CN106543327A - A kind of method that control stir speed (S.S.) prepares low-viscosity EVA emulsions - Google Patents
A kind of method that control stir speed (S.S.) prepares low-viscosity EVA emulsions Download PDFInfo
- Publication number
- CN106543327A CN106543327A CN201510590697.7A CN201510590697A CN106543327A CN 106543327 A CN106543327 A CN 106543327A CN 201510590697 A CN201510590697 A CN 201510590697A CN 106543327 A CN106543327 A CN 106543327A
- Authority
- CN
- China
- Prior art keywords
- stir speed
- vac
- initiator
- monomer
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The present invention relates to a kind of method that control stir speed (S.S.) prepares low-viscosity EVA emulsions, including：The pre-emulsification stage：Vinyl acetate (VAc) monomer is dissolved in into water in the presence of emulsifying agent, is stirred with the first stir speed (S.S.), obtain monomer solubilization micelle；Polymerization stage：Initiator is added in the monomer solubilization micelle obtained to step one, ethene is passed through, is stirred with the second stir speed (S.S.), make ethene emulsion copolymerization reaction be carried out with VAc monomers；Second stir speed (S.S.) is more than the first stir speed (S.S.).The present invention controls stir speed (S.S.) using two steps, and in being prevented effectively from prior art, stir speed (S.S.) is too low, and monomer droplet disperses autohemagglutination phenomenon that is uneven and occurring, and the too high gel demulsifying phenomenon brought of stir speed (S.S.), improves emulsion adhesive strength and stability.And system viscosity can be effectively reduced, and particle shape being maintained, prevents from being adhered generation, the stable exquisiteness of product emulsion, period of storage are long.
Description
Technical field
The present invention relates to a kind of method that control stir speed (S.S.) prepares 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
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 ethene 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, reaction 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, reaction 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, ethene 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, reaction time 10-15mim and 1.5-3.0h.Product VAc contains
Amount 54.50wt%, viscosity 1162mpa.s.Patent CN 103665241A 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 that control stir speed (S.S.) prepares low-viscosity EVA emulsions, can significantly reduce
Product viscosity, maintains particle shape and ductile strength.The EVA product emulsion good stabilities for obtaining, VAc contents
Moderate, excellent performance can meet different demands.
The method that control stir speed (S.S.) of the present invention prepares low-viscosity EVA emulsions, including：
Step one, pre-emulsification stage：Vinyl acetate (VAc) monomer is dissolved in into water in the presence of emulsifying agent,
It is stirred with the first stir speed (S.S.), obtains monomer solubilization micelle；
Step 2, polymerization stage：Initiator is added in the monomer solubilization micelle obtained to step one, is passed through
Ethene, is stirred with the second stir speed (S.S.), makes ethene carry out emulsion copolymerization reaction with VAc monomers.
Wherein, second stir speed (S.S.) is more than the first stir speed (S.S.).
In a particular embodiment of the present invention, first stir speed (S.S.), i.e. the stir speed (S.S.) in pre-emulsification stage is
40-70r/min；The stir speed (S.S.) of the second stir speed (S.S.), i.e. polymerization stage is 80-160r/min.
According to the present invention, the pre-emulsification stage be go it is known in the industry.Specially emulsifying agent is added with optional
The colloid protective agent one or many for entering is dissolved in water and forms micella, and being subsequently adding VAc monomers makes which by micella bag
Cover, obtain the monomer solubilization micelle of stable existence.Initiator is added, ethene is passed through, in pH value regulator
With emulsion polymerization is carried out in the presence of colloid protective agent.As long as being added without initiator in other words, can be seen as
The pre-emulsification stage.
In an embodiment of the present invention, the emulsifying agent be nonionic surfactant, preferred alkyl phenol polyoxy second
Alkene ether OP-10,0.1-22.0wt% of the emulsifier for VAc monomer consumptions.
In an embodiment of the present invention, the colloid protective agent is polyvinyl alcohol (PVA), and its consumption is VAc
The 1.5-8.0wt% of monomer consumption.PVA is typically added when initiator formation monomer micella is not added with, and
In the polymerization the phase growth of colloidal particles stage add, purpose is all to stablize polymerization system, keep particle shape.
In an embodiment of the present invention, the initiator is water-soluble free radical initiator, is drawn selected from inorganic salts
Send out agent, azo-initiator, inorganic peroxygen species initiator and inorganic oxide reduction class initiator at least
One kind, selects one or more to use cooperatively in initiator of the same race.The inorganic salts initiator is selected from over cure
At least one in sour ammonium, sodium peroxydisulfate and potassium peroxydisulfate；The azo-initiator is selected from two isobutyl miaow of azo
At least one in oxazoline hydrochloride, azo dicyano valeric acid and azo diisobutyl amidine hydrochloride；It is described inorganic
At least one of the peroxide type initiators in hydrogen peroxide, sodium peroxide and potassium peroxide.The initiator
0.1-4.5wt% of the consumption for VAc monomer consumptions.
In an embodiment of the present invention, the pH value regulator is alkaline matter, and which is selected from NaOH, carbon
At least one in sour hydrogen sodium, sodium carbonate, potassium hydroxide, saleratus and potassium carbonate, more preferably bicarbonate
Sodium.0.05-5.0wt% of the consumption of the pH value regulator for VAc monomer consumptions.
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
3.5-25.0MPa, reaction time are 1.5-8.5 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 75-150mpa.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 ethene 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.
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, transmission device, shaft and the paddle that are sequentially connected.The 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 transmission 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,
Ethene is added to carry out polymerisation 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.
The present invention is prepared on the basis of existing EVA emulsion polymerization techniques by the way of two steps control stir speed (S.S.)
Low-viscosity EVA emulsions, including：1) the pre-emulsification stage：Coated by micella in this stage VAc monomers, shape
Into the monomer solubilization micelle of stable existence.A monomer part is present in micella, and a part is in aqueous phase system with list
Body droplet form is present.Now it is stirred with middling speed, is conducive to emulsifying agent, colloid protective agent and monomer dispersion,
Maintain pre-emulsification system balance；2) copolymerization stage：Stir speed (S.S.) is improved in this stage, is conducive to monomer
More droplet is dispersed into, the emulsifying agent and glue on monomer droplet surface is adsorbed in the total surface area increase of monomer droplet
Body protective agent increases, and system micella quantity is reduced, and the emulsion particle number of generation is reduced, particle diameter increase, breast
The combination water of micelle outer layer absorption is reduced, and Free water increases, and emulsion viscosity is reduced.
Therefore, the present invention prepares low-viscosity EVA emulsions using two steps control stir speed (S.S.), can be prevented effectively from existing
In having technology, stir speed (S.S.) is too low, and monomer droplet disperses autohemagglutination phenomenon that is uneven and occurring, and stir speed (S.S.) mistake
The gel demulsifying phenomenon that height brings, improves emulsion adhesive strength and stability.And can effectively reduce system viscosity,
Particle shape is maintained, prevents from being adhered generation, the stable exquisiteness of product emulsion, period of storage are long.In addition, of the invention
Cost of material it is low, easy to operate, target good emulsion stability.And adopt one-pot batch technology, it is to avoid it is many
The problems such as kettle operation difficulty height, installation cost high energy consumption, 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 emulsification
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, paddle and stirring
The rabbling mechanism of axle.The rabbling mechanism includes stirring motor, transmission device (not shown in figure) and stirring
Axle and the paddle being fixed on shaft.When reactor works, 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, rabbling mechanism is opened,
This is the pre-emulsification stage.Initiator and pH value regulator are subsequently adding, are changed stir speed (S.S.), is passed through N2Deoxygenation,
By in ethene press-in copolyreaction kettle 1, ethylene-vinyl acetate emulsion copolyreaction after pressure is constant, is carried out.Instead
After should terminating, the material discharged from copolyreaction kettle 1 enters material foam removal tank 7, adds pH value regulator
Product postprocessing is carried out with defoamer.The material discharged from material foam removal tank 7 finally pumps into de- foam machine 9 and removes
Unreacting ethylene gas.In polymerization and last handling process, the addition and derivation of raw material and product adopt high pressure measurement
Pump 6-2,6-3,6-4,6-5,6-7 and 6-9 are pumped.
The VAc in product EVA is determined using nuclear-magnetism, elementary analysis, 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 the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 40r/min, and the stir speed (S.S.) of polymerization stage is 80r/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 61.9wt%, and emulsion viscosity is 146mpa.s, stability of emulsion
Preferably, emulsion stably can be stored 6 months.
Embodiment 2
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 45r/min, and the stir speed (S.S.) of polymerization stage is 85r/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 61.8wt%, and emulsion viscosity is 120mpa.s, stability of emulsion
Preferably, emulsion stably can be stored 7 months.
Embodiment 3
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 50r/min, and the stir speed (S.S.) of polymerization stage is 90r/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 62.2wt%, and emulsion viscosity is 111mpa.s, stability of emulsion
Preferably, emulsion stably can be stored 8 months.
Embodiment 4
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 55r/min, and the stir speed (S.S.) of polymerization stage is 100r/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 62.1wt%, and emulsion viscosity is 101mpa.s, stability of emulsion
Good, emulsion stably can be stored 10 months.
Embodiment 5
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 60r/min, and the stir speed (S.S.) of polymerization stage is 110r/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 61.7wt%, and emulsion viscosity is 98mpa.s, stability of emulsion
Good, emulsion stably can be stored 10 months.
Embodiment 6
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 65r/min；, the stir speed (S.S.) of polymerization stage is 120/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 61.8wt%, and emulsion viscosity is 91mpa.s, stability of emulsion
Good, emulsion stably can be stored 11 months.
Embodiment 7
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 70r/min, and the stir speed (S.S.) of polymerization stage is 130/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 62.0wt%, and emulsion viscosity is 85mpa.s, stability of emulsion
Good, emulsion stably can be stored 11 months.
Embodiment 8
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 70r/min, and the stir speed (S.S.) of polymerization stage is 140/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 62.3wt%, and emulsion viscosity is 75mpa.s, stability of emulsion
Preferably, emulsion stably can be stored 12 months.
Embodiment 9
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 70r/min, and the stir speed (S.S.) of polymerization stage is 150/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 62.1wt%, and emulsion viscosity is 72mpa.s, stability of emulsion
Good, emulsion stably can be stored 13 months.
Embodiment 10
Ammonium persulfate is adopted for initiator, 0.3wt% of the consumption for vinyl acetate；O/W systems, surface are lived
Property agent op-10 consumptions for VAc monomer consumptions 10.0wt%；Colloid protective agent PVA consumptions are VAc monomers
The 3.0wt% of consumption；0.5wt% of the pH value regulator sodium acid carbonate consumption for VAc monomer consumptions；Polymerization is anti-
Temperature is answered for 80 DEG C, ethylene reaction pressure 75.0MPa, the pH value of course of reaction are controlled 6.5.Pre-emulsification rank
The stir speed (S.S.) of section is 70r/min, and the stir speed (S.S.) of polymerization stage is 160/min, polymerization reaction time 4.5h.
Under the conditions of this, in polymerizate, VAc contents are 62.0wt%, and emulsion viscosity is 70mpa.s, stability of emulsion
Good, emulsion stably can be stored 12 months.
Comparative example 1
The stir speed (S.S.) of pre-emulsification stage and polymerization stage is 30r/min, and other chargings and reaction condition are with enforcement
Example 1.Under the conditions of this, polymerizate VAc contents are 75.1wt%, and emulsion viscosity is 511mpa.s.Monomer is certainly
Poly- obvious, product latexes particle is adhered seriously, and emulsion was put to 1 week precipitation occurs.
Comparative example 2
The stir speed (S.S.) of pre-emulsification stage and polymerization stage is 170r/min, and other chargings and reaction condition are with real
Apply example 1.Under the conditions of this, be polymerized mid-term system breakdown of emulsion, polymerization failure.
Comparative example 3
Using Two-step control stir speed (S.S.), pre-emulsification stage stir speed (S.S.) is 30r/min, the stirring of polymerization stage
Speed is 60r/min, and other chargings and reaction condition are with embodiment 1.Under the conditions of this, polymerizate VAc contents
For 67.4wt%, emulsion viscosity is 325mpa.s.Monomer autohemagglutination substantially, product latexes particle be adhered it is more serious,
Emulsion was put to 3 weeks there is precipitation.
Comparative example 4
Using Two-step control stir speed (S.S.), the stir speed (S.S.) in pre-emulsification stage is 80r/min, and polymerization stage is stirred
It is 170r/min to mix speed, and other chargings and reaction condition are with embodiment 1.Under the conditions of this, polymerization mid-term is same
System breakdown of emulsion, polymerization failure.
In embodiment 1-10, the stir speed (S.S.) of pre-emulsification stage and polymerization stage gradually rises, emulsion-stabilizing storage
Time first raises and reduces afterwards.Under relatively, the emulsion combination property of embodiment 6-10 is preferable.
Embodiment and comparative example 1 and 2 are carried out into Data Comparison, is illustrated according to the method for the present invention, in pre-emulsification
With polymerization stage adopt different stir speed (S.S.)s, the VAc contents of product emulsion and moderate viscosity, stable system,
Occur without gel and demulsifying phenomenon, product period of storage is long.Embodiment and comparative example 3 and 4 are carried out into data pair
Than illustrating that the stir speed (S.S.) that two steps are adopted can not exceed the framework of the present definition.
To sum up, the present invention is stirred using the control of two steps in ethylene-vinyl acetate c one-pot batch production process
Speed production low-viscosity ethylene-vinyl acetate emulsion product is mixed, system viscosity can be significantly reduced, particle is obtained
Form is excellent, the EVA product emulsions of good stability, widens significantly EVA emulsion applications scopes, meets different
Demand.And one-pot batch technology to avoid many kettle operation difficulties high, the problems such as installation cost high energy consumption, with compared with
High 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 that control stir speed (S.S.) prepares low-viscosity EVA emulsions, including：
Step one, pre-emulsification stage：VAc monomers are dissolved in into water in the presence of emulsifying agent, with the first stir speed (S.S.)
It is stirred, obtains monomer solubilization micelle；
Step 2, polymerization stage：Initiator is added in the monomer solubilization micelle obtained to step one, is passed through
Ethene, is stirred with the second stir speed (S.S.), makes ethene carry out emulsion copolymerization reaction with VAc monomers；
Wherein, second stir speed (S.S.) is more than the first stir speed (S.S.).
2. method according to claim 1, it is characterised in that first stir speed (S.S.) is 40-70r/min；
Second stir speed (S.S.) is 80-160r/min.
3. method according to claim 1 and 2, it is characterised in that the emulsifying agent is non-ionic surface
Activating agent, preferred APES OP-10.
4. the method according to right wants 3, it is characterised in that the consumption of the emulsifying agent is VAc monomers
The 0.1-22.0wt% of consumption.
5. method according to any one of claim 1 to 4, it is characterised in that in the process,
Using polyvinyl alcohol as colloid protective agent, preferably 1.5-8.0wt% 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
At least one in class initiator is reduced with inorganic oxide, the preferably initiator amount is VAc monomer consumptions
0.1-4.5wt%.
7. the method according to any one of claim 1 to 6, it is characterised in that in the copolyreaction
During, using alkaline matter as pH value regulator, its be selected from NaOH, sodium acid carbonate, sodium carbonate,
At least one in potassium hydroxide, saleratus and potassium carbonate, preferably sodium acid carbonate, the preferably pH value
0.05-5.0wt% of the consumption of conditioning agent for VAc monomer consumptions.
8. the method according to any one of claim 1 to 7, it is characterised in that the bar of the copolyreaction
Part is：Reaction temperature is 40-125 DEG C, and ethylene pressure is 3.5-25.0MPa, and the reaction time is 1.5-8.5 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 75-150mpa.s.
10. the method according to any one of claim 1 to 9, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510590697.7A CN106543327B (en) | 2015-09-16 | 2015-09-16 | A method of control stirring rate prepares low-viscosity EVA lotion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510590697.7A CN106543327B (en) | 2015-09-16 | 2015-09-16 | A method of control stirring rate prepares low-viscosity EVA lotion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106543327A true CN106543327A (en) | 2017-03-29 |
| CN106543327B CN106543327B (en) | 2019-02-19 |
Family
ID=58361635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510590697.7A Active CN106543327B (en) | 2015-09-16 | 2015-09-16 | A method of control stirring rate prepares low-viscosity EVA lotion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106543327B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372813A (en) * | 2010-08-24 | 2012-03-14 | 中国石油化工集团公司 | Low-viscosity vinyl acetate-ethylene (VAE) copolymer emulsion and synthetic method and application thereof |
| CN102372814A (en) * | 2010-08-24 | 2012-03-14 | 中国石油化工集团公司 | High-solid content vinyl acetate-ethylene (VAE) copolymer emulsion and production method thereof |
| CN103665241A (en) * | 2012-09-11 | 2014-03-26 | 中国石油化工集团公司 | Cationic ethylene-vinyl acetate copolymer emulsion and production method thereof |
-
2015
- 2015-09-16 CN CN201510590697.7A patent/CN106543327B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372813A (en) * | 2010-08-24 | 2012-03-14 | 中国石油化工集团公司 | Low-viscosity vinyl acetate-ethylene (VAE) copolymer emulsion and synthetic method and application thereof |
| CN102372814A (en) * | 2010-08-24 | 2012-03-14 | 中国石油化工集团公司 | High-solid content vinyl acetate-ethylene (VAE) copolymer emulsion and production method thereof |
| CN103665241A (en) * | 2012-09-11 | 2014-03-26 | 中国石油化工集团公司 | Cationic ethylene-vinyl acetate copolymer emulsion and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 朱宝轩 编: "《化工工人岗位培训教材 化工工艺基础》", 30 June 2004, 化学工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106543327B (en) | 2019-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW293826B (en) | ||
| CN102471418A (en) | Composite polymer emulsion | |
| EP0115468B1 (en) | Process for producing stable large particle size latices | |
| CN103596989B (en) | For the vinyl ester/ethylene copolymer dispersion used in tackiness agent formulation | |
| US20010053814A1 (en) | Acrylic pressure-sensitive adhesive and process for producing the same | |
| CN104861107B (en) | The preparation method of silicon third miniemulsion | |
| CN106543298B (en) | A method of addition assistant for emulsifying agent prepares EVA lotion | |
| CN111187376B (en) | Saponification-free acrylic emulsion and preparation method thereof | |
| WO2019126913A1 (en) | A method for preparing aqueous copolymer dispersions | |
| CN106543327A (en) | A kind of method that control stir speed (S.S.) prepares low-viscosity EVA emulsions | |
| CN106543342A (en) | A kind of method that employing acrylic acid prepares low-viscosity EVA emulsions | |
| CN106543340B (en) | A method of EVA elastomer emulsions are prepared using high-pressure process | |
| CN106543337B (en) | A kind of method that ethylene segmentation pressurization prepares EVA lotion | |
| CN106543338B (en) | A method of preparing low-viscosity EVA lotion | |
| CN106543335B (en) | A method of seed monomer is added and prepares low-viscosity EVA lotion | |
| CN106543339A (en) | A kind of method that employing low polymerization degree PVA prepares low-viscosity EVA emulsions | |
| CN106543326A (en) | A kind of method for preparing low-viscosity EVA emulsions | |
| CN107793518A (en) | Application of the nertralizer in the emulsion particle diameter of control EVA elastomer emulsions | |
| CN106543329A (en) | A kind of method for preparing low-viscosity EVA emulsions | |
| CN106543325A (en) | A kind of method for preparing low-viscosity EVA emulsions | |
| CN107793517A (en) | A kind of method for preparing EVA elastomer microemulsions | |
| CN107793511A (en) | A kind of method for preparing EVA elastomer microemulsions | |
| CN107793520A (en) | A kind of method for preparing polyethylene polyvinyl acetate ester elastomer emulsifies free microemulsion | |
| EP1281739B1 (en) | Acrylic pressure-sensitive adhesive and process for producing the same | |
| CN107793519A (en) | A kind of method for preparing EVA elastomer microemulsions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |