CN107793511A - A kind of method for preparing EVA elastomer microemulsions - Google Patents
A kind of method for preparing EVA elastomer microemulsions Download PDFInfo
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- CN107793511A CN107793511A CN201610806541.2A CN201610806541A CN107793511A CN 107793511 A CN107793511 A CN 107793511A CN 201610806541 A CN201610806541 A CN 201610806541A CN 107793511 A CN107793511 A CN 107793511A
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- dosage
- activating agent
- surface activating
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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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
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
Abstract
This application discloses a kind of method for preparing EVA elastomer microemulsions, including：First surface activating agent is added in aqueous phase and obtains micella; add vinyl acetate; then second surface activating agent is added; colloid protective agent and water-soluble free radical initiator are added afterwards; and it is passed through ethene; vinyl acetate carries out copolyreaction with ethene under the initiation of water-soluble free radical initiator; obtain EVA elastomer microemulsions; wherein; the critical micelle concentration of first surface activating agent is less than the critical micelle concentration of second surface activating agent, and the mol ratio of second surface activating agent and first surface activating agent is less than 1/1.According to method provided by the invention, emulsion particle diameter, and good emulsion stability can be controlled.
Description
Technical field
The present invention relates to field of polymer technology, and in particular to a kind of to prepare EVA elastomer microemulsions using compound emulsifying agent
Method
Background technology
The EVA elastomer emulsions of emulsion polymerization production, vinyl acetate (VAc) content is moderate, and product has excellent
Pliability, the transparency, 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 CN1302027C triggers polymerization to prepare high solid EVA latex at 40-60 DEG C, and pressure is disregarded in reacting ethylene weight calculation
Power, initiator amount 0.01-3.0wt%, reaction time 10.0h.VAc contents 7.5-99.0wt% in polymer.Due to being formed
Emulsion and suspension polymer, so obtained dispersion has a bimodal size distribution, such as maximum at 0.2-0.5 μm and
At 3.0-6.0 μm of peak.Patent CN101200518A uses hydrogen peroxide-ferrous sulfate system, 70-75,75-80 DEG C of two benches ranks
Terraced temperature control triggers polymerization, ethylene reaction pressure 9.0-10.0MPa, 1.85 μm of particle diameter.Invention prepares gained EVA glue above
Breast, particle skewness, particle diameter are excessive, and latex particle is easily reunited, and stability is poor, and application is significantly limited.
Patent CN102695725A uses multi-floating bodies technique, and 50-90 DEG C, 1.0-9.0MPa prepares EVA latex, emulsion particle
Sub- 1 μm of diameter.Invention prepares gained EVA emulsions above, and latex particle is bigger than normal, and particle is easily reunited, and product stability is general, application
Scope is narrower, complex process.
Micro-emulsion polymerization prepares nano rubber latex, and emulsion average grain diameter is small, penetrating power is strong, wetability is excellent and stability
Height, have a extensive future.For preparing EVA elastomer nano particle micro emulsions, because its formula is complicated, technique controlling difficulty
Height, it is rarely reported at present.
The content of the invention
For deficiency of the prior art, the present invention prepares EVA elastomer microemulsions using compound emulsifying agent technique.It is existing
Traditional EVA emulsion polymerization techniques, latex particle is excessive, be easily adhered, particle shape and stability of emulsion are poor, and product is not easy to store,
Application is limited.From compound emulsifying agent technique, variety classes emulsifying agent compounding, latex particle particle diameter can be significantly reduced,
Particle shape is maintained, greatly improves stability of emulsion.This invention preparation gained EVA elastomer microemulsion product stability is good, VAc
Content is moderate, excellent performance, can meet different demands.
According to an aspect of the present invention, there is provided a kind of method for preparing EVA elastomer microemulsions, including：By the first table
Face activating agent, which is added in aqueous phase, obtains micella, adds vinyl acetate, then adds second surface activating agent, add afterwards
Colloid protective agent and water-soluble free radical initiator, and ethene is passed through, vinyl acetate triggers with ethene in water-soluble free radical
Copolyreaction is carried out under the initiation of agent, obtains EVA elastomer microemulsions, wherein, the critical micelle concentration of first surface activating agent
Mol ratio less than the critical micelle concentration of second surface activating agent, and second surface activating agent and first surface activating agent is less than
1/1。
According to method provided by the invention, critical micelle concentration (CMC) is lower, emulsifying agent needed for system generation solubilization micelle
Concentration is lower, the easier generation of micella, therefore first surface activating agent is added in the pre-emulsification stage and (added before adding VAc monomers),
System generation micella quantity is more, and product particles particle diameter reduces；Second surface activating agent adds after VAc monomers are added, and belongs to
Added in the polymerization incipient stage, high CMC emulsifying agents compound with low CMC emulsifying agents, to improve latex particle boundary strength.
According to a kind of preferred embodiment of method provided by the present invention, the second surface activating agent and first surface
The mol ratio of activating agent is not more than 1/3, such as 1/3-1/7.Within the above range, control emulsion particle diameter can be more preferably dripped, improves emulsion
Stability.
In some specific embodiments, the second surface activating agent includes nonionic surfactant, and the first table
Face activating agent includes anion surfactant.The CMC of anion surfactant is less than the CMC of nonionic surfactant.
Using nonionic surfactant and the complexed surfactant of anion surfactant, and the nonionic surfactant
Be less than 1/1 with the mol ratio of anion surfactant, different types of surfactant produces cooperative effect, certain anti-
Under the conditions of answering, latex particle particle diameter can be rationally reduced, micella boundary strength is improved, stable micella, maintains particle shape, prevent from sticking
Running fire is given birth to, and greatly improves stability of emulsion.The simple cost of material of inventive formulation is low, easy to operate, target good emulsion stability.
According to a kind of preferred embodiment of method provided by the present invention, the nonionic surfactant and anion
The mol ratio of surfactant is not more than 1/3, such as 1/3-1/7.Within the above range, control emulsion particle diameter can be more preferably dripped, is improved
Stability of emulsion.CMC (critical micelle concentration) is lower, and emulsifier concentration needed for system generation solubilization micelle is lower, and micella is easier
Generation, therefore anion surfactant adds in the pre-emulsification stage, system generation micella quantity is more, and product particles particle diameter reduces；
Nonionic surfactant adds in the polymerization incipient stage, and high CMC emulsifying agents compound with low CMC emulsifying agents, to improve emulsion particle
Sub-interface intensity.
According to a kind of preferred embodiment of method provided by the present invention, the nonionic surfactant gathers selected from fat alcohol
Oxygen vinethene, APES, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, alkylolamides polyoxy second
At least one of alkene ether and Block polyoxyethylene-polyethenoxy ether, such as may be selected from fat alcohol APEO OP-10, OP-4,
At least one of OP-7, OP-20, TX-10 and TX20.The anion surfactant is selected from alkyl sulfate, alkyl sulphur
Hydrochlorate, alkyl carboxylate, alkylsurfuric acid fat salt and alkylsurfuric acid fat salt, such as may be selected from lauryl sodium sulfate SDS and dodecane
At least one of base benzene sulfonic acid sodium salt SDBS.
According to a kind of preferred embodiment of method provided by the present invention, the dosage of the complexed surfactant is acetic acid
The 0.05-12.5wt% of vinyl acetate dosage, such as 1-10.0wt%.
According to a kind of preferred embodiment of method provided by the present invention, the colloid protective agent is selected from polyvinyl alcohol, gathered
Ether, etherified cellulose and water-soluble cellulose derivative.In specific example, the dosage of the colloid protective agent is acetic acid second
The 2.0-8.0wt% of alkene ester dosage, such as 2.5-5.0wt%.
According to a kind of preferred embodiment of method provided by the present invention, methods described, which is additionally included in, adds the initiator
PH adjusting agent is added afterwards.In some specific embodiments, the pH adjusting agent is those pH adjusting agents commonly used in the art,
Such as selected from sodium acid carbonate, ammoniacal liquor.The dosage of the pH adjusting agent is the 0.05-5.0wt%, such as 0.5- of vinyl acetate dosage
2.0wt%.By adding a certain amount of pH adjusting agent so that the pH of reaction system is controlled in 1.5-9.0.
According to a kind of preferred embodiment of method provided by the present invention, the water-soluble free radical initiator is from inorganic
One or more in salt, azo-compound, inorganic peroxide and inorganic oxide reduction class initiator, are such as 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 the water-soluble free radical initiator is used for vinyl acetate
The 0.01-5.0wt% of amount, such as 0.1-2.0wt%.
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.Reaction temperature is 40-125 DEG C, and the reaction time is 3.0-8.0 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 is 35.0-75.0wt% in property body, preferably 45.0-70.0wt%；It is preferred that the EVA elastomer emulsions
For EVA elastomer microemulsions, microemulsion average grain diameter is 30-130nm, preferably 40-110nm.
According to a kind of preferred embodiment of method provided by the present invention, using one-pot batch technology, more kettle behaviour are avoided
Make difficulty height, the problems such as installation cost high energy consumption, there is higher industrial application value.
The present invention under certain reaction condition, is compounded on the basis of existing EVA emulsion polymerizations production technology using emulsifying agent
Technique, latex particle particle diameter is reduced, improve stability of emulsion.Traditional EVA emulsion polymerization techniques, emulsion particle is bigger than normal to be easily adhered,
The difficult control of reaction, causes copolymerization stage to be easily demulsified.Variety classes emulsifying agent, its critical micelle concentration (CMC) are different：
CMC is big, and the more difficult generation of micella, micella can be stabilized；CMC is smaller, the easier generation of micella, but unstable, the life of same amount emulsifying agent
More into micella quantity, latex particle particle diameter reduces；If latex particle interface relatively loosens unstable, initiator and monomer between particle
It is excessive etc. mass exchange speed, particle size distribution can be caused uneven, particle and it is poly- be adhered, have a strong impact on that emulsion polymerization enters
Journey and product quality.The present invention selects compound emulsifying agent, and variety classes/CMC surfactant produces collaboration as emulsifying agent
Effect, under certain reaction condition, latex particle particle diameter can be rationally reduced, improve micella boundary strength, stable micella, maintain grain
Sub- form, prevent from being adhered generation, greatly improve stability of emulsion.The simple cost of material of inventive formulation is low, easy to operate, target
Good emulsion stability；The present invention uses one-pot batch technology, avoids more kettle operation difficulties height, and installation cost energy consumption height etc. is asked
Topic, has higher industrial application value.
According to the present invention, using one-pot batch technology, raw material is directly pumped into polymerisation from kettle top by high-pressure metering pump
Kettle.Commercially available VAC monomers usually contain polymerization inhibitor, and VAc monomers used remove polymerization inhibitor before use by distilling.Preparing
During EVA elastomers, generally system must lead to nitrogen deoxygenation before the reaction.The present invention is used for the copolyreaction device bag of the above method
Include：Copolyreaction kettle, for providing reacting environment for ethene and vinyl acetate emulsion copolyreaction；And rabbling mechanism, it is used for
Realize the raw material mixing inside copolyreaction kettle.In one embodiment of the invention, the copolyreaction kettle top is provided with table
Face activating agent, colloid protective agent, initiator, pH adjusting agent and vinyl acetate liquid phase feeding mouth, and N2Ethylene feed, under
Portion is provided with discharging opening, connects material foam removal tank and degassing tank.Material foam removal tank top is provided with pH adjusting agent groove and defoamer groove.It is poly-
The addition export for closing whole raw material and product is pumped using high-pressure metering pump.In one embodiment of the invention, it is described to stir
Mix mechanism and be located at copolyreaction kettle axis line inside position, by drive device, transmission device, agitating shaft and the stirring being sequentially connected
Oar forms.Anchor formula oar, vane wheel oar, ribbon oar or anchor formula oar can be used to be combined with the compound oar of vane wheel oar for the agitating paddle.At this
In one specific embodiment of invention, agitating shaft is longitudinally provided with copolyreaction kettle center, and blade is provided with agitating shaft,
Motor on the upside of kettle drives agitating shaft to rotate by transmission mechanism.Kettle lower end is provided with end socket and left in end socket bottom
Discharging opening.Raw material and initiator are pumped into kettle from liquid phase feeding mouth, ethene progress polymerisation is added after leading to nitrogen deoxygenation,
Using one-pot batch technology.
Based on above-mentioned copolyreaction device, in one embodiment of the invention, EVA elasticity is prepared using compound emulsifying agent
Body microemulsion technique is included emulsifying agent/colloid protective agent, vinyl acetate, initiator, pH adjusting agent and ethene in charging
It is continuously introduced into copolyreaction kettle, and continuously exports copolyreaction product from foregoing copolyreaction kettle in discharging, carries out
The processing of product 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.
According to the present invention, the particle diameter of EAV elastomer microemulsions can be controlled using method provided by the invention, improves emulsion
Stability.The simple cost of material of inventive formulation is low, easy to operate, target good emulsion stability, emulsion can store 7 months with
On, such as more than 10 months.The present invention uses one-pot batch technology, avoids more kettle operation difficulties height, installation cost energy consumption height etc.
Problem, there is higher industrial application value.
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- surfactants/colloid protective agent groove；3- initiator grooves；4-pH conditioning agent grooves；
5- monomer grooves；6- high-pressure metering pumps；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 microemulsions are prepared using compound emulsifying agent as shown in Figure 1.This technique uses
One-pot intermittently operated, including copolyreaction kettle 1, rabbling mechanism and product postprocessing part；The rabbling mechanism includes stirring electricity
Machine, transmission device (being not shown in figure) and agitating shaft and the agitating paddle being fixed on agitating shaft.When reactor works, stirring
Oar and part agitating shaft are below reaction liquid level.In process of production, anion surfactant, non-ionic surface active
Agent, colloid protective agent, initiator, pH adjusting agent, vinyl acetate are pumped into copolyreaction kettle 1 by high-pressure metering pump 6 respectively, lead to N2
Deoxygenation, ethene is pressed into copolyreaction kettle 1 from ethylene feed and reaches that predetermined pressure is constant, is entered under suitable reaction condition
Row ethane-acetic acid ethyenyl ester microemulsion reacts.After reaction terminates, discharged from discharging opening by reaction mass.Material, which enters, to be removed
Foam tank 7, pH adjusting agent and defoamer add material foam removal tank from pH adjusting agent groove 4 and defoamer groove 8 and carry out product postprocessing, thing
Material is finally pumped into de- foam machine 9 and removes unreacting ethylene 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：Anion surfactant is added in aqueous phase (deionized water) and obtains glue
Beam, vinyl acetate is then added, afterwards nonionic surfactant again, then add colloid protective agent, initiator and pH and adjust
Agent is saved, and is passed through ethene, when being increased to reaction temperature, started copolymer reaction.With select ammonium persulfate water soluble starter, it is non-from
Sub- emulsifying agent op-10, anion emulsifier SDS compound emulsifying agent, sodium acid carbonate are pH adjusting agent, polyvinyl alcohol (PVA, its board
Number be 17-88) be colloid protective agent exemplified by：
Embodiment 1
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.7wt%, microemulsion average grain diameter
127nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Embodiment 2
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3.5mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.7wt%, microemulsion average grain diameter
112nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Embodiment 3
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/4mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.6wt%, microemulsion average grain diameter
98nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Embodiment 4
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/4.5mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.4wt%, microemulsion average grain diameter
81nm.Stability of emulsion is preferable, and emulsion can stablize storage 8 months.
Embodiment 5
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/5mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.5wt%, microemulsion average grain diameter
70nm.Stability of emulsion is preferable, and emulsion can stablize storage 9 months.
Embodiment 6
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/5.5mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.5wt%, microemulsion average grain diameter
58nm.Stability of emulsion is preferable, and emulsion can stablize storage 9 months.
Embodiment 7
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/6mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.6wt%, microemulsion average grain diameter
49nm.Stability of emulsion is preferable, and emulsion can stablize storage 9.5 months.
Embodiment 8
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/6.5mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.6wt%, microemulsion average grain diameter
40nm.Stability of emulsion is preferable, and emulsion can stablize storage 10 months.
Embodiment 9
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/7mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 60.7wt%, microemulsion average grain diameter
32nm.Stability of emulsion is preferable, and emulsion can stablize storage 10 months.
Embodiment 10
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 3.0MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 75.9wt%, microemulsion average grain diameter
133nm.Stability of emulsion is general, and emulsion can stablize storage 6 months.
Embodiment 11
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 12.0MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 56.5wt%, the average grain of microemulsion
Footpath 125nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Embodiment 12
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 16.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 55.1wt%, the average grain of microemulsion
Footpath 127nm.Stability of emulsion is preferable, and emulsion can stablize storage 8 months.
Embodiment 13
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 21.0MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 51.9wt%, the average grain of microemulsion
Footpath 127nm.Stability of emulsion is preferable, and emulsion can stablize storage 8 months.
Embodiment 14
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 25.0MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 42.5wt%, the average grain of microemulsion
Footpath 120nm.Stability of emulsion is preferable, and emulsion can stablize storage 8 months.
Embodiment 15
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 65 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 65.1wt%, microemulsion average grain diameter
121nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Embodiment 16
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 85 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 5h.Under the conditions of this, polymerizate VAc contents are 58.8wt%, microemulsion average grain diameter
124nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Embodiment 17
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 4h.Under the conditions of this, polymerizate VAc contents are 61.1wt%, microemulsion average grain diameter
129nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Embodiment 18
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant use
It is monomer to measure as the 10.0wt% of monomer VAc dosages, op-10/SDS dosages=1/3mol/mol, colloid protective agent PVA dosages
The 2.5wt% of VAc dosages, pH adjusting agent dosage are the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, and ethene is anti-
Answer pressure 7.5MPa, polymerization reaction time 7h.Under the conditions of this, polymerizate VAc contents are 63.2wt%, microemulsion average grain diameter
135nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Comparative example 1
Compound emulsifying agent technique is not used, and single nonionic surfactant op-10 is emulsifying agent, and other reaction conditions are same
Embodiment 1.Under the conditions of this, polymerizate VAc contents are 69.1wt%, and latex particle particle diameter is 128nm.VAc contents are higher, grain
Sub- small part is adhered, and emulsion, which is put to 4 months i.e., demulsification precipitation occurs.
Comparative example 2
Compound emulsifying agent technique is not used, and single anion surfactant SDS is emulsifying agent, and other reaction conditions are the same as real
Apply example 1.Under the conditions of this, polymerizate VAc contents are 68.9wt%, and latex particle particle diameter is 225nm.VAc contents are higher, emulsion
Particle diameter is bigger than normal, and particle fraction is adhered, and emulsion, which is put to 3 months i.e., demulsification precipitation occurs.
Comparative example 3
Using compound emulsifying agent technique, op-10/SDS dosages=1/2.5mol/mol, other reaction conditions are the same as embodiment 1.
Under the conditions of this, polymerizate VAc contents are 65.1wt%, and latex particle particle diameter is 132nm.VAc contents are higher, particle small part
It is adhered, emulsion, which is put to 3.5 months i.e., demulsification precipitation occurs, and compound emulsifying agent proportioning dosage is improper, then reduces SDS dosage meanings
Less.
Comparative example 4
Using compound emulsifying agent technique, op-10/SDS dosages=1/7.5mol/mol, other reaction conditions are the same as embodiment 1.
Under the conditions of this, polymerizate VAc contents are 70.1wt%, and latex particle particle diameter is 270nm.VAc contents are higher, and emulsion particle diameter is inclined
Greatly, particle fraction is adhered, and emulsion, which is put to 3 months i.e., demulsification precipitation occurs, and compound emulsifying agent proportioning dosage is improper.
Comparative example 5
Using compound emulsifying agent technique, op-10/SDS dosages=1/3mol/mol, the op-10 pre-emulsification stages add；SDS
Added after vinyl acetate adds, belong to the addition of polymerization incipient stage；Other reaction conditions are the same as embodiment 1.Under the conditions of this,
Polymerizate VAc contents are 62.8wt%, and latex particle particle diameter is 482nm.Emulsion particle diameter is bigger than normal, and particle is adhered seriously, emulsion
Put to 2.5 months i.e. occur demulsification precipitation, high CMC nonionic emulsifiers the pre-emulsification stage add and it is improper.
By embodiment and comparative example 1,2 data comparisons, EVA elasticity is prepared using compound emulsifying agent used in present invention design
Body microemulsion technique, product emulsion VAc contents and particle size are moderate, stable system；Pass through embodiment and comparative example 3,4 data
Contrast, EVA elastomer microemulsion techniques are prepared using compound emulsifying agent used in present invention design, variety classes surfactant exists
Compounding uses as emulsifying agent in certain proportioning amount ranges, and product emulsion VAc contents and particle size are moderate, stable system；
By embodiment and the data comparison of comparative example 5, EVA elastomer microemulsion works are prepared using compound emulsifying agent used in present invention design
Skill, low CMC nonionic surfactants add in the pre-emulsification stage, and high CMC anion surfactants are in the polymerization incipient stage
Add, product emulsion VAc contents and particle size are moderate, and emulsion system is stable, product period of storage length.
In summary, the present invention is in ethylene-vinyl acetate c one-pot batch production process, using compound emulsifying agent
Technique prepares EVA elastomer microemulsion products.Compound emulsifying agent technique of the present invention, low CMC nonionic surfactants are in pre- breast
The change stage is added, and high CMC anion surfactants add in the polymerization incipient stage, and variety classes emulsifying agent is used in certain proportioning
It is used cooperatively in the range of amount, latex particle particle diameter can be significantly reduced, obtains that particle shape is excellent, the good EVA micro emulsions of stability
Liquid product, EVA emulsion applications scopes are widened significantly, meet different demands.The present invention uses one-pot batch technology, avoids more kettles
Operation difficulty 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 (12)
1. a kind of method for preparing EVA elastomer microemulsions, including：First surface activating agent is added in aqueous phase and obtains glue
Beam, vinyl acetate is added, then adds second surface activating agent, added colloid protective agent afterwards and water-soluble free radical draws
Agent is sent out, and is passed through ethene, vinyl acetate carries out copolyreaction with ethene under the initiation of water-soluble free radical initiator, obtains
EVA elastomer microemulsions, wherein, the critical micelle concentration of first surface activating agent is less than the critical micell of second surface activating agent
Concentration, and the mol ratio of second surface activating agent and first surface activating agent is less than 1/1.
2. according to the method for claim 1, it is characterised in that the second surface activating agent and first surface activating agent
Mol ratio is not more than 1/3, preferably 1/3-1/7.
3. method according to claim 1 or 2, it is characterised in that the first surface activating agent includes anion
Surfactant, the anion surfactant preferably are selected from alkyl sulfate, alkylsulfonate, alkyl carboxylate, alkyl sulfide
Sour fat salt and alkylsurfuric acid fat salt, is more preferably selected from lauryl sodium sulfate SDS and neopelex SDBS extremely
Few one kind.
4. according to the method described in any one in claim 1-3, it is characterised in that second surface activating agent includes nonionic
Surfactant, the nonionic surfactant preferably are selected from AEO, APES, aliphatic acid
Polyoxyethylene ester, aliphatic amine polyoxyethylene ether, alkylolamides APEO, Block polyoxyethylene-polyethenoxy ether, it is more excellent
Choosing is selected from least one of APES OP-10, OP-4, OP-7, OP-20, TX-10 and TX20.
5. according to the method described in any one in claim 1-4, it is characterised in that the first surface activating agent and second
Total dosage of surfactant is the 0.05-12.5wt%, preferably 1-10wt% of vinyl acetate dosage.
6. according to the method described in any one in claim 1-5, it is characterised in that the colloid protective agent is selected from polyethylene
Alcohol, polyethers, etherified cellulose and water-soluble cellulose derivative, preferably its dosage are the 2.0- of vinyl acetate dosage
8.0wt%, more preferably its dosage are the 2.5-5.0wt% of vinyl acetate dosage.
7. according to the method described in any one in claim 1-6, it is characterised in that methods described is additionally included in described in addition
PH adjusting agent is added after initiator, preferably described pH adjusting agent is selected from sodium acid carbonate and ammoniacal liquor, and more preferably its dosage is acetic acid
The 0.05-5.0wt% of vinyl acetate dosage, its further preferred dosage are the 0.5-2.0wt% of vinyl acetate dosage.
8. according to the method described in any one in claim 1-7, it is characterised in that the water-soluble free radical initiator choosing
The one or more in class initiator are reduced with inorganic salts, azo-compound, inorganic peroxide and inorganic oxide, preferably were selected from
Ammonium sulfate, sodium peroxydisulfate, potassium peroxydisulfate, the isobutyl imidazoline hydrochloride of azo two, azo dicyano valeric acid, azo diisobutyl amidine
One or more in hydrochloride, hydrogen peroxide and sodium peroxide；Preferably, the dosage of the water-soluble free radical initiator is second
The 0.01-5.0wt% of vinyl acetate dosage, preferably 0.1-2.0wt%.
9. according to the method described in any one in claim 1-8, it is characterised in that the ethylene pressure is 3.0-
25.0MPa, preferably 7.5-16.5MPa；Methods described is one-pot batch technology.
10. according to the method described in any one in claim 1-9, it is characterised in that reaction temperature is 40-125 DEG C, preferably
65-85℃；Reaction time is 3.0-8.0 hours, preferably 4.0-7.0 hours.
11. according to the method described in any one in claim 1-10, it is characterised in that in the EVA elastomer emulsions, institute
The content for stating vinyl acetate unit in EVA elastomers is 35.0-75.0wt%, preferably 45.0-70.0wt%；It is and/or described
The average grain diameter of EVA elastomer microemulsions is 30-130nm, preferably 40-110nm.
12. according to the method described in any one in claim 1-11, it is characterised in that methods described includes：Into system
Add other comonomers to be copolymerized, other comonomers preferably are selected from propylene, n-butene, isobutene, 1- hexenes and 1-
Octene.
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| CN101041704A (en) * | 2007-04-20 | 2007-09-26 | 上海三瑞化学有限公司 | Novel ethane-acetic acid ethyenyl ester copolymer emulsion |
| CN101484474A (en) * | 2006-07-03 | 2009-07-15 | 塞拉尼斯乳剂股份有限公司 | Method for producing aqueous vinyl ester dispersions |
| CN101503485A (en) * | 2008-02-09 | 2009-08-12 | 塞拉尼斯乳剂股份有限公司 | Method for manufacturing polymer dispersions, dispersions created thereby and their application |
| CN102695725A (en) * | 2010-07-14 | 2012-09-26 | 瓦克化学股份公司 | Process for continuous emulsion polymerization |
| CN104718227A (en) * | 2012-09-26 | 2015-06-17 | 瓦克化学公司 | Process for the preparation of an aqueous emulsifier-stabilized vinyl acetate-ethylene copolymer dispersion with fine particle size |
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- 2016-09-07 CN CN201610806541.2A patent/CN107793511B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101484474A (en) * | 2006-07-03 | 2009-07-15 | 塞拉尼斯乳剂股份有限公司 | Method for producing aqueous vinyl ester dispersions |
| CN101041704A (en) * | 2007-04-20 | 2007-09-26 | 上海三瑞化学有限公司 | Novel ethane-acetic acid ethyenyl ester copolymer emulsion |
| CN101503485A (en) * | 2008-02-09 | 2009-08-12 | 塞拉尼斯乳剂股份有限公司 | Method for manufacturing polymer dispersions, dispersions created thereby and their application |
| CN102695725A (en) * | 2010-07-14 | 2012-09-26 | 瓦克化学股份公司 | Process for continuous emulsion polymerization |
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