CN107793516A - The method for preparing EVA elastomer microemulsions - Google Patents
The method for preparing EVA elastomer microemulsions Download PDFInfo
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- CN107793516A CN107793516A CN201610806106.XA CN201610806106A CN107793516A CN 107793516 A CN107793516 A CN 107793516A CN 201610806106 A CN201610806106 A CN 201610806106A CN 107793516 A CN107793516 A CN 107793516A
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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
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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Abstract
The present invention relates to a kind of preparation method of EVA elastomers microemulsion, including：Using deionized water as aqueous phase, response type sulfonate anionic surfactant is emulsifying agent, adds pH adjusting agent and colloid protective agent, vinyl acetate and ethene carry out copolyreaction under the initiation of water-soluble free radical initiator, obtain EVA elastomer microemulsions.The method according to the invention, microemulsion particle diameter can be controlled, improve stability.
Description
Technical field
The present invention relates to a kind of method for preparing EVA elastomer microemulsions using response type sulfonate anionic emulsifying agent.
Background technology
EVA (Ethylene/vinyl acetate) elastomer emulsions of emulsion polymerization production, vinyl acetate (VAc) content are fitted
In, product have excellent pliability, the transparency, cold flexibility, weatherability, resistance to corrosive chemicals and with filler and color
The compatibility of masterbatch；EVA product emulsions intensity height, asepsis environment-protecting, adhesive property are excellent, available for weave, light industry, coating, modeling
Expect toughness reinforcing, formulation for building, polymer blending coating, modified rubber etc. field, be widely used, its domestic and international demand is continuous
Increase, quickly grows in recent years.
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
Existing traditional EVA emulsion polymerization techniques, emulsifiers formula are complicated, latex particle is excessive, be easily adhered, particle shape and
Stability of emulsion is poor, and product is not easy to store, and application is limited.The present invention is prepared using response type sulfonate anionic emulsifying agent
EVA elastomer microemulsions, latex particle particle diameter can be significantly reduced, maintain particle shape, greatly improve stability of emulsion.This hair
EVA elastomer microemulsion product stability obtained by bright preparation is good, VAc contents are moderate, excellent performance, can meet different demands.
According to an aspect of the invention, there is provided a kind of preparation method of EVA elastomers microemulsion, including：With go from
Sub- water is aqueous phase, and response type sulfonate anionic surfactant is emulsifying agent, adds pH adjusting agent and colloid protective agent, acetic acid
Vinyl acetate and ethene carry out copolyreaction under the initiation of water-soluble free radical initiator, obtain EVA elastomer microemulsions.
According to method provided by the invention, response type sulfonate emulsifier has double bond structure, and there is higher reaction to live
Property, response type functional group can participate in emulsion polymerization, in solubilising cladding monomer/polymer and protection latex particle simultaneously,
It can react and be bonded in EVA copolymer particle surface, both reduce the emulsifier content that dissociates in copolymerization system continuous phase, turn avoid
Emulsifying agent desorbs from copolymer latices particle surface, further enhancing protective effect of the emulsifying agent to particle, prevents micelle
Between be adhered coalescence, particle diameter is further reduced.The present invention selects response type sulfonate anionic emulsifying agent, a kind of or more
Kind is used cooperatively, and under certain reaction condition, can rationally be reduced latex particle particle diameter, stable micella, be maintained particle shape, prevent
Generation is adhered, greatly improves stability of emulsion.The simple cost of material of inventive formulation is low, easy to operate, target stability of emulsion
It is good.
According to described method specific embodiment, the response type sulfonate anionic surfactant is selected from alkene
Propoxyl group hydroxypropyl azochlorosulfonate acid sodium, vinyl alkyl sodium sulfonate, mono maleate sulfonate, propenyl succinic acid diester sulfonic acid
Sodium and isobutenyl succinic acid diester sodium sulfonate.The dosage of the response type sulfonate anionic surfactant is vinyl acetate
The 0.5-20.0wt% of ester dosage.
According to described method 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.According to described method specific embodiment, the water-soluble free radical
The dosage of initiator is the 0.01-5.0wt%, such as 0.1-2.0wt% of vinyl acetate dosage.
According to described method specific embodiment, the pH adjusting agent is reagent commonly used in the art, is such as selected from
At least one of sodium acid carbonate and ammoniacal liquor etc..The dosage of the pH adjusting agent is the 0.05- of vinyl acetate dosage
5.0wt%, such as 0.5-2.0wt%.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 described method specific embodiment, the colloid protective agent be selected from polyvinyl alcohol, polyethers, etherificate
Cellulose and water-soluble cellulose derivative.The dosage of the colloid protective agent is the 2.0-8.0wt% of vinyl acetate dosage,
Such as 2.5-5.0wt%.
According to described method specific embodiment, the pressure of the ethene, that is, the pressure of system when reacting, it is
3.0-25.0MPa such as 7.5-16.5MPa.The reaction temperature of the polymerization is 40-125 DEG C, and such as 65-82 DEG C, the reaction time is
3.0-8.0h such as 4.0-7.0h.
According to described method specific embodiment, methods described is one-pot batch technology, avoids more kettle operations
Difficulty is high, the problems such as installation cost high energy consumption, has higher industrial application value.
According to described method specific embodiment, in EVA elastomers, the content of VAC units is 35-75wt%,
It is preferred that 40-70wt%；The particle diameter of the microemulsion is 15-130nm, preferably 30-100nm.Emulsion can stablize storage 7 months with
On, preferably more than 10 months.
The present invention is on the basis of existing EVA emulsion polymerizations production technology, using response type sulfonate anionic emulsifying agent, drop
Low latex particle particle diameter, improve stability of emulsion.Response type sulfonate emulsifier has double bond structure, and there is higher reaction to live
Property, response type functional group can participate in emulsion polymerization, in solubilising cladding monomer/polymer and protection latex particle simultaneously,
It can react and be bonded in EVA copolymer particle surface, both reduce the emulsifier content that dissociates in copolymerization system continuous phase, turn avoid
Emulsifying agent desorbs from copolymer latices particle surface, further enhancing protective effect of the emulsifying agent to particle, prevents micelle
Between be adhered coalescence, particle diameter is further reduced.The present invention selects response type sulfonate anionic emulsifying agent, a kind of or more
Kind is used cooperatively, and under certain reaction condition, can rationally be reduced latex particle particle diameter, stable micella, be maintained particle shape, prevent
Generation is adhered, greatly improves stability of emulsion.The simple cost of material of inventive formulation is low, easy to operate, target stability of emulsion
It is good；The present invention use one-pot batch technology, and it is high to avoid more kettle operation difficulties, the problems such as installation cost high energy consumption, with 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 copolyreaction device that the present invention is used for the above method includes：Copolymerization
Reactor, for providing reacting environment for ethene and vinyl acetate emulsion copolyreaction；And rabbling mechanism, it is copolymerized for realizing
Raw material mixing inside reactor.In one embodiment of the invention, the copolyreaction kettle top be provided with surfactant,
Colloid protective agent, initiator, pH adjusting agent and vinyl acetate liquid phase feeding mouth, and N2Ethylene feed, bottom are provided with out
Material mouth, connect material foam removal tank and degassing tank.Material foam removal tank top is provided with pH adjusting agent groove and defoamer groove.Polymerization is whole former
The addition export of material and product is pumped using high-pressure metering pump.In one embodiment of the invention, the rabbling mechanism position
In copolyreaction kettle axis line inside position, it is made up of the drive device, transmission device, agitating shaft and the agitating paddle that are sequentially connected.
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.The one of the present invention
In individual specific embodiment, agitating shaft is longitudinally provided with copolyreaction kettle center, and blade is provided with agitating shaft, positioned at kettle
The motor of upside drives agitating shaft to rotate by transmission mechanism.Kettle lower end is provided with end socket and leaves discharging opening in end socket bottom.
Raw material and initiator are pumped into kettle from liquid phase feeding mouth, ethene progress polymerisation is added after leading to nitrogen deoxygenation, using list
Kettle batch technology.
In one embodiment of the invention, EVA elastomer micro emulsions are prepared using response type sulfonate anionic emulsifying agent
Liquid technique includes in charging continuously leading vinyl acetate, initiator, emulsifying agent/colloid protective agent, pH adjusting agent and ethene
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.In a specific example, these
The addition proportioning selection of polymerized monomer 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 that EVA elastomer microemulsions are prepared using response type sulfonate anionic emulsifying agent as shown in Figure 1
Device.This technique uses one-pot intermittently operated, including copolyreaction kettle 1, rabbling mechanism and product postprocessing part；The stirring
Mechanism includes stirring motor, transmission device (being not shown in figure) and agitating shaft and the agitating paddle being fixed on agitating shaft.Anti-
When answering the kettle to work, agitating paddle and part agitating shaft are below reaction liquid level.In process of production, surfactant, colloid are protected
Shield agent, initiator, pH adjusting agent, vinyl acetate are pumped into copolyreaction kettle 1 by high-pressure metering pump 6 respectively, lead to N2Deoxygenation, by second
Alkene reaches that predetermined pressure is constant out of ethylene feed press-in copolyreaction kettle 1, and ethene-second is carried out under suitable reaction condition
Vinyl acetate microemulsion reacts.After reaction terminates, discharged from discharging opening by reaction mass.Material enters foam removal tank 7, and pH is adjusted
Save agent and defoamer and add material foam removal tank progress product postprocessing from pH adjusting agent groove 4 and defoamer groove 8, material is finally pumped into
De- foam machine 9 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 embodiments of the invention includes：Addition deionized water is aqueous phase, adds surfactant and forms O/W bodies
System, colloid protective agent, initiator, pH adjusting agent and vinyl acetate are added, ethene is passed through, is total under polymeric reaction temperature
Poly- reaction, by certain polymerization reaction time, obtains EVA microemulsions.
With select ammonium persulfate water soluble starter, allyloxy hydroxypropyl azochlorosulfonate acid sodium (COPS-1) anion emulsifier,
Exemplified by sodium acid carbonate is pH adjusting agent and PVAC polyvinylalcohol (its trade mark is 17-88) is colloid protective agent：
Embodiment 1
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 58.4wt%, microemulsion average grain diameter 16nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 2
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 18.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 58.4wt%, microemulsion average grain diameter 27nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 3
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 16.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 58.2wt%, microemulsion average grain diameter 36nm.Microemulsion stability
It is good, storage 11 months can be stablized.
Embodiment 4
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 14.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 58.1wt%, microemulsion average grain diameter 48nm.Microemulsion stability compared with
It is good, storage 10 months can be stablized.
Embodiment 5
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 12.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 58.3wt%, microemulsion average grain diameter 59nm.Microemulsion stability compared with
It is good, storage 9 months can be stablized.
Embodiment 6
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 10.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 58.3wt%, microemulsion average grain diameter 70nm.Microemulsion stability compared with
It is good, storage 9 months can be stablized.
Embodiment 7
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 8.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt% of monomer VAc dosages, and pH is adjusted
The 0.5wt% that agent dosage is monomer VAc dosages is saved, polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, polymerisation
Time 5h.Under the conditions of this, polymerizate VAc contents are 58.4wt%, microemulsion average grain diameter 89nm.Microemulsion stability compared with
It is good, storage 8 months can be stablized.
Embodiment 8
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 6.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt% of monomer VAc dosages, and pH is adjusted
The 0.5wt% that agent dosage is monomer VAc dosages is saved, polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, polymerisation
Time 5h.Under the conditions of this, polymerizate VAc contents are 58.4wt%, microemulsion average grain diameter 99nm.Microemulsion stability compared with
It is good, storage 7.5 months can be stablized.
Embodiment 9
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 4.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt% of monomer VAc dosages, and pH is adjusted
The 0.5wt% that agent dosage is monomer VAc dosages is saved, polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, polymerisation
Time 5h.Under the conditions of this, polymerizate VAc contents are 58.1wt%, microemulsion average grain diameter 115nm.Microemulsion stability compared with
It is good, storage 7.5 months can be stablized.
Embodiment 10
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 2.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt% of monomer VAc dosages, and pH is adjusted
The 0.5wt% that agent dosage is monomer VAc dosages is saved, polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, polymerisation
Time 5h.Under the conditions of this, polymerizate VAc contents are 58.2wt%, microemulsion average grain diameter 121nm.Microemulsion stability compared with
It is good, storage 7.5 months can be stablized.
Embodiment 11
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 0.5wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt% of monomer VAc dosages, and pH is adjusted
The 0.5wt% that agent dosage is monomer VAc dosages is saved, polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, polymerisation
Time 5h.Under the conditions of this, polymerizate VAc contents are 58.2wt%, microemulsion average grain diameter 129nm.Microemulsion stability compared with
It is good, storage 7 months can be stablized.
Embodiment 12
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 3.0MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 74.5wt%, microemulsion average grain diameter 22nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 13
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 12.0MPa, polymerization
Reaction time 5h.Under the conditions of this, polymerizate VAc contents are 52.6wt%, microemulsion average grain diameter 21nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 14
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 16.5MPa, polymerization
Reaction time 5h.Under the conditions of this, polymerizate VAc contents are 48.9wt%, microemulsion average grain diameter 21nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 15
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 21.0MPa, polymerization
Reaction time 5h.Under the conditions of this, polymerizate VAc contents are 48.9wt%, microemulsion average grain diameter 23nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 16
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 25.0MPa, polymerization
Reaction time 5h.Under the conditions of this, polymerizate VAc contents are 46.4wt%, microemulsion average grain diameter 20nm.Stability of emulsion
Good, emulsion can stablize storage 12 months.
Embodiment 17
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 65 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 70.2wt%, microemulsion average grain diameter 22nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 18
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 85 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
5h between seasonable.Under the conditions of this, polymerizate VAc contents are 54.6wt%, microemulsion average grain diameter 26nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 19
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
4h between seasonable.Under the conditions of this, polymerizate VAc contents are 70.3wt%, microemulsion average grain diameter 21nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Embodiment 20
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
COPS-1 dosages are the 20.0wt% of monomer VAc dosages, and colloid protective agent PVA dosages are the 2.5wt%, pH of monomer VAc dosages
Conditioning agent dosage is the 0.5wt% of monomer VAc dosages, and polymeric reaction temperature is 75 DEG C, ethylene reaction pressure 7.5MPa, and polymerization is anti-
7h between seasonable.Under the conditions of this, polymerizate VAc contents are 52.2wt%, microemulsion average grain diameter 21nm.Microemulsion stability
It is good, storage 12 months can be stablized.
Comparative example 1
Response type sulfonate anionic emulsifying agent is not used, using common sulfonate anionic emulsifying agent dodecyl sodium sulfonate
Sodium, other reaction conditions are the same as embodiment 1.Under the conditions of this, polymerizate VAc contents are 64.7wt%, and latex particle particle diameter is
139nm.VAc contents are higher, and particle diameter is bigger than normal, and particle small part is adhered, and emulsion, which is put to 4 months i.e., demulsification precipitation occurs.
Comparative example 2
Response type sulfonate anionic emulsifying agent is not used, using common sulfate anion emulsifying agent dodecyl sulphate
Sodium, other reaction conditions are the same as embodiment 1.Under the conditions of this, polymerizate VAc contents are 66.9wt%, and latex particle particle diameter is
189nm.VAc contents are higher, and particle diameter is bigger than normal, and particle small part is adhered, and emulsion, which is put to 3.5 months i.e., demulsification precipitation occurs.
Comparative example 3
Using response type sulfonate anionic emulsifying agent COPS-1, dosage is the 0.4wt% of monomer VAc dosages, and other are anti-
Condition is answered with embodiment 1.Under the conditions of this, monomer add after i.e. produce precipitation, emulsion copolymerization reaction without.Emulsifier mistake
Low, system generation micella is very few, and bag does not live monomer.
Comparative example 4
Using response type sulfonate anionic emulsifying agent COPS-1, dosage is the 20.1wt% of monomer VAc dosages, and other are anti-
Condition is answered with embodiment 1.Under the conditions of this, polymerizate VAc contents are 58.6wt%, emulsion particle diameter 17nm.Emulsifier is inclined
Height, system is complicated, and continuing increases dosage is had little significance with reducing latex particle size.
By embodiment and comparative example 1-3 data comparisons, using response type sulfonate anionic breast used in present invention design
Agent prepares EVA elastomer microemulsion techniques, and product emulsion VAc contents and particle size are moderate, stable system；Pass through embodiment
With comparative example 4,5 data comparisons, it is micro- that EVA elastomers are prepared using response type sulfonate anionic emulsifying agent used in present invention design
Emulsion process, emulsifying agent is in certain amount ranges, and product emulsion VAc contents and particle size are moderate, stable system.
In summary, the present invention is in ethylene-vinyl acetate c one-pot batch production process, using response type sulfonic acid
Salt anionic emulsifying agent prepares EVA elastomer microemulsion products.The selection of response type sulfonate anionic emulsifying agent of the present invention,
In certain amount ranges, latex particle particle diameter can be significantly reduced, obtains that particle shape is excellent, the good EVA microemulsions of stability
Product, EVA emulsion applications scopes are widened significantly, meet different demands.The present invention uses one-pot batch technology, avoids more kettle behaviour
Make difficulty height, the problems such as installation cost high energy consumption, there is 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 EVA elastomers microemulsion, including：Using deionized water as aqueous phase, response type sulfonate anionic
Surfactant is emulsifying agent, adds pH adjusting agent and colloid protective agent, vinyl acetate and ethene draw in water-soluble free radical
Send out and carry out copolyreaction under the initiation of agent, obtain EVA elastomer microemulsions.
2. according to the method for claim 1, it is characterised in that the response type sulfonate anionic surfactant is selected from
Allyloxy hydroxypropyl azochlorosulfonate acid sodium, vinyl alkyl sodium sulfonate, mono maleate sulfonate, propenyl succinic acid diester sulphur
Sour sodium and isobutenyl succinic acid diester sodium sulfonate；It is preferred that its dosage is the 0.5-20.0wt% of vinyl acetate dosage, preferably
2-18wt%.
3. method according to claim 1 or 2, it is characterised in that the water-soluble free radical initiator selects nothing
One or more in machine 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.
4. according to the method described in any one in claim 1-3, it is characterised in that the water-soluble free radical initiator
Dosage is the 0.01-5.0wt%, preferably 0.1-2.0wt% of vinyl acetate dosage.
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；It is preferred that the dosage of the pH adjusting agent is the 0.05-5.0wt%, more preferably 0.5- of vinyl acetate dosage
2.0wt%.
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%, preferably 2.5-5.0wt%.
7. according to the method described in any one in claim 1-6, it is characterised in that the pressure of the ethene is 3.0-
25.0MPa, preferably 7.5-16.5MPa；Preferably, methods described is one-pot batch technology.
8. according to the method described in any one in claim 1-7, it is characterised in that the reaction temperature of the polymerization is 40-
125 DEG C, preferably 65-85 DEG C；Reaction time is 3-8h, preferably 4-7h.
9. according to the method described in any one in claim 1-8, it is characterised in that in EVA elastomers, VAC units contain
Measure as 35-75wt%, preferably 40-70wt%, the particle diameter of the microemulsion is 15-130nm, preferably 30-100nm；Preferably, it is newborn
Liquid can stablize storage more than 7 months, preferably more than 10 months.
10. according to the method described in any one in claim 1-9, it is characterised in that it is other common that methods described includes addition
Polycondensation monomer is copolymerized, and other comonomers preferably are selected from propylene, n-butene, isobutene, 1- hexenes and 1- octenes.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050050792A1 (en) * | 2003-08-13 | 2005-03-10 | The Lubrizol Corporation, A Corporation Of The State Of Ohio | Low temperature stable concentrate containing fatty acid based composition and fuel composition and method thereof |
| 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 |
| CN102030858A (en) * | 2009-09-30 | 2011-04-27 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion (VAE emulsion) and synthesis method thereof |
| EP2314636A1 (en) * | 2009-10-23 | 2011-04-27 | Universidad Del Pais Vasco-Euskal Herriko Unibertsitatea | Aqueous hybrid polyurethane-acrylic adhesives |
| CN102712722A (en) * | 2009-12-03 | 2012-10-03 | Ppg工业俄亥俄公司 | Waterborne coating compositions, related methods and coated substrates |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050050792A1 (en) * | 2003-08-13 | 2005-03-10 | The Lubrizol Corporation, A Corporation Of The State Of Ohio | Low temperature stable concentrate containing fatty acid based composition and fuel composition and method thereof |
| 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 |
| CN102030858A (en) * | 2009-09-30 | 2011-04-27 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion (VAE emulsion) and synthesis method thereof |
| EP2314636A1 (en) * | 2009-10-23 | 2011-04-27 | Universidad Del Pais Vasco-Euskal Herriko Unibertsitatea | Aqueous hybrid polyurethane-acrylic adhesives |
| CN102712722A (en) * | 2009-12-03 | 2012-10-03 | Ppg工业俄亥俄公司 | Waterborne coating compositions, related methods and coated substrates |
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