CN107793517A - 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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- CN107793517A CN107793517A CN201610808228.2A CN201610808228A CN107793517A CN 107793517 A CN107793517 A CN 107793517A CN 201610808228 A CN201610808228 A CN 201610808228A CN 107793517 A CN107793517 A CN 107793517A
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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
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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Abstract
The present invention relates to a kind of method for preparing EVA elastomer microemulsions, including：Using high polyoxyethylene groups nonionic surfactant as emulsifying agent, using deionized water as aqueous phase, the vinyl acetate of addition and the ethene being passed through carry out copolyreaction under the initiation of water-soluble free radical initiator, obtain EVA elastomer microemulsions.According to method provided by the invention, emulsion particle diameter can be reduced, improve stability of emulsion.
Description
Technical field
The present invention relates to a kind of EVA elastomers field, and in particular to one kind prepares EVA elastomers using the pre-emulsification seed law
The method of microemulsion.
Background technology
EVA (copolymer of Ethylene/vinyl acetate) 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 emulsions intensity height, asepsis environment-protecting, adhesive property are excellent, available for weave,
Light industry, coating, plastic toughening, formulation for building, polymer blending coating, modified rubber etc. field, are widely used, it is domestic
Outer demand is continuously increased, and is quickly grown 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
For deficiency of the prior art, this application provides a kind of method for preparing EVA elastomer microemulsions, using height
Polyoxyethylene groups (EO) number nonionic emulsifier prepares EVA elastomer microemulsions.Existing traditional more emulsifying agents of EVA emulsion polymerizations and
Assistant for emulsifying agent is used cooperatively, and formula is complicated, latex particle is excessive, be easily adhered, particle shape and stability of emulsion are poor, and product is not easy
Storage, application are limited.From single high EO numbers nonionic emulsifier, EVA elastomer emulsions emulsion particles can be significantly reduced
Seed footpath, particle shape is maintained, greatly improves stability of emulsion.It is stable that this invention prepares gained EVA elastomers microemulsion product
Property is good, VAc contents are 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：It is poly- using height
Oxyethylene group nonionic surfactant is as emulsifying agent, using deionized water as aqueous phase, the vinyl acetate of addition and is passed through
Ethene carries out copolyreaction under the initiation of water-soluble free radical initiator, obtains EVA elastomer microemulsions.
According to the present invention, using the molecular weight surfactant of high EO numbers as emulsifying agent, emulsion polymerization can be simplified and matched somebody with somebody
Square technique, latex micelle particle diameter is controlled, improve stability of emulsion.
According to the method for the invention preferred embodiment, the high polyoxyethylene groups nonionic surfactant
EO numbers be 20-30, such as 20-28.Using the nonionic surfactant more than EO numbers as emulsifying agent, it can be assigned to latex
The strong stereoscopic stable effect of ion, reduces latex intergranular mass exchange speed and collision probability, prevents from particle and gather to be adhered, so as to
Reduce the average grain diameter of emulsion.Using the nonionic surfactant more than EO numbers as emulsifying agent, emulsifying effectiveness is good, single kind
Class use can replace traditional colloid protective agent, in certain amount ranges, can rationally reduce latex ion particle diameter completely, maintain
Ionic formses, prevent from being adhered generation, simplify emulsion formulations, greatly improve stability of emulsion.It is described in a specific example
The dosage of nonionic surfactant is the 0.5-15.0wt%, such as 1.5-12wt% of vinyl acetate dosage.At one preferably
Embodiment in, the nonionic surfactant is selected from APES, high-carbon fatty alcohol polyoxyethylene ether and fat
At least one of fat acid polyoxyethylene ester, preferably is selected from alkyl polyoxyethylene ether Emulsogen LCN287 and alkyl polyoxyethylene
At least one of ether EmulsogenLCN217.Nonionic surfactant used, its polyoxyethylene groups (EO) number is high, energy
Enough function well as the effect above.
According to the method for the invention preferred embodiment, the water-soluble free radical initiator is from inorganic
One or more in salt, azo-compound, inorganic peroxide and inorganic oxide reduction class initiator.In ketone initiator
One or more can be used cooperatively.It is preferred that the water-soluble free radical initiator is selected from ammonium persulfate, sodium peroxydisulfate, persulfuric acid
Potassium, the isobutyl imidazoline hydrochloride of azo two, azo dicyano valeric acid, azo diisobutyl amidine hydrochloride, hydrogen peroxide and peroxidating
One or more in sodium.In a specific embodiment, the dosage of the water-soluble free radical initiator is vinyl acetate
The 0.01-5.0wt% of ester dosage, preferably 0.1-2wt%.
According to the method for the invention preferred embodiment, methods described also includes adding pH adjusting agent.Pass through
The pH value of pH value regulator regulation system is between 1.5-9.0.In a specific embodiment, the pH adjusting agent such as ability
Those pH adjusting agents commonly used in domain, are such as selected from least one of sodium acid carbonate and ammoniacal liquor.The dosage of the pH adjusting agent
For the 0.05-5.0wt% of vinyl acetate dosage, preferably 0.5-2wt%.
According to some specific embodiments of the present invention, colloid protective agent need not be added in methods described.
According to the method for the invention preferred embodiment, the body during pressure, i.e. copolyreaction of the ethene
It is pressure, is 3.0-25.0MPa, preferably 3.0-7.5MPa.The reaction temperature of the polymerization is 40-125 DEG C, preferably 75-90 DEG C；
Reaction time is 3.0-8.0h, preferably 4.0-5.0h.In the EVA elastomers of the product finally obtained, the content of VAC units is
35-75wt%, such as 60-70wt%.The average grain diameter of the elastomer microemulsion is 35-150nm, preferably 60-100nm.
The present invention on the basis of existing EVA emulsion polymerizations production technology, under certain polymerizing condition, using high EO numbers it is non-from
Sub- emulsifying agent prepares EVA elastomer microemulsions, to simplify emulsion polymerization Recipe, reduces latex particle particle diameter, improves emulsion
Stability.Traditional EVA emulsion polymerization techniques, emulsifying agent complex process is complicated, and emulsion particle particle diameter is bigger than normal to be easily adhered, and reaction is difficult
Control, causes copolymerization stage to be easily demulsified.Nonionic emulsifier in molecular structure more than EO numbers, it can be assigned to latex particle
Strong stereoscopic stable effect, reduces latex intergranular mass exchange speed and collision probability, prevents from particle and gather to be adhered, so as to reduce
Emulsion average grain diameter.Nonionic emulsifier emulsifying effectiveness more than EO numbers is good, and single kind use can replace traditional colloid completely
Protective agent, in certain amount ranges, latex particle particle diameter can be rationally reduced, particle shape is maintained, prevents from being adhered generation, letter
Change emulsion formulations, greatly improve stability of emulsion.The simple cost of material of inventive formulation is low, easy to operate, target emulsion-stabilizing
Property is good.
According to the method for the invention preferred embodiment, methods described is one-pot batch technology.Using one-pot
Batch technology, it is high to avoid more kettle operation difficulties, the problems such as installation cost high energy consumption, has higher industrial application value.
Before reaction, system palpus deoxygenation, such as logical nitrogen deoxygenation.Polymerization inhibitor is usually contained in commercially available VAC, VAc monomers used in the present invention are
Through removing polymerization inhibitor, such as polymerization inhibitor is removed by distilling.
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.This
Invent includes for the copolyreaction device of the above method：Copolyreaction kettle, for being copolymerized for ethene and vinyl acetate emulsion
Reaction provides reacting environment；And rabbling mechanism, for realizing the raw material mixing inside copolyreaction kettle.In the reality of the present invention
Apply in example, the copolyreaction kettle top is provided with surfactant, initiator, pH adjusting agent and vinyl acetate liquid phase feeding
Mouthful, and N2Ethylene feed, bottom are provided with discharging opening, connect material foam removal tank and degassing tank.Material foam removal tank top is provided with
PH adjusting agent groove and defoamer groove.The addition export for polymerizeing whole raw material and product is pumped using high-pressure metering pump.In this hair
In bright one embodiment, the rabbling mechanism is located at copolyreaction kettle axis line inside position, is filled by the driving being sequentially connected
Put, transmission device, agitating shaft and agitating paddle composition.The agitating paddle can be used anchor formula oar, vane wheel oar, ribbon oar or anchor formula oar with
The compound oar combination of vane wheel oar.In one particular embodiment of the present invention, it is longitudinally provided with stirring at copolyreaction kettle center
Axle, and blade is provided with agitating shaft, the motor on the upside of kettle drives agitating shaft to rotate by transmission mechanism.Kettle lower end
Discharging opening is left provided with end socket and in end socket bottom.Raw material and initiator are pumped into kettle from liquid phase feeding mouth, lead to nitrogen row
Ethene is added after oxygen and carries out polymerisation, using one-pot batch technology.
Based on above-mentioned copolyreaction device, in one embodiment of the invention, using high EO numbers nonionic emulsifier system
The method of standby EVA elastomer microemulsions includes：During charging, by vinyl acetate, initiator, emulsifying agent, pH adjusting agent
It is continuously introduced into copolyreaction kettle with ethene, and continuously leads copolyreaction product from foregoing copolyreaction kettle in discharging
Go out, carry out processing and the later separation of product.Product demulsification extraction polymer can carry out related polymer performance characterization.
The present invention can also add other polymerized monomers while combined polymerization and is copolymerized.It is poly- as what is used in copolymerization
The alkene such as propylene, n-butene, isobutene, 1- hexenes, 1- octenes can be enumerated by closing monomer.The addition proportioning choosing of these polymerized monomers
Select in the range of not hindering the present invention to realize goal of the invention.
According to the present invention, using the particle diameter provided by the invention that can reduce EAV elastomer microemulsions, emulsion-stabilizing is improved
Property.The simple cost of material of inventive formulation is low, easy to operate, target good emulsion stability, and emulsion can store more than 7 months, such as
More than 10 months.The present invention use one-pot batch technology, avoids more kettle operation difficulties height, the problems such as installation cost high energy consumption,
With 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；3- initiator grooves；4-pH conditioning agent grooves；5- monomer grooves；6- is high
Press measuring 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 that EVA elastomer microemulsions are prepared as emulsifying agent using high EO numbers nonionic surfactant as shown in Figure 1
Copolyreaction device.This technique 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 stirring being fixed on agitating shaft
Oar.When reactor works, agitating paddle and part agitating shaft are below reaction liquid level.In process of production, surfactant,
Initiator, pH adjusting agent, vinyl acetate are pumped into copolyreaction kettle 1 by high-pressure metering pump 6 respectively, lead to N2Deoxygenation, by ethene from
Reach that predetermined pressure is constant in ethylene feed press-in copolyreaction kettle 1, ethylene-acetate second is carried out under suitable reaction condition
Alkene ester microemulsion copolyreaction.After reaction terminates, discharged from discharging opening by reaction mass.Material enters foam removal tank 7, pH adjusting agent
Material foam removal tank being added from pH adjusting agent groove 4 and defoamer groove 8 with defoamer and carrying out product postprocessing, 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, using high polyoxyethylene groups nonionic surfactant as emulsification
Agent, using deionized water as aqueous phase, O/W systems are formed, add pH value regulator, the vinyl acetate of addition and the ethene being passed through exist
Copolyreaction is carried out under the initiation of water-soluble free radical initiator, obtains EVA elastomer microemulsions.To select ammonium persulfate as water
Soluble radical initiator, EO numbers are 28 nonionic emulsifier LCN287, and sodium acid carbonate is exemplified by pH adjusting agent：
Embodiment 1
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 15.0wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.1wt%, microemulsion average grain diameter 36nm.Stability of emulsion is preferable, and emulsion can stablize storage 11 months.
Embodiment 2
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 13.5wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.1wt%, microemulsion average grain diameter 48nm.Stability of emulsion is preferable, and emulsion can stablize storage 10.5 months.
Embodiment 3
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 12.0wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.0wt%, microemulsion average grain diameter 61nm.Stability of emulsion is preferable, and emulsion can stablize storage 10.5 months.
Embodiment 4
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 10.5wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.2wt%, microemulsion average grain diameter 75nm.Stability of emulsion is preferable, and emulsion can stablize storage 9.5 months.
Embodiment 5
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 9.0wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.1wt%, microemulsion average grain diameter 85nm.Stability of emulsion is preferable, and emulsion can stablize storage 9.5 months.
Embodiment 6
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 7.5wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.1wt%, microemulsion average grain diameter 96nm.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
LCN287 dosages be monomer VAc dosages 6.0wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.0wt%, microemulsion average grain diameter 109nm.Stability of emulsion is preferable, and emulsion can stablize storage 8 months.
Embodiment 8
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 4.5wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.1wt%, microemulsion average grain diameter 118nm.Stability of emulsion is preferable, and emulsion can stablize storage 8 months.
Embodiment 9
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 3.0wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.2wt%, microemulsion average grain diameter 129nm.Stability of emulsion is preferable, and emulsion can stablize storage 7.5 months.
Embodiment 10
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 1.5wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.0wt%, microemulsion average grain diameter 138nm.Stability of emulsion is preferable, and emulsion can stablize storage 7.5 months.
Embodiment 11
Ammonium persulfate is used as initiator, total dosage be vinyl acetate 0.1wt%, O/W systems, surfactant
LCN287 dosages be monomer VAc dosages 0.5wt%, pH adjusting agent dosage be monomer VAc dosages 0.5wt%, polymerisation
Temperature is 75 DEG C, and under the conditions of this, polymerizate VAc contents are by ethylene reaction pressure 7.5MPa, polymerization reaction time 5h.
62.0wt%, microemulsion average grain diameter 149nm.Stability of emulsion is preferable, and emulsion can stablize storage 7 months.
Comparative example 1
Using surfactant LCN287, dosage is the 0.4wt% of monomer VAc dosages, the same embodiment of other reaction conditions
11.Under the conditions of this, monomer add after i.e. be layered, emulsion copolymerization reaction without.Emulsifier is too low, system generation micella mistake
Few, bag does not live monomer.
Comparative example 2
Using surfactant LCN287, dosage is the 15.1wt% of monomer VAc dosages, the same embodiment of other reaction conditions
1.Under the conditions of this, polymerizate VAc contents are 63.3wt%, and viscosity is higher, emulsion particle diameter 38nm.Emulsifier is higher, after
Continuous increase dosage is had little significance with reducing latex particle size.
Comparative example 3
Using surfactant LCN118, EO numbers are 11, and dosage is the 15.0wt% of monomer VAc dosages, other reaction bars
Part is the same as embodiment 1.Under the conditions of this, polymerizate VAc contents are 63.9wt%, and viscosity is higher, and emulsion particle diameter 198nm, emulsion is put
To 3 months, i.e. nonionic emulsifier EO numbers selected by appearance demulsification precipitation were relatively low, and emulsifying agent is acted on the stereoscopic stable of latex particle
Reduce, particle is easy and gathers growth, and particle diameter is bigger than normal, and stability of emulsion reduces.
Comparative example 4
Using surfactant LCN407, EO numbers are 40, and dosage is the 15.0wt% of monomer VAc dosages, other reaction bars
Part is the same as embodiment 1.Under the conditions of this, polymerizate discharging is to precipitate.The too high nonionic emulsifier of EO numbers " rigidity " is too strong,
Dissolubility reduces in water body, does not have emulsifying agent and maintains latex particle stabilization, from the too high nonionic emulsifier of EO numbers
It is and improper.
By embodiment and the data comparison of comparative example 1 and 2, the high EO numbers non-ionic emulsifier of addition used is designed using the present invention
Agent prepares EVA elastomer microemulsion techniques, adds appropriate species emulsifying agent, in certain amount ranges, product emulsion VAc contains
Amount and particle size are moderate, and emulsion system is stable, product period of storage length；By embodiment and the data comparison of comparative example 3 and 4,
The high EO numbers nonionic emulsifier of addition used is designed using the present invention and prepares EVA elastomer microemulsion techniques, adds appropriate kind
Class emulsifying agent, for EO numbers in certain excursion, product emulsion VAc contents and particle size are moderate, and emulsion system is stable, product
Period of storage is grown.
To sum up, the present invention is in ethylene-vinyl acetate c one-pot batch production process, using high EO numbers nonionic Emulsion
Agent prepares EVA elastomer microemulsion products.The selection of appropriate high EO numbers nonionic emulsifier of the invention, can significantly reduce breast
Glue particle diameter, obtains that particle shape is excellent, the good EVA microemulsion products of stability, widens EVA emulsion applications scopes significantly,
Meet different demands.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.
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 method for preparing EVA elastomer microemulsions, including：Using high polyoxyethylene groups nonionic surfactant conduct
Emulsifying agent, using deionized water as aqueous phase, the vinyl acetate of addition and ethene the drawing in water-soluble free radical initiator being passed through
Carry out copolyreaction is given, obtains EVA elastomer microemulsions.
2. according to the method for claim 1, it is characterised in that the EO of the high polyoxyethylene groups nonionic surfactant
Number is 20-30, preferably 20-28；Preferably, the dosage of the nonionic surfactant is the 0.5- of vinyl acetate dosage
15.0wt%, preferably 1.5-12wt%.
3. method according to claim 1 or 2, it is characterised in that the nonionic surfactant gathers selected from alkyl phenol
At least one of oxygen vinethene, high-carbon fatty alcohol polyoxyethylene ether and polyoxyethylene carboxylate, it preferably is selected from alkyl polyoxy second
At least one of alkene ether Emulsogen LCN287 and alkyl polyoxyethylene ether EmulsogenLCN217.
4. according to the method described in any one in claim 1-3, 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.
5. according to the method described in any one in claim 1-4, it is characterised in that the water-soluble free radical initiator
Dosage is the 0.01-5.0wt%, preferably 0.1-2wt% of vinyl acetate dosage.
6. according to the method described in any one in claim 1-5, it is characterised in that methods described also includes adding pH regulations
Agent, preferably described pH adjusting agent are selected from sodium acid carbonate and ammoniacal liquor.
7. according to the method for claim 6, it is characterised in that the dosage of the pH adjusting agent is vinyl acetate dosage
0.05-5.0wt%, preferably 0.5-2wt%.
8. according to the method described in any one in claim 1-7, it is characterised in that the pressure of the ethene is 3-25MPa,
It is preferred that 3.0-7.5MPa；Preferably, 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 reaction temperature of the polymerization is 40-
125 DEG C, preferably 75-90 DEG C, preferably reaction time 3.0-8.0h, 4.0-5.0h；Preferably, in EVA elastomers, VAC units
Content be 35-75wt%, preferably 60-70wt%, the average grain diameter of the microemulsion is 35-150nm, preferably 60-100nm；
Preferably, emulsion 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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| CN201610808228.2A CN107793517A (en) | 2016-09-07 | 2016-09-07 | A kind of method for preparing EVA elastomer microemulsions |
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| CN201610808228.2A Pending CN107793517A (en) | 2016-09-07 | 2016-09-07 | A kind of method for preparing EVA elastomer microemulsions |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5665816A (en) * | 1994-09-02 | 1997-09-09 | Hoechst Aktiengesellschaft | Aqueous dispersions for adhesives |
| JP2004161951A (en) * | 2002-11-15 | 2004-06-10 | Sumitomo Chem Co Ltd | Method for producing aqueous emulsion |
| CN104093679A (en) * | 2012-01-31 | 2014-10-08 | 国际人造丝公司 | Vinyl acetate-ethylene copolymer emulsion and polymer cement waterproof composition based on the same |
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2016
- 2016-09-07 CN CN201610808228.2A patent/CN107793517A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5665816A (en) * | 1994-09-02 | 1997-09-09 | Hoechst Aktiengesellschaft | Aqueous dispersions for adhesives |
| JP2004161951A (en) * | 2002-11-15 | 2004-06-10 | Sumitomo Chem Co Ltd | Method for producing aqueous emulsion |
| CN104093679A (en) * | 2012-01-31 | 2014-10-08 | 国际人造丝公司 | Vinyl acetate-ethylene copolymer emulsion and polymer cement waterproof composition based on the same |
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Application publication date: 20180313 |