Vinyl-vinyl acetate copolymer (EVA) is one of most important ethylene copolymer.EVA is after high-density polyethylene
The fourth-largest ethene copolymer after alkene (HDPE), low density polyethylene (LDPE) (LDPE), linear low density polyethylene (LLDPE) (LLDPE).
Commonly called EVA product refers mainly to EVA resin, VAc content be 5.0-40.0wt%.EVA resin can by injection molding, extrusion molding, blow
The forming methods such as modeling, foaming, thermoforming, heat-sealing, coating, welding are processed into various products, and purposes is very extensive；VAc content
40.0-70.0wt%EVA product is known as EVA elastomer, and the fourth nitrile rubber viscosity of this and easy processing is on close level, flexible and table
Reveal rubbery state feature.EVA elastomer is mainly used as rubber elastomer, polyvinylchloride modifier etc..The higher VAc content of product is determined
Determine EVA elastomer nearly or completely and be amorphous, glass transition temperature (Tg) is about -35 DEG C, the oil resistant with moderate
Property.Currently, mainly using improved high-voltage bulk technique, middle pressure emulsion polymerization with the EVA production firm that Lang Shengwei is represented
Technique and middle pressure solution polymerization process produce EVA elastomer, wherein middle pressure solution polymerization process is suitable for production VAc content 40.0-
The EVA elastomer of 70.0wt%, product VAc changes of contents range is wide, and application range is wider.This technique has compared with bulk polymerization
There is higher molecular weight.Pressure needed for middle pressure solution polymerization process system is lower, formula is simple, polymerization temperature is easily controllable, operation
Simplicity is to prepare the main method of EVA elastomer.There is EVA excellent elasticity, flexibility, the transparency, adherence, low temperature to scratch
Qu Xing, weatherability, resistance to corrosive chemicals and the compatibility with filler and color masterbatch can be used for the blending coating of polymer,
It is widely used in the fields such as modified rubber, shoemaking, agricultural film, cable, solar energy.
In the prior art, ethylene reaction pressure is higher, the wide difficult control of pressure range, cannot achieve to copolyreaction into
The more control accurate of journey, the content of the VAc of obtained product is relatively low, and properties of product are poor, and application range is narrow, is made in synthesis
Solvent selection is improper.Although having been reported that, the content of VAc and the performance of product can be improved using improved technique,
However there are reaction pressures higher, complex operation, polymerization control difficulty are high, the problems such as cost and energy consumption height.
Summary of the invention
According to the present invention, a kind of method for preparing EVA elastomer is provided, the ethylene in control copolyreaction process is passed through
Pressure can reasonably adjust the content (40.0-70.0%) of VAc in polymerizate (vinyl acetate), realize to elastomer point
Son amount and molecular weight distribution regulation, are prepared the EVA elastomer for meeting different needs.
According to an aspect of the invention, there is provided a kind of method for preparing EVA elastomer, comprising: use alcohols chemical combination
Object is as solvent, and in single copolyreaction kettle, ethylene and vinyl acetate carry out free radical polymerization under the initiation of initiator,
Chain initiating stage, chain growth stage and the termination step in polymerization process are controlled respectively in the first ethylene pressure, the second ethylene
It is carried out under pressure and third ethylene pressure, wherein controlling the first ethylene pressure and the second ethylene pressure and third ethylene pressure are equal
It is not identical.By the ethylene pressure of the three phases in control reaction process, so that it is adjusted the content of product VAc, thus
The VAc elastomer for meeting different needs is made.
In a preferred embodiment of the invention, the second ethylene pressure is preferably controlled higher than third ethylene pressure, and
Third ethylene pressure is higher than the first ethylene pressure.In a specific embodiment, the range of first ethylene pressure is
3.5-6.5MPa preferably 4-7MPa；And/or second ethylene pressure range be 5.5-8.5MPa, preferably 6-9MPa；And/or the
The range of triethylene pressure is 5.0-9.0MPa, preferably 5.5-8.5MPa.Under the different ethylene pressure, with react into
The progress of journey, under lower ethylene pressure, in chain initiating stage, the reaction system of polymerization is solution-air copolymerization；In chain growth rank
Section, higher ethylene pressure, ethylene moiety vaporization, system are changed to solution-air copolymerization by solution-air copolymerization and are copolymerized and deposit with liquid-liquid,
To improve the monomer contacting efficiency that ethylene is copolymerized, the solubility of ethylene in the liquid phase is improved, greatly improves monomer copolymerization
The diffusion and efficiency of initiation of rate and free radical in monomer.Enter chain termination rank after the chain growth stage of copolyreaction terminates
Section, system maintain higher ethylene pressure, can guarantee that polymerization reaction equation balance continues to move right, avoid system not anti-
The free basal orientation low molecule answered shifts and reduces the molecular weight of product.
A specific embodiment of the method according to the present invention, the alcohol compound are C1-C6Alcohol compound.
Using C1-C6At least one of alcohol compound be used as solvent, dicyandiamide solution is relatively simple, can reasonably adjust in polymerization
The viscosity of system.Wherein, the C1-C6The example of alcohol compound include but are not limited to: it is methanol, ethyl alcohol, normal propyl alcohol, different
Propyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, ethylene glycol, propylene glycol and glycerine.But use C1-C6Alcohol compound in two kinds
Mixture as solvent in use, the volume ratio of two kinds of alcohol is preferably 1:100-100:1.
Another specific embodiment of the method according to the present invention, the reaction temperature of the polymerization is 40-125 DEG C, excellent
Select 50-90 DEG C.The reaction time of the polymerization is 2-10 hours, preferably 3-6 hours.
The volume ratio of another specific embodiment of the method according to the present invention, the vinyl acetate and solvent is 2:
1-1:5.By controlling the amount ratio of solvent, is conducive to the dispersion of the viscosity and heat of more preferable control system, it is anti-to be conducive to control
The progress answered.
Method according to the present invention, the initiator can be azo and/or peroxide compound, be preferably selected from
At least one of azodiisobutyronitrile, azobisisoheptonitrile, cumyl hydroperoxide and dibenzoyl peroxide.Wherein, institute
The dosage for stating initiator is preferably the 0.4-5wt% of vinyl acetate dosage.
Other copolymerization can also be added in the polymerization process in another specific embodiment of the method according to the present invention
Monomer is copolymerized.Other described comonomers include at least one in propylene, n-butene, isobutene, 1- hexene and 1- octene
Kind.The selection of the additive amount of these other comonomers is not in the range of hindering the present invention to realize goal of the invention.
Method according to the present invention, interior to be equipped with rabbling mechanism for the copolyreaction kettle, upper part is equipped with molten
The feed inlet and ethylene feed of agent and vinyl acetate liquid, its underpart are equipped with discharge port, are also connected with temperature regulating device.Very
It is clear, for a reactor, it can be connected with the device of pressure control, details are not described herein again.
Copolyreaction kettle of the invention, for solution copolymerization reaction to occur and provides reacting field for ethylene and vinyl acetate
Institute；And rabbling mechanism, for realizing the raw material mixing inside copolyreaction kettle.The rabbling mechanism can be located in copolyreaction kettle
Portion's axis line position, is made of sequentially connected driving device, transmission device, agitating shaft and agitating paddle.The agitating paddle can make
It is combined with anchor formula paddle, vane wheel oar, ribbon paddle or anchor formula paddle with the compound paddle of vane wheel oar.In a specific embodiment of the invention
In, it is longitudinally provided with agitating shaft at copolyreaction kettle center, and blade is equipped on agitating shaft, the motor on the upside of autoclave body is logical
Cross transmission mechanism driving agitating shaft rotation.Autoclave body lower end is equipped with end socket and there are discharge ports in end socket bottom.By solvent from charging
In mouth injection kettle, vinyl acetate is added after leading to nitrogen deoxygenation and ethylene carries out polymerization reaction, passes through the pressure in ethylene control kettle
Power controls pressure of the ethylene of addition in the differential responses stage, to control reaction.
In a specific embodiment, the polymerization uses batch technology.Of course it is to be understood that the monomer of industrial buyers
Polymerization inhibitor need to would generally be removed, such as be removed by way of distillation between polymerization containing some polymerization inhibitors.
Another example of the method according to the present invention (is controlled not in different phase using ethylene substep pressure control method
With ethylene pressure) method that prepare EVA elastomer includes being continuously introduced into vinyl acetate, solvent, initiator and ethylene to be total to
In poly- reaction kettle, and copolyreaction product is continuously exported from aforementioned copolyreaction kettle, carries out later separation and the place of product
Reason.
The method provided according to the present invention is significantly improving high glutinous system Copolycondensation rate, reactivity ratio and high solids content
While, it avoids and used VAc content brought by multicomponent mixed solvent slightly lower and the more post-processing difficulties height of solvent composition
The problems such as, industrial application value with higher.
The present invention is poly- using ethylene substep pressure control solution in ethylene-vinyl acetate c one-pot batch production process
It closes technique and produces vinyl-vinyl acetate copolymer, use C1-C6Alcohols solvent, control copolymerization different phase ethylene reaction pressure
Power.In the course of the polymerization process, ethylene pressure is increased, so that ethylene moiety is liquefied, solution-air, liquid-liquid coexist, and are remarkably improved second
The solubility of alkene in the liquid phase mixes it more preferably with vinyl acetate and solvent and improves comonomer contact probability, causes certainly
It is copolymerized by base.The solution-air that compares copolyreaction, it is glutinous in polymerisation in solution height that free radical is greatly improved in three sections of ethylene pressure control techniques
Diffusion efficiency of initiation in system.The ethylene pressure for reasonably adjusting and controlling copolyreaction process three phases, by regulating and controlling gas-
Liquid copolymerization and the double copolymerization systems of liquid-liquid list two-phase, can produce and meet different production and living needs, the EVA elasticity of different VAc contents
Body, industrial application value with higher.
According to another aspect of the present invention, it additionally provides the above method and is preparing the application in EVA elastomer.According to
Method provided by the invention can be used to prepare EVA elastomer, and wherein the content of VAc is high, and the product can show typical case
Elastomer, properties of product are excellent.And the method in the present invention is used to prepare EVA elastomer, and reaction pressure is low, it is easy to control,
Simple process, cost and low energy consumption.
Detailed description of the invention
Fig. 1 is that one-pot of the invention is copolymerized batch technology schematic device.
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.
The copolyreaction device that EVA elastomer is prepared using ethylene stepped pressure method as shown in Figure 1.This technique is using single
Kettle intermittently operated, including copolyreaction kettle 1 and rabbling mechanism；The rabbling mechanism includes stirring motor 2, and transmission device is (in figure
It is not shown) and agitating shaft and the agitating paddle 3 being fixed on agitating shaft.In reaction kettle work, agitating paddle and part stirring axle position
Below reaction liquid level.In process of production, copolyreaction is added from liquid phase feeding mouth 4 in solvent, vinyl acetate and initiator
Kettle 1, ethylene feed 5, which is pressurizeed, to inject in copolyreaction kettle 1 reaches predetermined pressure, controls the ethylene being passed through from ethylene feed 5
Pressure is under three sections of different pressure limits.Carry out the reaction of ethane-acetic acid ethyenyl ester solution copolymerization.After reaction, from discharging
Reaction mass is discharged mouth 6.The reaction kettle 1 is also connected with pressure control device, is not shown in the figure.
The measurement of content of monomer:
Using the VAc content in nuclear-magnetism, elemental analysis, thermogravimetric and infrared four kinds of methods measurement product EVA in embodiment.
In the reaction of the present invention, technical staff usually starts reaction to cause rank to 1/8 referred to as chain of total reaction time
Section；It is known as the chain growth stage from the 1/8 to the 5/8 of total reaction time of total reaction time；It is tied from the 5/8 of total reaction time to reaction
Beam is termination step.
Reaction kettle volume in following embodiment is 10L, and vinyl acetate 6L is added.
Embodiment 1
Use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Initiator is two isobutyl of azo
Nitrile, dosage are the 3wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and total reaction time 4 hours, copolyreaction chain caused
Phase ethylene reaction pressure is 4.0MPa；Chain growth phase ethylene reaction pressure is 6.0MPa；Chain termination phase ethylene reaction pressure maintains
Under this condition for 5.5MPa., VAc content is 64.2wt% in polymerizate.
Embodiment 2
Use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Initiator is two isobutyl of azo
Nitrile, dosage are the 3wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and total reaction time 4 hours, copolyreaction chain caused
Phase ethylene reaction pressure is 5.0MPa；Chain growth phase ethylene reaction pressure is 7.0MPa；Chain termination phase ethylene reaction pressure maintains
Under this condition for 6.5MPa., VAc content is 59.1wt% in polymerizate.
Embodiment 3
Use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Initiator is two isobutyl of azo
Nitrile, dosage are the 3wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and total reaction time 4 hours, copolyreaction chain caused
Phase ethylene reaction pressure is 6.0MPa；Chain growth phase ethylene reaction pressure is 8.0MPa；Chain termination phase ethylene reaction pressure maintains
Under this condition for 7.5MPa., VAc content is 54.5wt% in polymerizate.
Embodiment 4
Use the tert-butyl alcohol for single solvent；The volume ratio of solvent and vinyl acetate is 2:1；Initiator is two isobutyl of azo
Nitrile, dosage are the 3wt% of vinyl acetate；Polymeric reaction temperature is 65 DEG C, and total reaction time 4 hours, copolyreaction chain caused
Phase ethylene reaction pressure is 7.0MPa；Chain growth phase ethylene reaction pressure is 9.0MPa；Chain termination phase ethylene reaction pressure maintains
Under this condition for 8.5MPa., VAc content is 51.5wt% in polymerizate.
Comparative example 1
With embodiment 1, the difference is that ethylene pressure is constant in the course of the polymerization process, control in 6.0MPa.Under this condition,
VAc content is 77.2wt% in polymerizate, and VAc content is higher, and copolymerization product is softer, large viscosity, and elastomeric characteristic shows not
Obviously.
It by embodiment and comparative example data comparison, uses alcohol used in the present invention for solvent, controls three sections of reacting ethylene pressures
EVA elastomer can be prepared in power, and product form is excellent, show typical elastomeric body characteristics, and EVA product VAc content is suitable
In, different production and living demands can be met.The present invention uses in ethylene-vinyl acetate c one-pot batch production process
Ethylene substep pressure control solution polymerization process produces vinyl-vinyl acetate copolymer, uses C1-C6Alcohols solvent, control copolymerization is not
With stage ethylene reaction pressure.In the course of the polymerization process, ethylene pressure is increased, ethylene moiety is made to liquefy, solution-air, liquid-liquid copolymerization are altogether
It deposits, is remarkably improved the solubility of ethylene in the liquid phase, mix it more preferably with vinyl acetate and solvent and improve comonomer
Contact probability causes free-radical polymerized.Freedom is greatly improved in the solution-air that compares copolyreaction, three sections of ethylene pressure control techniques
Base sticks the diffusion efficiency of initiation in system in polymerisation in solution height.Reasonably adjust and control the ethylene of copolyreaction process three phases
Pressure can produce by the copolymerization of regulation solution-air and the double copolymerization systems of liquid-liquid list two-phase and meet different production and living needs, different
The EVA elastomer of VAc content, industrial application value with higher.
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 (11)
1. a kind of method for preparing EVA elastomer, comprising: using alcohol compound as solvent, in single copolyreaction kettle,
Ethylene and vinyl acetate carry out free radical polymerization under the initiation of initiator, control chain initiating stage, chain in polymerization process
Build phase and termination step carry out under the first ethylene pressure, the second ethylene pressure and third ethylene pressure respectively, wherein
The second ethylene pressure is controlled higher than third ethylene pressure, and third ethylene pressure is higher than the first ethylene pressure；
Wherein, the range of first ethylene pressure is 3.5-7.5MPa；Range with the second ethylene pressure is 5.5-9.5MPa；
Range with third ethylene pressure is 5.0-9.0MPa；
The reaction temperature of the polymerization is 40-125 DEG C；The reaction time of the polymerization is 2-10 hours；
The volume ratio of the vinyl acetate and solvent is 2:1-1:5；
The initiator is azo and/or peroxide compound；
The dosage of the initiator is the 0.4-5wt% of ethyl acetate dosage.
2. the method according to claim 1, wherein the range of first ethylene pressure is 4.0-7.0MPa；
Range with the second ethylene pressure is 6-9MPa；Range with third ethylene pressure is 5.5-8.5MPa.
3. method according to claim 1 or 2, which is characterized in that the alcohol compound is C1-C6Alcohol compound.
4. method according to claim 3, which is characterized in that the alcohol compound is selected from methanol, ethyl alcohol, positive third
At least one of alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, ethylene glycol, propylene glycol and glycerine.
5. the method according to claim 1, wherein the solvent is C1-C6Alcohol compound in two kinds
Mixture.
6. according to the method described in claim 5, it is characterized in that, the volume ratio of two kinds of alcohol compounds is 1:100-
100:1。
7. method according to claim 1 or 2, which is characterized in that the reaction temperature of the polymerization is 50-90 DEG C；It is described
The reaction time of polymerization is 3-6 hours.
8. method according to claim 1 or 2, which is characterized in that interior to be equipped with blender for the copolyreaction kettle
Structure, upper part are equipped with the feed inlet and ethylene feed of solvent and vinyl acetate liquid, and its underpart is equipped with discharge port, also connects
It is connected to pressure control device.
9. the method according to claim 1, wherein the initiator is different selected from azodiisobutyronitrile, azo two
At least one of heptonitrile, cumyl hydroperoxide and dibenzoyl peroxide.
10. method according to claim 1 or 2, other comonomers are added in the polymerization process and are copolymerized, it is described
Other comonomers include at least one of propylene, n-butene, isobutene, 1- hexene and 1- octene.
11. any one of -10 the methods are preparing the application in EVA elastomer according to claim 1.
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| US2947735A (en) * | 1957-01-02 | 1960-08-02 | Bayer Ag | Process for the production of copolymers of ethylene |
| CN1270602A (en) * | 1997-09-18 | 2000-10-18 | 巴斯福股份公司 | Method for copolymerizing ethylene with vinyl carboxylates |
| CN1906246A (en) * | 2003-12-25 | 2007-01-31 | Jsr株式会社 | Thermoplastic elastomer composition, method for producing same and formed article |
-
2015
- 2015-09-16 CN CN201510591591.9A patent/CN106543344B/en active Active
Patent Citations (3)
| 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 |
| CN1270602A (en) * | 1997-09-18 | 2000-10-18 | 巴斯福股份公司 | Method for copolymerizing ethylene with vinyl carboxylates |
| CN1906246A (en) * | 2003-12-25 | 2007-01-31 | Jsr株式会社 | Thermoplastic elastomer composition, method for producing same and formed article |
Non-Patent Citations (1)
| Title |
|---|
| "乙烯-醋酸乙烯酯弹性体的制备和研究";陈博;《中国石油和化工标准与质量》;20131130(第11期);第21页 |
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