CN106543325A - A kind of method for preparing low-viscosity EVA emulsions - Google Patents
A kind of method for preparing low-viscosity EVA emulsions Download PDFInfo
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Abstract
The present invention relates to a kind of method for preparing low-viscosity EVA emulsions, is included in pre-emulsification stage addition alcohol compound, is subsequently adding initiator and causes emulsion polymerization, make ethylene carry out copolyreaction with vinyl acetate.The alcohol compound is preferably C6-C8Fatty alcohol, more preferably capryl alcohol and its isomerss.The present invention can significantly reduce system viscosity using alcohol compound as volatility emulsion stabilizer, obtain that particle shape is excellent, and the EVA product emulsions of good stability are widened significantly EVA emulsion applications scopes, meet different demands.And one-pot batch technology to avoid many kettle operation difficulties high, the problems such as installation cost high energy consumption, with higher industrial application value.
Description
Technical field
The present invention relates to a kind of method for preparing low-viscosity EVA emulsions.
Background technology
The EVA emulsions of emulsion polymerization production, vinyl acetate (VAc) content are moderate, and product has excellent
Pliability, the transparency, cold flexibility, weatherability, resistance to corrosive chemicals and with filler and color masterbatch
The compatibility.EVA product emulsions intensity height, asepsis environment-protecting, adhesive property are excellent, can be used to weaving, light industry,
The fields such as coating, plastic toughening, formulation for building, polymer blending coating, modified rubber, are widely used,
Its domestic and international demand is continuously increased, and quickly grows in recent years.In prior art, the method for preparing EVA emulsions
Be included in emulsifier aqueous solution and add VAc monomers and colloid protective agent, be subsequently adding initiator, make ethylene with
VAc monomers carry out copolyreaction.
Patent EP0373313A2 describes high solids content ethane-acetic acid ethyenyl ester latex preparation process.Polymerization is anti-
Ethylene pressure is answered for 47.0MPa, causes polymerization respectively at 40 DEG C and 65-82 DEG C, response time 15min and
3.0h.Product VAc contents are 65.0-80.0wt%, product viscosity 200-38000mpa.s.Patent CN1302027C
Polymerization is caused to prepare high solid EVA latex at 40-60 DEG C, pressure, response time are disregarded in reacting ethylene weight calculation
10.0h, product VAc contents 75.0-99.0wt%, viscosity 5000mpa.s.Patent CN101200518A is adopted
Hydrogen peroxide-ferrous sulfate system, causes polymerization, ethylene respectively at 70-75 and 75-80 DEG C of two benches ladder temperature control
Reaction pressure 9.0-10.0MPa, the EVA latex that product viscosity 3843mpa.s. above prior arts are prepared
Product viscosity is too high, and latex particle is easily reunited, and stability is poor, and application is limited significantly.
In addition, patent CN102030858B is respectively under the ethylene reaction pressure of 4.0-5.0 and 5.4-5.7MPa,
In 60-65 and 75-80 DEG C of initiated polymerization, response time 10-15mim and 1.5-3.0h.Product VAc contains
Amount 54.50wt%, viscosity 1162mpa.s.Patent CN103665241A describes a kind of cationic ethylene-acetic acid
Vinyl acetate copolymer emulsion production technology, invention are produced from cationic emulsifier and nonionic emulsifier compound system
Thing VAc contents 50.0wt%, viscosity 200-500mpa.s.The EVA emulsions that above prior art is prepared,
Product viscosity is higher, and particle is easily reunited, and product stability is general, and range of application is narrower.
Therefore, the product viscosity height for being prepared using existing EVA emulsion polymerization techniques, particle shape and breast
Liquid stability is poor, and product is difficult storage, and range of application is limited.
The content of the invention
The invention provides a kind of method for preparing low-viscosity EVA emulsions, which adopts alcohol compound as volatilization
Property emulsion stabilizer, can significantly reduce product viscosity, maintain particle shape and ductile strength.The EVA for obtaining
Product emulsion good stability, VAc contents are moderate, excellent performance, can meet different demands.
The method for preparing low-viscosity EVA emulsions of the present invention, including：Alcohols is added in the pre-emulsification stage
Compound, is subsequently adding initiator and causes emulsion polymerization, make ethylene carry out copolymerization with vinyl acetate (VAc) anti-
Should.
In an embodiment of the present invention, the alcohol compound is used as volatility emulsion stabilizer, preferred C6-C8
Fatty alcohol, more preferably capryl alcohol and its isomerss.The alcohol compound consumption is VAc monomer consumptions
0.05-1.0wt%.
In an embodiment of the present invention, the pre-emulsification stage use nonionic surfactant as emulsifying agent,
It is preferred that alkylphenol polyoxyethylene OP-10,5.0-25.0wt% of the emulsifier for VAc monomer consumptions.
In an embodiment of the present invention, methods described uses polyvinyl alcohol (PVA) as colloid protective agent, uses
Measure the 1.5-6.0wt% for VAc monomer consumptions.PVA typically is being not added with adding when initiator forms monomer micelle
Enter, and in the polymerization the phase growth of colloidal particles stage add, purpose is all to stablize polymerization system, keep particle
Form.
In an embodiment of the present invention, the initiator is water-soluble free radical initiator, is drawn selected from inorganic salts
The one kind in agent, azo-initiator, inorganic peroxygen species initiator and inorganic oxide reduction class initiator is sent out,
In initiator of the same race one or more are selected to use cooperatively.The inorganic salts initiator selected from Ammonium persulfate.,
At least one in sodium peroxydisulfate and potassium peroxydisulfate；The azo-initiator is selected from two isobutyl imidazoline salt of azo
At least one in hydrochlorate, azo dicyano valeric acid and azo diisobutyl amidine hydrochlorate；The inorganic peroxygen
At least one of the species initiator in hydrogen peroxide, sodium peroxide and potassium peroxide.The initiator amount is
The 0.01-5.0wt% of VAc monomer consumptions.
In an embodiment of the present invention, alkaline matter is used during copolyreaction as pH value regulator, institute
PH value regulator is stated selected from sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium bicarbonate and carbonic acid
At least one in potassium, more preferably sodium bicarbonate.The consumption of the pH value regulator is VAc monomer consumptions
0.05-5.0wt%.
The pre-emulsification stage is to go known in the industry, emulsifying agent one or many is dissolved in water specially and is prepared into
To emulsifier aqueous solution, being subsequently adding VAc monomers makes its solubilising in emulsifier aqueous solution.Alcohol compound can
Added with any one step in said process, such as water is dissolved in emulsifying agent, or is added to breast with VAc monomers
In agent aqueous solution.Initiator is subsequently adding, ethylene is passed through, is existed in pH value regulator and colloid protective agent
Under carry out emulsion polymerization.
The present invention can prepare EVA emulsions using one-pot batch technology, and raw material is passed through high pressure measurement from kettle top directly
Pump pumps into copolyreaction kettle.Copolyreaction condition is：Reaction temperature is 40-125 DEG C, and ethylene pressure is
3.0-25.0MPa, response time are 2.0-8.0 hours.The pH value of course of reaction is controlled in 1.5-9.0, preferably
6.5-7.5。
According to the present invention, in the EVA emulsions for obtaining, VAc contents in the copolymer are 35.0-95.0wt%；
Emulsion viscosity is 80-160mpa.s.During " the VAc contents in the copolymer " implication is EVA copolymer
The content of the corresponding polymerized unit of vinyl acetate.
In an embodiment of the present invention, methods described includes protecting VAc monomers, initiator, emulsifying agent, colloid
Shield agent, pH value regulator and ethylene are continuously introduced in copolyreaction kettle, and copolymerization product is continuously led from kettle
Go out, carry out later separation and the process of product.Product breakdown of emulsion extracts polymer and can carry out relevant polymerization physical performance
Characterize.
In one particular embodiment of the present invention, for the single reactor, which is copolyreaction kettle, its
Inside be provided with rabbling mechanism, its top be provided with for emulsifying agent/colloid protective agent, initiator, pH value regulator and
The liquid phase feeding mouth and nitrogen and ethylene feed of vinyl acetate charging, its underpart is provided with discharging opening, connects
Material foam removal tank and degassing tank, material foam removal tank top are provided with pH value regulator groove and defoamer groove.Polymerization is complete
The addition of journey raw material and product is derived and is pumped using high-pressure metering pump.Volatility emulsion stabilizer is in pre-emulsification rank
Section is added into system.
In one embodiment of the invention, the rabbling mechanism is located at copolyreaction kettle axis line inside position,
It is made up of the driving means, actuating device, shaft and the stirring paddle that are sequentially connected.The stirring paddle can use anchor
Formula oar, vane wheel oar, ribbon oar or anchor formula oar are combined with the compound oar of vane wheel oar.
In one particular embodiment of the present invention, shaft is longitudinally provided with copolyreaction kettle center, and
Shaft is provided with blade, and the motor on the upside of kettle drives shaft to rotate by drive mechanism.Under kettle
End is provided with end socket and leaves discharging opening in end socket bottom.By raw material and initiator from liquid phase feeding mouth injection kettle,
Ethylene is added to carry out polyreaction after logical nitrogen deoxygenation, using one-pot batch technology.
It should be understood that usually containing polymerization inhibitor in the monomer being purchased commercially such as VAc monomers, carrying out altogether
Certainly to be purified before poly-, such as distill to remove polymerization inhibitor.
The present invention can also add other polymerized monomers to carry out copolymerization while EVA is polymerized.As making in copolymerization
Polymerized monomer can enumerate the alkene such as propylene, n-butene, isobutene., 1- hexenes, 1- octenes.These polymerizations
The addition proportioning of monomer selects do not hindering the present invention to realize in the range of goal of the invention.
In traditional EVA emulsion polymerization techniques, the consumption of emulsifying agent is bigger, and copolymerization rate is faster, emulsion particle
Seed footpath is less, but emulsion viscosity is higher, the difficult control of reaction, product easily breakdown of emulsion.Alcohol compound is only due to which
Special molecular structure, both with lipophilic group, has hydrophilic group again, therefore can either be with emulsifying agent and colloid
Protective agent coordinates, and monomer and polymer latex particles stable existence, and the solubilized monomer of energy and swelling copolymerization is divided greatly
Subchain.The present invention is added in reaction system in the pre-emulsification stage on the basis of existing EVA emulsion polymerization techniques
Alcohol compound is used as volatility emulsion stabilizer, under a large amount of emulsifying agent existence conditions, appropriate alcohols chemical combination
Thing can notable stable particle, reduce system viscosity, prevent from being adhered generation, be prevented effectively from emulsion breaking and gel
Effect is produced, and greatly improves stability of emulsion.Alcohol compound has volatile simultaneously so as to can be rear
Processing stage easily remove, do not affect emulsion quality.In addition, the cost of material of the present invention is low, it is easy to operate,
Target good emulsion stability.And adopting one-pot batch technology, it is to avoid many kettle operation difficulties are high, installation cost energy
The problems such as consuming high, with higher industrial application value.
Description of the drawings
Fig. 1 is the ethylene-vinyl acetate emulsion one-pot copolymerization batch technology schematic device of the present invention.
In figure：1 is copolyreaction kettle；2 is emulsifying agent/colloid protective agent groove；3 is initiator groove；4-1 and 4-2
For pH value regulator groove；5 is VAc monomer grooves；6-2,6-3,6-4,6-5,6-7 and 6-9 are high-pressure gauge
Amount pump；7 is material foam removal tank；8 is defoamer groove；9 are de- foam machine.
Specific embodiment
The present invention is explained further below by embodiment.
The as shown in Figure 1 copolyreaction device for preparing low-viscosity EVA emulsions.Using one-pot intermittently operated, wrap
Include copolyreaction kettle 1, feeding mechanism and product postprocessing part.1 top of copolyreaction kettle is provided with emulsifying
Agent/colloid protective agent charging aperture, initiator feed mouth, pH value regulator charging aperture and vinyl acetate liquid phase are entered
Material mouth, and N2And ethylene feed.Emulsifying agent/colloid protective agent groove 2 passes through high-pressure metering pump 6-2 together
Poly- reactor 1 is connected, and initiator groove 3 is connected with copolymerization reactor 1 by high-pressure metering pump 6-3, and pH value is adjusted
Section agent groove 4-1 is connected with copolymerization reactor 1 by high-pressure metering pump 6-4, and VAc monomers groove 5 passes through high-pressure gauge
Amount pump 6-5 is connected with copolymerization reactor 1.It is provided with inside copolyreaction kettle 1 including motor, stirring paddle and stirring
The rabbling mechanism of axle.The rabbling mechanism includes stirring motor, actuating device (not shown in figure) and stirring
Axle and the stirring paddle being fixed on shaft.When reactor works, stirring paddle and part shaft are located at reaction
Below liquid level.
1 bottom of copolyreaction kettle is provided with discharging opening and is connected with the charging aperture of material foam removal tank 7.PH value is adjusted
Section agent groove 4-2 and defoamer groove 8 are connected with material foam removal tank 7 by high-pressure metering pump 6-7 respectively.Material is removed
The discharging opening of foam tank 7 is connected with the charging aperture of de- foam machine 9 by high-pressure metering pump 6-9.
Before reaction starts, emulsifier aqueous solution is added into copolyreaction kettle 1 by emulsifying agent/colloid protective agent groove 2
It is interior, VAc monomers are added into copolyreaction kettle 1 by VAc monomers groove 5 then, in above-mentioned pre-emulsification rank
Section adds alcohol compound by emulsifying agent/colloid protective agent groove 2 into copolyreaction kettle 1.It is subsequently adding initiation
Agent and pH value regulator, are passed through N2Deoxygenation, by ethylene press-in copolyreaction kettle 1, is carried out after pressure is constant
Ethylene-vinyl acetate emulsion copolyreaction.After reaction terminates, the material discharged from copolyreaction kettle 1 is entered
Material foam removal tank 7, adds pH value regulator and defoamer to carry out product postprocessing.From in material foam removal tank 7
The material of discharge finally pumps into de- foam machine 9 and removes unreacting ethylene gas.Polymerization and last handling process in, raw material and
The addition and derivation of product is pumped using high-pressure metering pump 6-2,6-3,6-4,6-5,6-7 and 6-9.
The VAc in product EVA is determined using nuclear-magnetism, elementary analysiss, thermogravimetric and infrared four kinds of methods in embodiment
Content.Emulsion viscosity is determined using NDJ-4 types rotational viscometer.
Embodiment 1
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.05wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.2wt% to close product VAc contents, and emulsion viscosity is 155mpa.s.Preferably, emulsion can be steady for stability of emulsion
Surely store 9 months.
Embodiment 2
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.15wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.1wt% to close product VAc contents, and emulsion viscosity is 141mpa.s.Preferably, emulsion can be steady for stability of emulsion
Surely store 9 months.
Embodiment 3
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.25wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.1wt% to close product VAc contents, and emulsion viscosity is 126mpa.s.Preferably, emulsion can be steady for stability of emulsion
Surely store 10 months.
Embodiment 4
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.35wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, ethylene reaction pressure
75.0MPa, polymerization reaction time 5h, the pH value of course of reaction are controlled 6.5.Under the conditions of this, polymerizate
VAc contents are 67.0wt%, and emulsion viscosity is 111mpa.s.Good emulsion stability, emulsion can stably store 11
Individual month.
Embodiment 5
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.45wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.2wt% to close product VAc contents, and emulsion viscosity is 90mpa.s.Good emulsion stability, emulsion can be stablized
Storage 13 months.
Embodiment 6
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.55wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.1wt% to close product VAc contents, and emulsion viscosity is 86mpa.s.Good emulsion stability, emulsion can be stablized
Storage 14 months.
Embodiment 7
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.65wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.1wt% to close product VAc contents, and emulsion viscosity is 81mpa.s.Good emulsion stability, emulsion can be stablized
Storage 14 months.
Embodiment 8
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.75wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.0wt% to close product VAc contents, and emulsion viscosity is 124mpa.s.Preferably, emulsion can be steady for stability of emulsion
Surely store 10 months.
Embodiment 9
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.85wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.2wt% to close product VAc contents, and emulsion viscosity is 143mpa.s.Preferably, emulsion can be steady for stability of emulsion
Surely store 8 months.
Embodiment 10
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 0.95wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.1wt% to close product VAc contents, and emulsion viscosity is 152mpa.s.Preferably, emulsion can be steady for stability of emulsion
Surely store 7 months.
Embodiment 11
Ammonium persulfate. is adopted for initiator, 0.3wt% of total consumption for vinyl acetate；O/W systems, surface
15.0wt% of the activating agent op-10 consumptions for VAc monomer consumptions；Volatility emulsion stabilizer capryl alcohol consumption is VAc
The 1.0wt% of monomer consumption；3.0wt% of the colloid protective agent PVA consumptions for VAc monomer consumptions；PH value
0.5wt% of the regulator sodium bicarbonate consumption for VAc monomer consumptions；Polymeric reaction temperature is 75 DEG C, and ethylene is anti-
Pressure 75.0MPa, polymerization reaction time 5h, the pH value of course of reaction is answered to control 6.5.Under the conditions of this, gather
It is 67.1wt% to close product VAc contents, and emulsion viscosity is 159mpa.s.Preferably, emulsion can be steady for stability of emulsion
Surely store 7 months.
Embodiment 12
Except adopting hexanol for volatility emulsion stabilizer, beyond consumption is for the 0.55wt% of VAc monomer consumptions, its
It feeds and reaction condition is with embodiment 1.Under the conditions of this, in polymerizate, VAc contents are 66.9wt%, newborn
Liquid viscosity is 91mpa.s.Good emulsion stability, emulsion stably can be stored 13 months.
Comparative example 1
The prepolymerization stage is not added with volatility emulsion stabilizer capryl alcohol, and other chargings and reaction condition are with enforcement
Example 1.Under the conditions of this, polymerizate VAc contents are 74.0wt%, and emulsion viscosity is 186mpa.s.Product breast
Micelle subdivision is adhered, and emulsion was put to 4 months breakdown of emulsion precipitation occurs.
Comparative example 2
0.04wt% of the volatility emulsion stabilizer capryl alcohol consumption for VAc monomer consumptions, other chargings and reaction bar
Part is with embodiment 1.Under the conditions of this, polymerizate VAc contents are 69.2wt%, and emulsion viscosity is 168mpa.s.
Product latexes particle fraction is adhered, and emulsion was put to 5 months breakdown of emulsion precipitation occurs, illustrates that capryl alcohol consumption is too low.
Comparative example 3
1.1wt% of the volatility emulsion stabilizer capryl alcohol consumption for VAc monomer consumptions, other chargings and reaction bar
Part is with embodiment 1.Under the conditions of this, polymerizate VAc contents are 69.1wt%, and emulsion viscosity is 191mpa.s.
Product latexes particle fraction is adhered, and emulsion was put to 3 months breakdown of emulsion precipitation occurs, illustrates to continue to increase capryl alcohol consumption
Have little significance.
Comparative example 4
1.1wt% of the volatility emulsion stabilizer capryl alcohol consumption for VAc monomer consumptions, capryl alcohol is in copolymerization stage
Add rather than the pre-emulsification stage adds, other chargings and reaction condition are with embodiment 1.Under the conditions of this, polymerization is produced
Thing VAc contents are 74.0.1wt%, and emulsion viscosity is that 219mpa.s. product stabilities are reduced, and emulsion is put to 4
There is within individual month breakdown of emulsion precipitation, illustrate that capryl alcohol should be added in the pre-emulsification stage, it is impossible to add during copolymerization
Enter.
In embodiment 1-11, emulsion viscosity is first reducing again elevated Long-term change trend.In general the too low body of viscosity
It is that solid content is too low, viscosity is high to cause stability to reduce again.The emulsion combination property of embodiment 3-8 under relatively
Preferably.
Embodiment 1-11 is contrasted with comparative example 1, is illustrated using capryl alcohol as volatility emulsion stabilizer, emulsion
VAc contents and moderate viscosity in product, emulsion-stabilizing, period of storage are long；By embodiment 1-11 and comparative example
2 and 3 contrasts, illustrate that capryl alcohol addition can not exceed the framework of the present definition；By embodiment 1-11 and contrast
Example 4 is contrasted, and is illustrated to add capryl alcohol in the pre-emulsification stage, be can be very good solubilized monomer, make monomeric small molecule exist
Stretch in micelle, free radical polymerization efficiency high；Such as add in copolymerization stage, capryl alcohol can swollen polymer
Macromole, causes particle diameter to increase, and stability of emulsion declines.
To sum up, it is of the invention in ethylene-vinyl acetate c one-pot batch production process, using alcohol compound
As volatility emulsion stabilizer, system viscosity can be significantly reduced, it is excellent to obtain particle shape, good stability
EVA product emulsions, widen significantly EVA emulsion applications scopes, meet different demands.And knock off between one-pot
The problems such as skill avoids many kettle operation difficulties height, installation cost high energy consumption, with higher industrial application value.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in which is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of method for preparing low-viscosity EVA emulsions, is included in pre-emulsification stage addition alcohol compound, so
Add initiator to cause emulsion polymerization afterwards, make ethylene copolyreaction be carried out with vinyl acetate.
2. method according to claim 1, it is characterised in that the alcohol compound is C6-C8Fat
Alcohol, preferred capryl alcohol and its isomerss.
3. method according to claim 1 and 2, it is characterised in that the alcohol compound consumption is
The 0.05-1.0wt% of VAc monomer consumptions.
4. according to the method in any one of claims 1 to 3, it is characterised in that make in the pre-emulsification stage
With nonionic surfactant as emulsifying agent, preferred alkylphenol polyoxyethylene OP-10, the preferably emulsifying
5.0-25.0wt% of the agent consumption for VAc monomer consumptions.
5. the method according to any one of Claims 1-4, it is characterised in that methods described uses poly- second
Enol is used as colloid protective agent, preferably 1.5-6.0wt% of its consumption for VAc monomer consumptions.
6. the method according to any one of claim 1 to 5, it is characterised in that the initiator is water-soluble
Free love base initiator, selected from inorganic salts initiator, azo-initiator, inorganic peroxygen species initiator
The one kind in class initiator is reduced with inorganic oxide, the preferably initiator amount is VAc monomer consumptions
0.01-5.0wt%.
7. the method according to any one of claim 1 to 6, it is characterised in that the copolyreaction process
Used in alkaline matter as pH value regulator, which is selected from sodium hydroxide, sodium bicarbonate, sodium carbonate, hydrogen-oxygen
Change at least one in potassium, potassium bicarbonate and potassium carbonate, preferably sodium bicarbonate, preferably described pH value is adjusted
0.05-5.0wt% of the consumption of agent for VAc monomer consumptions.
8. the method according to any one of claim 1 to 7, it is characterised in that the copolyreaction condition
For：Reaction temperature is 40-120 DEG C, and ethylene pressure is 3.0-25.0MPa, and the response time is 1.5-8.0 hours,
The pH value of course of reaction is controlled in 1.5-9.0, preferred 6.5-7.5.
9. the method according to any one of claim 1 to 8, it is characterised in that the EVA emulsions for obtaining
In, VAc contents in the copolymer are 35.0-95.0wt%；Emulsion viscosity is 80-160mpa.s.
10. the method according to any one of claim 1 to 8, it is characterised in that in the same of copolyreaction
When add other polymerized monomers to carry out copolymerization, in preferred propylene, n-butene, isobutene., 1- hexenes and 1- octenes
At least one.
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Citations (4)
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|---|---|---|---|---|
| US2703794A (en) * | 1951-09-04 | 1955-03-08 | Du Pont | Ethylene/vinyl acetate polymerization process |
| CN1272502A (en) * | 2000-05-30 | 2000-11-08 | 复旦大学 | High solid content nanometer polymer micro emulsion synthesizing method |
| CN1306015A (en) * | 2000-12-27 | 2001-08-01 | 中国科学院长春应用化学研究所 | Process for preparing high-ethylene ethylene vinylacetate latex |
| 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 |
-
2015
- 2015-09-16 CN CN201510590532.XA patent/CN106543325A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2703794A (en) * | 1951-09-04 | 1955-03-08 | Du Pont | Ethylene/vinyl acetate polymerization process |
| CN1272502A (en) * | 2000-05-30 | 2000-11-08 | 复旦大学 | High solid content nanometer polymer micro emulsion synthesizing method |
| CN1306015A (en) * | 2000-12-27 | 2001-08-01 | 中国科学院长春应用化学研究所 | Process for preparing high-ethylene ethylene vinylacetate latex |
| 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 |
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