CN107793520A - A kind of method for preparing polyethylene polyvinyl acetate ester elastomer emulsifies free microemulsion - Google Patents
A kind of method for preparing polyethylene polyvinyl acetate ester elastomer emulsifies free microemulsion Download PDFInfo
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- CN107793520A CN107793520A CN201610808853.7A CN201610808853A CN107793520A CN 107793520 A CN107793520 A CN 107793520A CN 201610808853 A CN201610808853 A CN 201610808853A CN 107793520 A CN107793520 A CN 107793520A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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Abstract
The application is related to a kind of preparation method of polyethylene polyvinyl acetate ester elastomer emulsifies free microemulsion, including：Mixed solvent is added into aqueous phase, adds pH adjusting agent, the ethene being passed through and the vinyl acetate added carry out copolyreaction in the presence of water soluble starter, obtain polyethylene polyvinyl acetate ester elastomer microemulsion；Wherein, emulsifying agent and colloid protective agent are not added in reaction system.EVA emulsifies free microemulsion product latexes particle diameters are smaller, and particle is evenly distributed, good emulsion stability.Mixed solvent addition proportioning is controlled, latex particle particle diameter can be rationally reduced, maintain particle shape, prevent from being adhered generation, greatly improve stability of emulsion；Emulsifying agent and colloid protective agent are not added, emulsion formulations can be simplified, emulsion production cost is reduced, green pollution-free, further expands emulsion applications field.The simple cost of material of inventive formulation is low, easy to operate, target good emulsion stability, or even can stablize storage more than 11 months.
Description
Technical field
The present invention relates to a kind of method for preparing EVA elastomer microemulsions, and in particular to one kind prepares EVA elastomers without soap
The method of microemulsion.
Background technology
The EVA elastomer emulsions of emulsion polymerization production, vinyl acetate (VAc) content is moderate, and product transparency is high, tool
There are excellent pliability, cold flexibility, weatherability, resistance to corrosive chemicals and the compatibility with filler and color masterbatch；EVA
Product emulsion intensity height, asepsis environment-protecting, adhesive property are excellent, available for weave, light industry, coating, plastic toughening, preparation for building
Material, polymer blending coating, modified rubber etc. field, are widely used, its domestic and international demand is continuously increased, and is developed in recent years fast
Speed.
Patent CN101200518A uses hydrogen peroxide-ferrous sulfate system, and two benches ladder temperature control triggers radical polymerization.
From anion emulsifier and nonionic emulsifier composite emulsifying system, colloid protective agent is used cooperatively；Patent
CN102333799A triggers polymerization to prepare EVA latex using redox initiator combinations.From non-ionic ethoxylated emulsification
Agent, polyvinyl alcohol and water-soluble cellulose derivative are assistant for emulsifying agent；Patent CN103665241 is emulsified from quaternary ammonium salt cationic
Agent and nonionic emulsifier composite emulsifying system, polyvinyl alcohol, polyethers, etherified cellulose are that assistant for emulsifying agent prepares solid content 50%
EVA latex；Patent CN102695725A describes a kind of continuity emulsion polymerisation process, and invention uses multi-floating bodies technique,
System is used cooperatively from nonionic emulsifier and polyvinyl alcohol.Invention prepares gained EVA latex above, and emulsifying agent helps emulsification
Agent prescription is complicated and dosage is larger, and complex operation, emulsifying agent, which exist, has a strong impact on emulsion quality, and product degree of purity is low, raw
It is high to produce cost.
In patent CN1302027C, polymerization is triggered to prepare high solid EVA latex at 40-60 DEG C.The present invention does not add table
Face activating agent, but it is colloid protective agent to need 1.0-15.0wt% polyvinyl alcohol；Patent CN1603350A ethylene reaction pressure
4.0-12.0MPa, 100-120 DEG C are triggered polymerization to prepare high solids content EVA latex.Colloid protective agent polyvinyl alcohol dosage is 4.0-
8.0wt%.Invention prepares gained EVA latex above, though unused emulsifying agent, the colloid protective agent dosage added is larger, work
Skill operation is more complicated, product degree of purity is relatively low, and production cost is high.
EVA microemulsion average grain diameters are small, penetrating power is strong, wetability is excellent and stability is high, have a extensive future.For
Traditional EVA emulsions, surfactant and colloid protective agent are present to polymer emulsion water resistance, spray dryness and dry powder particles
Redispersibility adversely affects；Emulsifier-free emulsion polymerization process is not added with emulsifying agent or only adds micro emulsifying agent completely, less than facing
The latex particle of cleaning can be obtained under conditions of boundary's micellar concentration (CMC), simplifies polymerization technique.Surfactant-free emulsion polymerization process disappears
Except influence of the emulsifying agent to particle, product quality is improved.
EVA nano particle micro emulsions are prepared for surfactant- free emulsion polymerization, because its technological difficulty is high, are rarely had at present
Report.
The content of the invention
The more emulsifying agents of existing traditional EVA emulsion polymerizations and assistant for emulsifying agent are used cooperatively, formula is complicated, latex particle is excessive,
Easily be adhered, particle shape and stability of emulsion it is poor；A large amount of emulsifying agents use, and add production cost, while cause dirt to environment
Dye, products application scope are limited.For deficiency of the prior art, prepared this application provides one kind using mixed solvent technique
The method of EVA (polyvinyl-polyvinylacetate) elastomer emulsifies free microemulsion.Gathered using mixed solvent method EVA elastomers without soap
Close technique, it is possible to achieve do not add emulsifying agent and colloid protective agent, significantly reduce EVA elastomer latex particle diameters, maintain grain
Sub- form, greatly improves stability of emulsion.This invention prepares gained EVA elastomer emulsifies free microemulsions, and product stability is good, does not add
Add that emulsifying agent is green, latex particle particle diameter is small, VAc contents are moderate, excellent performance, different demands can be met.
According to an aspect of the invention, there is provided a kind of preparation method of EVA elastomers emulsifies free microemulsion, including：To
Mixed solvent is added in aqueous phase, adds pH adjusting agent, the ethene being passed through and the vinyl acetate added draw in water-soluble free radical
Copolyreaction is carried out in the presence of hair agent, obtains EVA elastomer microemulsions；Wherein, emulsifying agent and glue are not added in reaction system
Body protective agent.
According to method provided by the invention, on the basis of existing EVA emulsion polymerizations production technology, in certain polymerizing condition
Under, emulsifying agent and colloid protective agent are not added, EVA elastomer emulsifies free microemulsions are prepared using mixed solvent technique, to simplify breast
Liquid polymerization formula, production cost is reduced, reduce latex particle particle diameter, improve stability of emulsion.Traditional EVA emulsion polymerizations, emulsification
Agent, assistant for emulsifying agent Recipe are complicated, and emulsion particle particle diameter is bigger than normal to be easily adhered, and react difficult control, cause copolymerization stage easily broken
Breast；The use of emulsifying agent, substantially increases production cost, brings certain pollution to environment, limits emulsion applications.For O/
W micro-emulsion polymerization systems, the low surface tension of emulsifying systems are advantageous to Nano latex generation, and monomer is not easy to reunite.This hair
In bright, small molecule ketones solvent and alcohol are added to copolymerization system, reduces system polarity and surface tension, two class solvent polarities
Complementation, monomer and latex particle is promoted to disperse.Under the conditions of this, EVA emulsifies free microemulsion product latexes particle diameters are smaller, particle point
Cloth is uniform, good emulsion stability.Mixed solvent addition proportioning is controlled, latex particle particle diameter can be rationally reduced, maintain particle shape
State, prevent from being adhered generation, greatly improve stability of emulsion；Emulsifying agent and colloid protective agent are not added, emulsion formulations can be simplified, is dropped
Low emulsion production cost, green pollution-free, further expand emulsion applications field.The simple cost of material of inventive formulation
It is low, easy to operate, target good emulsion stability.
According to the method for the invention specific embodiment, the mixed solvent includes ketone compounds and alcohols
Compound.The volume ratio of the mixed solvent and aqueous phase is 1/15-1/5.In the volume range, may advantageously facilitate monomer and
Latex particle disperses.In a specific embodiment, the volume ratio of the mixed solvent and aqueous phase is 1/10.
In the present invention, the mixed solvent includes C4-C8Ketone compounds and C1-C6Alcohol compound.The ketone
Class compound is selected from least one of butanone, the bronze medals of 2- penta, methyln-hexyl ketone, 3- octanones and its isomer.The alcohols chemical combination
Thing is in methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, ethylene glycol, propane diols and glycerine
It is at least one.The volume ratio of the ketone compounds and alcohol compound is 10/1-1/10.By controlling matching somebody with somebody for mixed solvent
Than advantageously reducing latex ion particle diameter, maintaining particle shape, prevent from being adhered generation, greatly improve stability of emulsion.Emulsion is total to
Under polymerizing condition, system adds alcohols solvent after first adding ketones solvent.
According to the method for the invention specific embodiment, the water-soluble free radical initiator from inorganic salts,
One or more in azo-compound, inorganic peroxide and inorganic oxide reduction class initiator, preferably are selected from ammonium persulfate, mistake
It is sodium sulphate, potassium peroxydisulfate, the isobutyl imidazoline hydrochloride of azo two, azo dicyano valeric acid, azo diisobutyl amidine hydrochloride, double
One or more in oxygen water and sodium peroxide.The dosage of the water-soluble free radical initiator is vinyl acetate dosage
0.5-5.0wt%, preferably 0.5-2.0wt%.
According to a specific embodiment of the method for the invention, the pH adjusting agent is selected from sodium acid carbonate and ammoniacal liquor.It is described
The dosage of pH adjusting agent is the 0.05-5.0wt% of vinyl acetate dosage, and its further preferred dosage is vinyl acetate dosage
0.5-2.0wt%.
According to the method for the invention specific embodiment, methods described includes：Under the first mixing speed, Xiang Shui
The ketone compounds of in the mixed solvent are added in phase, the alcohol compound of in the mixed solvent is added, adds pH adjusting agent, then
Under the second mixing speed, add vinyl acetate, add water-soluble free radical initiator, be passed through ethene, vinyl acetate and
Ethene carries out copolyreaction under the initiation of the initiator, obtains EVA elastomer microemulsions；Wherein the first mixing speed is more than
Second mixing speed.In some specific embodiments, the first mixing speed 250-350r/min, the second mixing speed 80-
200r/min；Second stir speed (S.S.) maintains to copolymerization to terminate.For example, first mixing speed is 300r/min；The
Two mixing speeds are 150r/min.
According to a kind of preferred embodiment of method provided by the present invention, the body during ethylene pressure, i.e. copolyreaction
It is pressure, is 3.0-25.0MPa, such as 7.5-16.5MPa.Reaction temperature is 40-125 DEG C, and such as 55-75 DEG C, the reaction time is
3.0-8.0 hour, such as 4.0-6.0 hours.
According to a kind of preferred embodiment of method provided by the present invention, in the EVA elastomer emulsions, the EVA bullets
The content of vinyl acetate unit is 35.0-75.0wt% in property body, such as 60.0-70.0wt%.The EVA elastomers microemulsion
Average grain diameter be 50-170nm, such as 50-150nm.
According to a kind of preferred embodiment of the method for the invention, using one-pot batch technology, more kettle operations are avoided
Difficulty is high, the problems such as installation cost high energy consumption, has higher industrial application value.
The present invention uses one-pot batch technology, and raw material is directly pumped into polymerization reaction kettle from kettle top by high-pressure metering pump.Business
The VAC monomers of purchase usually contain polymerization inhibitor, and VAc monomers used remove polymerization inhibitor before use by distilling.Preparing EVA bullets
During property body, generally system must lead to nitrogen deoxygenation before the reaction.
The present invention is without using emulsifying agent and colloid protective agent.The colloid protective agent contains assistant for emulsifying agent.
The copolyreaction device that the present invention is used for the above method includes：Copolyreaction kettle, for for ethene and vinyl acetate
Ester emulsion copolymerized reaction provides reacting environment；And rabbling mechanism, for realizing the raw material mixing inside copolyreaction kettle.In this hair
In bright one embodiment, the copolyreaction kettle top is entered provided with solvent, initiator, pH adjusting agent and vinyl acetate liquid phase
Material mouth, and N2Ethylene feed, bottom are provided with discharging opening, connect material foam removal tank and degassing tank.Material foam removal tank top is set
There are pH adjusting agent groove and defoamer groove.The addition export for polymerizeing whole raw material and product is pumped using high-pressure metering pump.At this
In one embodiment of invention, the rabbling mechanism is located at copolyreaction kettle axis line inside position, by the driving being sequentially connected
Device, transmission device, agitating shaft and agitating paddle composition.Anchor formula oar, vane wheel oar, ribbon oar or anchor formula oar can be used in the agitating paddle
Combined with the compound oar of vane wheel oar.In one particular embodiment of the present invention, it is longitudinally provided with and stirs at copolyreaction kettle center
Axle is mixed, and blade is provided with agitating shaft, the motor on the upside of kettle drives agitating shaft to rotate by transmission mechanism.Under kettle
Provided with end socket and leave discharging opening in end socket bottom in end.Raw material and initiator are pumped into kettle from liquid phase feeding mouth, lead to nitrogen
Ethene is added after deoxygenation and carries out polymerisation, using one-pot batch technology.
Based on above-mentioned copolyreaction device, in one embodiment of the invention, EVA bullets are prepared using mixed solvent technique
The method of property body emulsifies free microemulsion continuously leads solvent, vinyl acetate, initiator, pH adjusting agent and ethene when being included in charging
Enter in copolyreaction kettle, and continuously export copolyreaction product from foregoing copolyreaction kettle in discharging, carry out product
Processing and later separation.Product demulsification extraction polymer can carry out related polymer performance characterization.
The present invention can also add other polymerized monomers while EVA polymerize and is copolymerized.As what is used in copolymerization
Polymerized monomer can enumerate the alkene such as propylene, n-butene, isobutene, 1- hexenes, 1- octenes.The addition proportioning of these polymerized monomers
Selection is not in the range of hindering the present invention to realize goal of the invention.
Using method provided by the invention, small molecule ketones solvent and alcohol are added to copolymerization system, make system polarity and
Surface tension reduces, and two class solvent polarities are complementary, promotes monomer and latex particle to disperse.Under the conditions of this, the production of EVA emulsifies free microemulsions
Thing latex particle particle diameter is smaller, and particle is evenly distributed, good emulsion stability.Mixed solvent addition proportioning is controlled, can rationally be dropped
Low latex particle particle diameter, particle shape is maintained, prevents from being adhered generation, greatly improves stability of emulsion；Do not add emulsifying agent and glue
Body protective agent, emulsion formulations can be simplified, reduce emulsion production cost, green pollution-free, further expand emulsion applications neck
Domain.The simple cost of material of inventive formulation is low, easy to operate, target good emulsion stability, in addition can stablize storage 11 months with
On.
Brief description of the drawings
The ethylene-vinyl acetate emulsion one-pot that Fig. 1 is the present invention is copolymerized batch technology schematic device.
In figure：1- polymerization reaction kettles；2- flux baths；3- initiator grooves；4-pH conditioning agent grooves；5- monomer grooves；6- high-pressure gauges
Measure pump；7- material foam removal tanks；8- defoamer grooves；9- takes off foam machine/removing ethene.
Embodiment
The present invention is further explained below by embodiment.
It is the copolyreaction device that EVA elastomer emulsifies free microemulsions are prepared using mixed solvent technique as shown in Figure 1.This work
Skill uses one-pot intermittently operated, including copolyreaction kettle 1, rabbling mechanism and product postprocessing part；The rabbling mechanism includes
Stirring motor, transmission device (being not shown in figure) and agitating shaft and the agitating paddle being fixed on agitating shaft.Worked in reactor
When, agitating paddle and part agitating shaft are below reaction liquid level.In process of production, solvent, initiator, pH adjusting agent, acetic acid
Vinyl acetate is pumped into copolyreaction kettle 1 by high-pressure metering pump 6 respectively, leads to N2Deoxygenation, ethene is anti-from ethylene feed press-in copolymerization
Answer and reach that predetermined pressure is constant in kettle 1, it is anti-that the copolymerization of ethane-acetic acid ethyenyl ester emulsifies free microemulsion is carried out under suitable reaction condition
Should.After reaction terminates, discharged from discharging opening by reaction mass.Material enters foam removal tank 7, pH adjusting agent and defoamer and adjusted from pH
Agent groove 4 and defoamer groove 8 add material foam removal tank and carry out product postprocessing, and material is finally pumped into de- foam machine 9 and removes unreacted second
Alkene gas.
The VAc contents in product EVA are characterized using nuclear-magnetism, elementary analysis, thermogravimetric and infrared four kinds of methods in embodiment；Adopt
Particle diameter and form are characterized with Hitachi's H-800 transmission electron microscopes.
Technique in the present embodiment includes：, will under the first mixing speed (the mechanical agitation rotating speed not plus before VAc monomers)
Anion surfactant and nonionic surfactant are added sequentially in aqueous phase, are added pH adjusting agent, are then stirred second
Mix and vinyl acetate (machinery mixing speed when monomer VAc is added) added under speed, add water soluble starter, be passed through ethene,
Vinyl acetate and ethene carry out copolyreaction under the initiation of the initiator, obtain EVA elastomer microemulsions.To select
Ammonium sulfate water soluble starter, butanone and methanol mixed solvent, sodium acid carbonate is exemplified by pH adjusting agent：
Embodiment 1
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 10/1；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.1wt%, emulsion particle diameter 50nm.Good emulsion stability, storage 13 months can be stablized.
Embodiment 2
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 9/2；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.2wt%, emulsion particle diameter 64nm.Good emulsion stability, storage 12 months can be stablized.
Embodiment 3
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 8/3；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.3wt%, emulsion particle diameter 76nm.Good emulsion stability, storage 12 months can be stablized.
Embodiment 4
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 7/4；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.0wt%, emulsion particle diameter 91nm.Good emulsion stability, storage 12 months can be stablized.
Embodiment 5
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 6/5；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.2wt%, emulsion particle diameter 105nm.Good emulsion stability, storage 11 months can be stablized.
Embodiment 6
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 5/6；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.1wt%, emulsion particle diameter 122nm.Good emulsion stability, storage 11 months can be stablized.
Embodiment 7
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 4/7；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.2wt%, emulsion particle diameter 134nm.Stability of emulsion is preferable, can stablize storage 11 months.
Embodiment 8
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 3/8；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.2wt%, emulsion particle diameter 141nm.Stability of emulsion is preferable, can stablize storage 11 months.
Embodiment 9
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 2/9；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.2wt%, emulsion particle diameter 145nm.Stability of emulsion is preferable, can stablize storage 11 months.
Embodiment 10
Ammonium persulfate is used as initiator, total dosage is the 0.5wt% of vinyl acetate, O/W systems, butanone and methanol body
Product is than being 1/10；Mixed solvent is 1/10 with copolymerization system aqueous phase volume ratio, and system does not add mechanical agitation rotating speed before monomer VAc
Machinery mixing speed 150r/min when 300r/min, monomer VAc are added, pH adjusting agent dosage are monomer VAc dosages
0.5wt%, polymeric reaction temperature are 75 DEG C, ethylene reaction pressure 7.5MPa, polymerization reaction time 6h.Under the conditions of this, polymerization production
Thing VAc contents are 62.0wt%, emulsion particle diameter 150nm.Stability of emulsion is preferable, can stablize storage 11 months.
Comparative example 1
Mixed solvent is not used, other reaction conditions are constant.Under the conditions of this, polymerizate VAc contents are 67.3wt%, breast
Liquid particle diameter 560nm, stability of emulsion are general.Do not obtain being expected particle size nano particle micro emulsion.
Comparative example 2
Butanone and methanol volume ratio are 10.5/0.5, and other reaction conditions are constant.Under the conditions of this, polymerizate VAc contents
It is preferable for 62.0wt%, emulsion particle diameter 52nm, stability of emulsion.Methanol is on the low side, and butanone is excessive, and no methanol carries out polarity allotment,
Latex particle size goes up not down, and is further continued for addition butanone and has little significance.(each O/W emulsion systems polarized lower limit, polarity are less than
Lower limit, no longer helpful to reducing tension force)
Comparative example 3
Butanone and methanol volume ratio are 0.5/10.5, other reaction conditions are constant.Under the conditions of this, polymerizate VAc contents
It is general for 62.1wt%, emulsion particle diameter 210nm, stability of emulsion.Methanol is excessive, and butanone is on the low side, and system polarity is higher, monomer liquid
Coalescence is dripped, latex particle size increased dramatically.
By embodiment and comparative example 1-3 data comparisons, EVA bullets are prepared using mixed solvent technique used in present invention design
Property body emulsifies free microemulsion technique, using mixed solvent and mixed solvent proportioning in certain excursion, product emulsion VAc contents
And particle size is moderate, emulsion system is stable, product period of storage length.
To sum up, the present invention is in ethylene-vinyl acetate c one-pot batch production process, using mixed solvent technique system
Standby EVA elastomer emulsifies free microemulsion products.The present invention does not add emulsifying agent and colloid protective agent, mixed from appropriate species and proportioning
Bonding solvent, latex particle particle diameter can be significantly reduced, obtain that particle shape is excellent, the good EVA emulsifies free microemulsion products of stability,
EVA emulsion applications scopes are widened significantly, meet different demands.The present invention uses one-pot batch technology, and it is difficult to avoid more kettle operations
Degree is high, the problems such as installation cost high energy consumption, has higher industrial application value.
Any numerical value mentioned in the present invention, if simply having two between any minimum and any of the highest value
The interval of unit, then include all values of one unit of each increase from minimum to peak.For example, if statement is a kind of
The amount of component, or the value of the state-variable such as temperature, pressure, time is 50-90, it is in this manual it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1st, 0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
Formula, the combination that is possible to of the numerical value between cited minimum and peak are considered to disclose.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used 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 wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of preparation method of polyvinyl-polyvinylacetate elastomer emulsifies free microemulsion, including：Mixing is added into aqueous phase
Solvent, adds pH adjusting agent, and the ethene being passed through and the vinyl acetate added enter in the presence of water-soluble free radical initiator
Row copolyreaction, obtain polyvinyl-polyvinylacetate elastomer microemulsion；Wherein, do not added in reaction system emulsifying agent and
Colloid protective agent.
2. according to the method for claim 1, it is characterised in that the mixed solvent includes ketone compounds and alcohols chemical combination
Thing, preferably include C4-C8Ketone compounds and C1-C6Alcohol compound, the volume ratio of preferably described mixed solvent and aqueous phase
For 1/15-1/5.
3. method according to claim 1 or 2, it is characterised in that the ketone compounds are selected from butanone, the bronze medals of 2- penta, 2-
At least one of octanone, 3- octanones and its isomer；And/or the alcohol compound is selected from methanol, ethanol, positive third
At least one of alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, ethylene glycol, propane diols and glycerine；It is preferred that the ketone
Compound and the volume ratio of alcohol compound are 10/1-1/10.
4. according to the method described in any one in claim 1-3, it is characterised in that the water soluble starter is from inorganic
One or more in salt, azo-compound, inorganic peroxide and inorganic oxide reduction class initiator, preferably are selected from persulfuric acid
Ammonium, sodium peroxydisulfate, potassium peroxydisulfate, the isobutyl imidazoline hydrochloride of azo two, azo dicyano valeric acid, azo diisobutyl amidine hydrochloric acid
One or more in salt, hydrogen peroxide and sodium peroxide, the dosage of preferably described water-soluble free radical initiator is vinyl acetate
The 0.5-5.0wt% of ester dosage, more preferably 0.5-2.0wt%.
5. according to the method described in any one in claim 1-4, it is characterised in that the pH adjusting agent is selected from sodium acid carbonate
And ammoniacal liquor, preferably its dosage is the 0.05-5.0wt%, more preferably 0.5-2.0wt% of vinyl acetate dosage.
6. according to the method described in any one in claim 1-5, it is characterised in that methods described includes：In the first stirring
Under speed, the ketone compounds of in the mixed solvent are added into aqueous phase, add the alcohol compound of in the mixed solvent, add pH
Conditioning agent, then under the second mixing speed, vinyl acetate is added, water soluble starter is added, is passed through ethene, vinyl acetate
Ester and ethene carry out copolyreaction under the initiation of the initiator, obtain EVA elastomer microemulsions；Wherein the first mixing speed
More than the second mixing speed；It is preferred that the first mixing speed 250-350r/min, the second mixing speed 80-200r/min.
7. according to the method described in any one in claim 1-6, it is characterised in that the ethylene pressure is 3.0-
25.0MPa, preferably 7.5-16.5MPa；Reaction temperature is 40-125 DEG C, preferably 55-75 DEG C；Reaction time is 3.0-8.0
Hour, preferably 4.0-6.0 hours.
8. according to the method described in any one in claim 1-7, it is characterised in that methods described is one-pot batch technology.
9. according to the method described in any one in claim 1-8, it is characterised in that the polyvinyl-polyvinylacetate
The content of vinyl acetate unit is 35.0-75.0wt%, preferably 60-70wt% in elastomer；And/or the polyethylene-
The average grain diameter of polyvinyl acetate ester elastomer microemulsion is 50-170nm, preferably 50-150nm.
10. according to the method described in any one in claim 1-9, it is characterised in that methods described includes：Add into system
Enter other comonomers to be copolymerized, it is pungent that other comonomers preferably are selected from propylene, n-butene, isobutene, 1- hexenes and 1-
Alkene.
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