CN104231173B - carboxylic styrene butadiene latex preparation system and preparation method thereof - Google Patents
carboxylic styrene butadiene latex preparation system and preparation method thereof Download PDFInfo
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- CN104231173B CN104231173B CN201410475370.0A CN201410475370A CN104231173B CN 104231173 B CN104231173 B CN 104231173B CN 201410475370 A CN201410475370 A CN 201410475370A CN 104231173 B CN104231173 B CN 104231173B
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Abstract
The present invention discloses a kind of preparation system of carboxylic styrene butadiene latex, including assisted reaction kettle, reaction kettle and degassing kettle, the assisted reaction kettle is connect with the material inlet of the reaction kettle, the material outlet of the reaction kettle is connect with the feeding mouth of the degassing kettle, the reaction kettle includes inner cylinder and is encapsulated in the end socket at inner cylinder both ends, jacket cylinder, several ultrasonic treatment units of inner cylinder side wall array are set outside the inner cylinder.The present invention also provides a kind of preparation methods of carboxylic styrene butadiene latex.The beneficial effects of the invention are as follows：Reaction efficiency is can effectively improve, side reaction is reduced and generates, monomer conversion can be improved to 99% or more, and the reaction time can shorten to 4~7 hours, reduce energy expenditure；With performances such as superior tensile strength, wear resistence, bond strength, water-fastness, alkali resistance and pollution resistances, and there is superior mechanical stability and chemical stability；In addition for system there are simple in structure, failure rate is low, it is easy to operate the advantages that.
Description
Technical field
The present invention relates to carboxylic styrene butadiene latex production and apparatus field, specifically a kind of carboxylic styrene butadiene latex preparation system and
Preparation method.
Background technology
With the rapid development of social economy, paper using amount is increasing per capita in China, reaches 60 kilograms or so per capita.In
Papermaking association of state counts, 2004~2013 years, and paper and production amount increase by 8.26% every year, and consumption figure increases every year
6.74%, wherein national paper in 2013 and 101,100,000 tons of production enterprise about 3400, national paper and production amount, compared with
Last year increases -1.37%.97,820,000 tons of consumption figure increases -2.65% compared with last year, and annual consumption is 72 kilogram (13.61 hundred million per capita
People).In major product, in major product：3,600,000 tons of newsprint output accounts for paper and cardboard total output 3.56%, consumption figure
3620000 tons, account for paper and cardboard aggregate consumption 3.70%；17,200,000 tons of uncoated writing and printing paper output, accounts for paper and cardboard is total
Yield 17.01%, 16,270,000 tons of consumption figure account for paper and cardboard aggregate consumption 16.63%；7,700,000 tons of coated printing paper output,
Paper and cardboard total output 7.62% are accounted for, 6,230,000 tons of consumption figure accounts for paper and cardboard aggregate consumption 6.37%；Wherein art paper produces
6,850,000 tons are measured, the 6.78% of paper and cardboard total output is accounted for, 5,770,000 tons of consumption figure accounts for paper and cardboard aggregate consumption 5.90%, together
Than increasing -0.69%；7,950,000 tons of paper for daily use output, accounts for paper and cardboard total output 7.86%, and 7,340,000 tons of consumption figure accounts for paper
And cardboard aggregate consumption 7.50%, increase by 0.41% on a year-on-year basis；6,350,000 tons of package paper output accounts for paper and cardboard total output
6.28%, 6,500,000 tons of consumption figure accounts for paper and cardboard aggregate consumption 6.64%；13,600,000 tons of white board output, accounts for paper and cardboard
Total output 13.45%, 13,100,000 tons of consumption figure account for paper and cardboard aggregate consumption 13.39%, wherein coated white paperboard output
13100000 tons, paper and cardboard total output 12.96% are accounted for, 12,590,000 tons of consumption figure accounts for paper and cardboard aggregate consumption 12.87%；Case
20,400,000 tons of production amount, accounts for paper and cardboard total output 20.18%, and 21,060,000 tons of consumption figure accounts for paper and cardboard aggregate consumption
21.53%；20,150,000 tons of production of fluting base paper amount, accounts for paper and cardboard total output 19.93%, 20,130,000 tons of consumption figure, account for paper and
Cardboard aggregate consumption 20.58%；2,300,000 tons of speciality paper and production amount, account for paper and cardboard total output 2.27%, consumption figure
1880000 tons, account for paper and cardboard aggregate consumption 1.92%.
Now, people are higher and higher to the quality requirement of paper.Surface coating is to improve an important way of paper quality
Diameter.With the increase of high-grade packaging demand, coating paper by be Future Development trend.In coating paper production process, to coating
The requirement of performance is very high, i.e., to have good rheological property：Under high shear condition, the viscosity of coating wants low, defeated in this way
It send with regard to very convenient, and low energy consumption；After coated, dope viscosity is replied, but cannot be too fast, and coating has certain levelability
Can, keep coating surface smooth.And it is required that improving the solid content of coating as far as possible, it can thus reduce the cost of drying.It wants
Coating is set to reach above-mentioned requirement, the performance of latex is crucial.Latex will ensure there is good adhesion strength, improve coating paper
Surface strength；When preparing the coating of high solids content, viscosity cannot be too high, the requirement of symbol conveying；After coating, there is preferable stream
Levelling energy improves the glossiness on coating paper surface.
Carboxylic styrene butadiene latex is to produce the most wide latex of upper application range in coating paper at present, but these latex binders are strong
Degree and rheological property are poor, cannot meet the requirements；Water resistance and heat resistance are all poor, after coating, the flow leveling of coating
It is poor, lead to coated face out-of-flatness.
Invention content
One of the objects of the present invention is to provide a kind of production cost is low, high conversion rate, the fast Carboxy of reaction speed
The preparation system of latex.
It is a further object of the present invention to provide a kind of production cost is low, high conversion rate, reaction speed is fast, excellent product performance
Carboxylic styrene butadiene latex preparation method.
In order to achieve the above objectives, present invention employs the following technical solutions：The preparation system of carboxylic styrene butadiene latex, packet
It includes assisted reaction kettle, reaction kettle and degassing kettle, the assisted reaction kettle to connect with the material inlet of the reaction kettle, the reaction
The material outlet of kettle is connect with the feeding mouth of the degassing kettle, and the reaction kettle includes inner cylinder and is encapsulated in inner cylinder both ends
Jacket cylinder, several ultrasonic treatment units of inner cylinder side wall array, ultrasonication is arranged outside in end socket, the inner cylinder
Device can improve reflection speed and improve reaction efficiency, monomer conversion is allow to carry to carrying out ultrasonic irradiation in inner cylinder
Height is to 99% or more.
The degassing kettle includes cylinder and is encapsulated in the end socket at cylinder both ends, and the cylinder includes large cylinder and small cylinder,
It is connected by conical ring between the large cylinder and small cylinder；Agitating shaft is set in the cylinder, if being installed on the agitating shaft
Do the blade for stirring homogeneous, the output axis connection of the one end of the mixing shaft and stirring motor, the other end of the agitating shaft
It is placed on the bearing being fixed on low head, ultrasonic treatment unit is installed in the large cylinder and small cylinder outer surface, is led to
The irradiation of ultrasonic wave is crossed, degassing process process can be improved, efficiency can improve 30% or more, and the time is also effectively contracted
It is short.
Carboxylic styrene butadiene latex, by including that following parts by weight component is made：
The emulsifier is by anion emulsifier and nonionic emulsifier with (3~4): 1 mass ratio is combined；It is described
Anion emulsifier is C8~C18 sodium alkyl benzene sulfonates, C8~C18 sodium alkyl sulfates, two phenolic ether sodium disulfonate of C8~C18 alkyl
In it is one or more；The nonionic emulsifier is C8~C12 alkylphenol-polyethenoxies that ethoxymer distribution is 5~20
C8~C12 the fatty alcohol polyoxyethylene ether and expoxy propane adduct numbers that ether, ethoxymer distribution are 5~20 are 2~10
It is one or more in C4~C8 fatty alcohol polyoxypropylene ethers.
The seed glue is selected from guar gum or locust bean gum.
The seed glue can be carboxylic styrene butadiene latex seed emulsion, and the carboxylic styrene butadiene latex seed emulsion is by following heavy
Amount number component is made：
Above-mentioned carboxylic styrene butadiene latex seed emulsion prepares in advance when in use, and main body is then added according to the above ratio
In formula, reaction system can be made more steady, it is effective improve the self leveling of carboxylic styrene butadiene latex, it being optimal
Emulsion solid content, conversion ratio, mechanical stability and chemical stability.
The mercaptan optimizing alkyl mercaptan, such as dithioglycol, ethyl mercaptan, cysteine or dialkyl group mercaptan.
The chelating agent is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate.
The function monomer can be acrylamide or N hydroxymethyl acrylamide, and addition accounts for the third of gross mass 6~8%
Acrylamide or N hydroxymethyl acrylamide comonomer, introduce amide groups on latex segment, in film forming procedure behind,
Other groups between amide groups and on amide groups and latex segment, such as carboxyl, hydroxyl, occur condensation reaction between itrile group etc. and
Next year makes cross-bond into, forms cross-linked polymer, to make linear emulsion polymer be crosslinked, produces tridimensional network, in this way
Impart the condensate more preferably performances such as tensile strength, wear resistence, bond strength, water-fastness, alkali resistance and pollution resistance.
Preferably, the function monomer is acrylonitrile, acrylamide and N hydroxymethyl acrylamide composition, wherein described
The mass ratio of acrylonitrile, acrylamide and N hydroxymethyl acrylamide is 1: 3-6: 2-3.Most preferably, the acrylonitrile, propylene
The mass ratio 1: 3: 2 of amide and N hydroxymethyl acrylamide.The carboxylic styrene butadiene latex for accessing aforementioned proportion acrylonitrile, can be used for
Improve paper printability because access acrylonitrile latex polymer coating printing when, coating and printing ink between phase
Interreaction force greatly reduces, and printing ink transfer to paper surface and absorption are more if the ink in coating, to improve paper printing
Glossiness afterwards, because acrylonitrile glass transition temperature is relatively high, on latex grafting after acrylonitrile, the glass transition temperature of latex also becomes
Height can improve the glossiness and smoothness of coating paper.According to the above ratio with the acrylamide and N hydroxymethyl acrylamide
It is used in mixed way, said effect more, keeps polymerization rate moderate, and latex stability is more preferable, and property indices are more excellent；
By introducing hydroxyl, carboxyl, amide groups functional group in proportion, the distribution sex chromosome mosaicism for solving functional monomer can be very good.
Hydroxyl effect is to be not easy to flocculate, and increases stability；Amide groups can improve cohesive force, to improve coating surface intensity.
The preparation method of carboxylic styrene butadiene latex comprising following steps：
(1) reaction kettle puts into 40~80% water, 20~40% in composition of raw materials respectively after nitrogen displacement, vacuumizing
Emulsifier, 20~40% acrylic acid, sodium pyrophosphate, function monomer, seed glue and chelating agent；
(2) after being warming up to 83~94 DEG C, butadiene and styrene, mercaptan, remaining third are at the uniform velocity added dropwise in 2~4 hours
70~80% ammonium persulfate, 5~8% caustic soda and remaining emulsifier in olefin(e) acid, composition of raw materials；
(3) after monomer dropping, reaction temperature is improved to 93~98 DEG C, the reaction was continued 2~3 hours；When monomer participates in
When the total conversion of polymerization reaches 98.0% of monomer gross mass or more, 65~75 DEG C are cooled to, turns material to degassing kettle, is added surplus
50~70% caustic soda in remaining ammonium persulfate and composition of raw materials, control degassing kettle vacuum degree are -0.07~-0.09MPa, decompression
Flash liberation 3.5~4.5 hours then proceedes to remaining caustic soda pH value to 7~9, cool to 35~45 DEG C.
Ultrasonic irradiation device is arranged in the side wall of the reaction kettle, in production, regulation power 600-1000W, and ultrasound
Wave frequency rate can be 60~80khz, and the power density of sound wave can be 2~5w/cm2.The ultrasonic wave of said frequencies is in reactant
When being propagated in system, variety classes corpuscle in liquid will be promoted to carry out appropriate intense vibration, cause to send out between liquid particle
Vigorous strong effect of impact, plays good stirring action, to make two kinds of immiscible liquid (Ru Shui and oil) emulsify,
And accelerates solute to dissolve, accelerate chemical reaction.
Preferably, the ultrasonic irradiation device is that pulsed carries out ultrasonic irradiation to the reaction kettle, often irradiates 3-6
Minute closes 3 minutes, is then then turned on and is irradiated to reaction kettle.It in this way can be to avoid material in reactor in ultrasonic irradiation
Lower excessive cavitation elevates the temperature excessively, side reaction is caused to generate.
Compared with prior art, the beneficial effects of the invention are as follows：Reaction efficiency is can effectively improve, side reaction production is reduced
Raw, monomer conversion can be improved to 99% or more, and the reaction time can shorten to 4~7 hours, greatly reduce recycling amount of monomer,
Reduce energy expenditure；Destruction of the residual monomer to system stability and the pollution to environment are farthest eliminated, is had
The performances such as superior tensile strength, wear resistence, bond strength, water-fastness, alkali resistance and pollution resistance, and there is superior machinery
Stability and chemical stability；In addition for system there are simple in structure, failure rate is low, it is easy to operate the advantages that.
Description of the drawings
Fig. 1 is the main structure diagram of reaction kettle；
Fig. 2 is the overlooking structure diagram of reaction kettle；
Fig. 3 is the structural schematic diagram of wall-attaching type ultrasound transducer apparatus；
Fig. 4 is the structural schematic diagram of forceps-shaped ultrasonic transducer apparatus；
Fig. 5 is the main structure diagram of degassing kettle；
Fig. 6 is the overlooking structure diagram of degassing kettle；
Fig. 7 is the system structural map of the preparation system of carboxylic styrene butadiene latex of the present invention.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be described in detail.
Embodiment 1
Carboxylic styrene butadiene latex, by including that following parts by weight component is made：
Embodiment 2
Carboxylic styrene butadiene latex, by including that following parts by weight component is made：
Embodiment 3
Carboxylic styrene butadiene latex, by including that following parts by weight component is made：
Embodiment 4
Carboxylic styrene butadiene latex, by including that following parts by weight component is made：
The emulsifier is by anion emulsifier and nonionic emulsifier with (3~4): 1 mass ratio is combined；It is described
Anion emulsifier is C8~C18 sodium alkyl benzene sulfonates, C8~C18 sodium alkyl sulfates, two phenolic ether sodium disulfonate of C8~C18 alkyl
In it is one or more；The nonionic emulsifier is C8~C12 alkylphenol-polyethenoxies that ethoxymer distribution is 5~20
C8~C12 the fatty alcohol polyoxyethylene ether and expoxy propane adduct numbers that ether, ethoxymer distribution are 5~20 are 2~10
It is one or more in C4~C8 fatty alcohol polyoxypropylene ethers.Preferably, the emulsifier is by neopelex: epoxy
The mass ratio that the C10 alkyl phenol polyoxyethylene ether that ethane adduct number is 15 is 3: 1 is combined.Above-mentioned anion emulsifier can be with
Control polymerization system in reaction speed appropriate, and the nonionic emulsifier added can improve the chemical stability of lotion,
Emulsifying effectiveness is improved, so as to improve performances such as the bond strength of carboxylic styrene butadiene latex, water-fastness, alkali resistance and pollution resistances.
The mercaptan optimizing alkyl mercaptan can select dithioglycol, ethyl mercaptan, cysteine or dialkyl group mercaptan one
Combination of the above in kind or two.The chelating agent is disodium ethylene diamine tetraacetate or tetrasodium ethylenediamine tetraacetate.
The function monomer can be acrylamide or N hydroxymethyl acrylamide, and addition accounts for the third of gross mass 6~8%
Acrylamide or N hydroxymethyl acrylamide comonomer, introduce amide groups on latex segment, in film forming procedure behind,
Other groups between amide groups and on amide groups and latex segment, such as carboxyl, hydroxyl, occur condensation reaction between itrile group etc. and
Next year makes cross-bond into, forms cross-linked polymer, to make linear emulsion polymer be crosslinked, produces tridimensional network, in this way
Impart the condensate more preferably performances such as tensile strength, wear resistence, bond strength, water-fastness, alkali resistance and pollution resistance.It is preferred that
, the function monomer is acrylonitrile, acrylamide and N hydroxymethyl acrylamide composition, wherein the acrylonitrile, propylene
The mass ratio of amide and N hydroxymethyl acrylamide is 1: 3-6: 2-3.Most preferably, the acrylonitrile, acrylamide and N- hydroxyls
The mass ratio 1: 3: 2 of Methacrylamide.The carboxylic styrene butadiene latex for accessing aforementioned proportion acrylonitrile can be used for improving the suitable of paper
Print property, because the latex polymer coating of access acrylonitrile, in printing, the interaction force between coating and printing ink is big
Big to reduce, printing ink transfer to paper surface and absorption are more if the ink in coating, to improve the glossiness after paper printing,
Because acrylonitrile glass transition temperature is relatively high, on latex grafting after acrylonitrile, the glass transition temperature of latex is also got higher, and can improve painting
The glossiness and smoothness of cloth paper.It is used in mixed way according to the above ratio with the acrylamide and N hydroxymethyl acrylamide, it is above-mentioned
Effect more, keeps polymerization rate moderate, and latex stability is more preferable, and property indices are more excellent；By in proportion
Hydroxyl, carboxyl, amide groups functional group are introduced, the distribution sex chromosome mosaicism for solving functional monomer is can be very good.Hydroxyl effect is not
Easily flocculation, increases stability；Amide groups can improve cohesive force, to improve coating surface intensity.
The seed glue is selected from guar gum or locust bean gum.
Preferably, the seed glue can be carboxylic styrene butadiene latex seed emulsion, and carboxylic styrene butadiene latex seed emulsion makes
With when prepare in advance, then according to the above ratio be added main body formula in, reaction system can be made more steady, effectively
Improve carboxylic styrene butadiene latex it is self leveling, being optimal emulsion solid content, conversion ratio, mechanical stability and chemistry
Stability.
Wherein, the carboxylic styrene butadiene latex seed emulsion can be made of following parts by weight component：
The improvement performance of formula see the table below, after practical above-mentioned carboxylic styrene butadiene latex seed emulsion, various performances are equal below
It can be more than following table.
Wherein, the carboxylic styrene butadiene latex seed emulsion can be made of following parts by weight component：
The improvement performance of formula see the table below, after practical above-mentioned carboxylic styrene butadiene latex seed emulsion, various performances are equal below
It can be more than following table.
Preferably, the carboxylic styrene butadiene latex seed emulsion is made of following parts by weight component：
The improvement performance of formula see the table below, after practical above-mentioned carboxylic styrene butadiene latex seed emulsion, various performances are equal below
It can be more than following table.
The carboxylic styrene butadiene latex seed emulsion that the present embodiment obtains, keeps reaction system more steady, Carboxy obtained
Latex it is self leveling preferably, conversion ratio, mechanical stability and chemical stability are all in optimum state.
The preparation method of above-mentioned carboxylic styrene butadiene latex seed emulsion comprising following steps：
(1) reaction kettle put into respectively 40~80% water in composition of raw materials, 20~40% neopelex,
20~40% acrylic acid, sodium pyrophosphate, acrylamide, guar gum and disodium ethylene diamine tetraacetate；
(2) after being warming up to 85~94 DEG C, butadiene and styrene is at the uniform velocity added dropwise in 2~3 hours, dialkyl group mercaptan, remains
70~80% ammonium persulfate, 5~8% caustic soda and remaining neopelex in remaining acrylic acid, composition of raw materials；
(3) after monomer dropping, reaction temperature is improved to 94~98 DEG C, the reaction was continued 2~3 hours；When monomer participates in
When the total conversion of polymerization reaches 98.0% of monomer gross mass or more, 67~75 DEG C are cooled to, turns material to degassing kettle, is added surplus
50~70% caustic soda in remaining ammonium persulfate and composition of raw materials, control degassing kettle vacuum degree are -0.07~-0.09MPa, decompression
Flash liberation 3~4 hours then proceedes to remaining caustic soda pH value to 7~9, cool to 35~45 DEG C.
Preferably, the preparation method of above-mentioned carboxylic styrene butadiene latex seed emulsion comprising following steps：
(1) 50% water in composition of raw materials, 30% neopelex, the third of 30% are put into respectively in reaction kettle
Olefin(e) acid, sodium pyrophosphate, acrylamide, guar gum and disodium ethylene diamine tetraacetate；
(2) after being warming up to 90 DEG C, butadiene and styrene, dialkyl group mercaptan, remaining third are at the uniform velocity added dropwise in 53 hours
75% ammonium persulfate, 6% caustic soda and remaining neopelex in olefin(e) acid, composition of raw materials；
(3) after monomer dropping, reaction temperature is improved to 95 DEG C, the reaction was continued 53 hours；When monomer participates in polymerization
When total conversion reaches 99.0% of monomer gross mass or more, 70 DEG C are cooled to, turns material to degassing kettle, remaining persulfuric acid is added
60% caustic soda in ammonium and composition of raw materials, control degassing kettle vacuum degree be -0.08MPa, vacuum flashing deaerate 4 hours, then after
Continuous remaining caustic soda pH value to 8, cools to 40 DEG C.
Embodiment 5
The preparation method of carboxylic styrene butadiene latex in above-described embodiment comprising following steps：
(1) reaction kettle through nitrogen displacement, vacuumize after, respectively put into composition of raw materials in 40% water, 20% emulsifier,
20% acrylic acid, sodium pyrophosphate, function monomer, seed glue and chelating agent, 280RPM rotating speeds are stirred.；
(2) after being warming up to 83 DEG C, butadiene and styrene, mercaptan, remaining acrylic acid, original are at the uniform velocity added dropwise in 2 hours
70% ammonium persulfate, 5% caustic soda and remaining emulsifier, 220RPM rotating speeds are stirred in material formula；
(3) after monomer dropping, reaction temperature is improved to 93 DEG C, the reaction was continued 2 hours, and 200RPM rotating speeds are stirred
It mixes；When the total conversion that monomer participates in polymerization reaches 98.0% or more of monomer gross mass, 65 DEG C are cooled to, turns material and extremely deaerates
In remaining ammonium persulfate and composition of raw materials 50% caustic soda is added in kettle, and control degassing kettle vacuum degree is -0.07MPa, and decompression is dodged
Degassing 3.5 hours is steamed, then proceedes to remaining caustic soda pH value to 7, cool to 35 DEG C.
Ultrasonic irradiation device is arranged in the side wall of the reaction kettle, and in reaction, power 600W, ultrasonic frequency can
Think 60khz, the power density of sound wave can be 2w/cm2.The ultrasonic irradiation device be pulsed to the reaction kettle into
Row ultrasonic irradiation is often irradiated 3 minutes and is closed 3 minutes.
Embodiment 6
The preparation method of carboxylic styrene butadiene latex in above-described embodiment comprising following steps：
(1) reaction kettle through nitrogen displacement, vacuumize after, respectively put into composition of raw materials in 80% water, 40% emulsifier,
40% acrylic acid, sodium pyrophosphate, function monomer, seed glue and chelating agent, 300RPM rotating speeds are stirred；
(2) after being warming up to 94 DEG C, butadiene and styrene, mercaptan, remaining acrylic acid, original are at the uniform velocity added dropwise in 4 hours
80% ammonium persulfate, 8% caustic soda and remaining emulsifier, 220RPM rotating speeds are stirred in material formula；
(3) after monomer dropping, reaction temperature is improved to 98 DEG C, the reaction was continued 3 hours, and 180RPM rotating speeds are stirred
It mixes；；When the total conversion that monomer participates in polymerization reaches 99.0% or more of monomer gross mass, 75 DEG C are cooled to, turns to expect to de-
Gas kettle, is added in remaining ammonium persulfate and composition of raw materials 70% caustic soda, and control degassing kettle vacuum degree is -0.09MPa, decompression
Flash liberation 4.5 hours then proceedes to remaining caustic soda pH value to 9, cool to 45 DEG C.
Ultrasonic irradiation device is arranged in the side wall of the reaction kettle, in reaction, power 1000W, and ultrasonic frequency
Can be 80khz, the power density of sound wave can be 5w/cm2.The ultrasonic irradiation device is pulsed to the reaction kettle
Ultrasonic irradiation is carried out, often irradiates 4 minutes and closes 3 minutes, be then then turned on and reaction kettle is irradiated.
Embodiment 7
The preparation method of carboxylic styrene butadiene latex in above-described embodiment comprising following steps：
(1) reaction kettle through nitrogen displacement, vacuumize after, respectively put into composition of raw materials in 50% water, 30% emulsifier,
30% acrylic acid, sodium pyrophosphate, function monomer, seed glue and chelating agent, 290RPM rotating speeds are stirred；
(2) after being warming up to 88 DEG C, butadiene and styrene, mercaptan, remaining acrylic acid, original are at the uniform velocity added dropwise in 3 hours
75% ammonium persulfate, 7% caustic soda and remaining emulsifier, 210RPM rotating speeds are stirred in material formula；
(3) after monomer dropping, reaction temperature is improved to 94 DEG C, the reaction was continued 3 hours；When monomer participates in the total of polymerization
When conversion ratio reaches 99.0% of monomer gross mass or more, 73 DEG C are cooled to, turns material to degassing kettle, remaining ammonium persulfate is added
With in composition of raw materials 60% caustic soda, control degassing kettle vacuum degree is -0.08MPa, and vacuum flashing deaerates 4 hours, then proceedes to
With remaining caustic soda pH value to 8,40 DEG C are cooled to.
Ultrasonic irradiation device is arranged in the side wall of the reaction kettle, and in reaction, power 800W, ultrasonic frequency can
Think 70khz, the power density of sound wave can be 4w/cm2.The ultrasonic irradiation device be pulsed to the reaction kettle into
Row ultrasonic irradiation is often irradiated 5 minutes and is closed 3 minutes, is then then turned on and irradiated to reaction kettle.
Experiment effect：
The product obtained for above-described embodiment is detected, and all detection methods are the sides provided by national standard
Method, concrete outcome are as follows.
It comes in and goes out although the detection data that the selection of heterogeneity obtains in above-described embodiment can exist, its big approximate number
Value is very nearly the same with above-mentioned data.Pass through above-mentioned testing result, it is seen that the carboxylic styrene butadiene latex that the present invention obtains has excellent
Physical and chemical performance, and physical stability and chemical stability are good, can assign paper excellent performance in the application.
The preparation system of carboxylic styrene butadiene latex, as shown in Figure 7 comprising for preparing carboxylic styrene butadiene latex seed emulsion
Assisted reaction kettle, the reaction kettle for carrying out polymerisation and degassing kettle, the assisted reaction kettle and an object in the reaction kettle
Expect that import connection, the material outlet of the reaction kettle are connect with the feeding mouth of the degassing kettle.The material of the assisted reaction kettle
Entrance is connect with mixer, and the mixer is reacted for being inputted in the assisted reaction kettle after being sufficiently mixed partial material,
The assisted reaction kettle stirring pressure is reduced, it can be effective energy saving.Wherein, the rotating speed of the assisted reaction kettle can be controlled
The low-speed running between 180-220rpm is made, the assisted reaction kettle service life can be extended in this way, also reduce failure
Rate.The reaction kettle is connect with water phase kettle and oil phase kettle, and the reaction kettle is connect with demineralized water tank measuring tank and oil phase manifold；Institute
Reaction kettle is stated to connect with initiator tank, it is described to be connect with initiator proportioning room；In addition, reaction kettle is connect with circulating water pipe, to carry
For adjusting the recirculated water of temperature.The reaction kettle is connect with recirculation return pipe and sewage effluent, for collecting recirculated water and discharge
Sewage.
The degassing kettle, as shown in Figure 5 and Figure 6, including cylinder and end socket (53, the 59) formation one for being encapsulated in cylinder both ends
A closed container.Wherein, the cylinder includes large cylinder 57 and small cylinder 54, is led between the large cylinder 57 and small cylinder 54
The connection of conical ring 56 is crossed, up big and down small structure is formed and agitating shaft 517 is set in the cylinder, installed on the agitating shaft 517
Several blades 518 for stirring homogeneous, the output axis connection of 517 one end of the agitating shaft and stirring motor 511, the stirring
The other end of axis 517 is placed on the bearing being fixed on low head 53, so that stirring is more stablized, and the agitating shaft can be permanent
Run at high speed, improve mixing effect, to improve degassing efficiency.In the large cylinder and small cylinder outer surface installation ultrasound
Wave processing unit 28 can be improved, the time is also effectively shortened by the irradiation of ultrasonic wave with efficiency.The ultrasound
The mounting means of wave processing unit 28 can be identical as the reaction kettle.But at work, the ultrasonic treatment unit 28
Power be 500-800W, ultrasonic frequency can be 70-110khz, the power density of sound wave can be 6-8w/cm2.It is preferred that
, at work, the power of the ultrasonic treatment unit 28 is 600W, and ultrasonic frequency can be 90khz, the power of sound wave
Density can be 7w/cm2 can shorten process cycle by the irradiation of ultrasonic wave, and efficiency can improve 40% or more, the time
Also effectively shortened.Manhole can be provided on upper cover 59, for personnel convenient to overhaul to being overhauled in cylinder
And cleaning.Visor 513 is set on the upper cover 59, for observing the working condition in the cylinder.In the upper cover
Two lifting lugs 515 are set on 59, are to be lifted for facilitating in installation.First charging aperture 52 is set on low head 53 in institute
The side wall setting first charging aperture 516 for stating large cylinder 57, for inputting material to be de-gassed simultaneously.In low head 53, discharge port is set
51 and vapor interface 520, for discharging and providing steam.And pressure gauge connection 521 is set in the low head, for connecting pressure
Power table.In 54 side wall of small cylinder, measuring mouth 519 is set.Setting four is fixed for installing on the side wall of the large cylinder 7
Ear mount 58, in order to install.Wherein, the stirring motor 511 is fixed on the flange 512 of upper cover 59, makes stirring electric in this way
Machine installation is more stablized.Mixing baffle 55 is set on 54 madial wall of small cylinder, to improve mixing effect.The upper envelope
Bend pipe 514 is arranged in first 59 Shanghai.Above-mentioned interface and bend pipe are both provided with flange, for facilitating connection.The material of the degassing kettle
The material outlet of entrance and reaction kettle connects, and the degassing kettle is connect with antifoaming agent tank, and the reaction kettle connects with gas-liquid separator
It connects, the degassing kettle is connect with vacuum tube, and the degassing kettle is connect with blow-down pipe；The material outlet and latex of the degassing kettle
Tank connects, and the latex after separation is stored；The degassing kettle is connect with nitrogen tube, for providing nitrogen.Proportioning room is allocated
Good antifoaming agent storage is stored with antifoaming agent tank, is then sent in degassing kettle.The gas-liquid separator is connect with water cooler, institute
It states water cooler to connect with two level gas-liquid separator, carries out two-stage gas-liquid separation, effectively improve separating effect.The two level gas-liquid
The exhaust gas liquid that separator generates is emitted into cesspool, is then handled.The water cooler is connect with circulating water pipe, for carrying
For the recirculated water of heat exchange.
The reaction kettle, as depicted in figs. 1 and 2, including inner cylinder 8 and the end socket 6 for being encapsulated in 8 both ends of inner cylinder, it is described
Jacket cylinder 7, one end of the jacket cylinder 7 and 8 airtight connection of the inner cylinder, the jacket cylinder 7 are set outside inner cylinder 8
The other end connect with jacket head 5；Agitating shaft 20 is set in the inner cylinder 8, several be used for is installed on the agitating shaft 20
The blade 21 of stirring, the output axis connection of 20 one end of the agitating shaft and stirring motor 14, the other end of the agitating shaft 20 are set
In on the bearing 23 being fixed in the lower end head 6, making stirring more stablize, and the high speed that the agitating shaft 20 can be permanent
Operating improves mixing effect, to improve product quality.The stirring motor 14 is fixed on the flange of end socket 6 of upper end, this
Sample makes stirring motor installation more stablize.Cooling component 19, the water outlet of the cooling component 19 are fixed in the inner cylinder 8
It is connect with the water inlet 17 of the jacket cylinder, the water inlet of the cooling component and the feeding mouth being arranged on upper cover connect
It connects.The cooling component 19 is fixed on by gusset component 12 on 8 madial wall of the inner cylinder.The setting in the inner cylinder 8
Temperature-measuring port 10 is provided with reinforced pipe 9 on the temperature-measuring port 10, and is provided on the temperature-measuring port 10 for being easily installed connection
Flange.Discharge port (1,22) is set in the lower end head 6, and the discharge port (1,22) passes through end socket 1 described in lower end and folder
Cover the space of end socket；In addition end socket 6 described in lower end also sets up pressure tap 2；Cooling water outlet 3 is set in jacket head, for leading
Go out cooling water.In addition, lower end temperature-measuring port 4 can also be arranged on the end socket described in lower end, it to be used for more accurate detection temperature.Institute
It states and is provided with deflector 18 in the jacket space between jacket cylinder 7 and inner cylinder 8.Water can be provided on the end socket of upper end
Flat manhole with hanging cover 13, for convenient to being overhauled and being cleared up in inner cylinder.Visor is set on the end socket of upper end, for observing
Working condition in the inner cylinder.Two lifting lugs 15 are set on the end socket of upper end, are lifted when mounted for convenient.
Four are arranged on the side wall of the jacket cylinder 7 for installing fixed ear mount 11, in order to install.The cooling component 19
It is formed by being fixed on several cooling tubes in the inner cylinder 8, the cooling tube grouping arrangement, by taking between every group of cooling tube
And flanged joint.The cooling tube is provided with four groups, is uniformly arranged on the inner cylinder madial wall.The functional interface packet
Include relief valve connection, drain, nitrogen inlet, initiator import 26, balance port, feed inlet 24, spare mouth 27 and pressure gauge
Interface etc., it is easy to use, and there is good expanded function.Several ultrasonic treatment units 28 of 8 side wall array of the inner cylinder,
For carrying out ultrasonic irradiation to inner cylinder 8.Ultrasonic treatment unit 28 can improve anti-to carrying out ultrasonic irradiation in inner cylinder
It reflects speed and improves reaction efficiency, monomer conversion is allow to be increased to 99% or more.
The ultrasonic treatment unit 28 can be fixed on 8 lateral wall of the inner cylinder.The ultrasonic treatment unit
28 can be wall-attaching type ultrasound transducer apparatus, shake and change as shown in figure 3, it includes supersonic generator 283 and ultrasonic wave
Can device 282, the supersonic generator 283 connect by electric wire and the ultrasonic wave energy converter 282 that shakes, and the ultrasonic wave shakes energy converter
It is fixed on preposition attached piece 281.The described preposition attached piece 281 installation cambered surface having as 8 lateral wall of the inner cylinder, passes through
What welding or screw were close to is fixed on 8 lateral wall of inner cylinder.Ultrasonic transducer is with its ultrasound wave irradiation direction
Perpendicular to the central axes of the inner cylinder 8, ultrasonic transducer is to 8 lateral wall internal irradiation ultrasonic wave of the inner cylinder.The patch
Wall type ultrasound transducer apparatus is uniformly fixed on 8 lateral wall of the inner cylinder, to avoid there are dead angles etc..
The ultrasonic treatment unit 28 can be forceps-shaped ultrasonic transducer apparatus, the forceps-shaped ultrasonic energy converter dress
It sets, includes as described in Figure 4 transducer assemblies and function fixture, the transducer assemblies include energy converter and amplitude transformer, energy converter
It is connect with amplitude transformer, minimum of one transducer assemblies are connect with function fixture, and the function fixture is located in the inner cylinder 8
Lateral wall.The function fixture may include predose along nearly bar block and predose along trustship block, predose is along nearly bar block and spoke
The function fixture chamber for the inner cylinder 8 for receiving ultrasound wave irradiation is accommodated according to setting in forward position trustship block, predose connects along nearly bar block
The predose is connect to clamp the inner cylinder 8 for receiving ultrasound wave irradiation along trustship block.The predose is along nearly bar block and/or spoke
It is connect by screw rod of plugging into amplitude transformer according to forward position trustship block.Energy converter can be piezoelectric type or mangneto formula.Energy converter with
Transducer assemblies made of amplitude transformer is combined by screw rod of plugging into, energy converter emit electric appliance by conducting wire and ultrasonic wave and connect
Connect, ultrasonic wave emit electric appliance generate ultrasonic wave by function fixture to 8 internal irradiation of the inner cylinder for receiving ultrasound wave irradiation, can
To significantly increase ultrasound functions.The function fixture that predose is formed along nearly bar block and predose along trustship block is by screwing screw rod group
Synthesis, predose screwed with amplitude transformer by screw rod of plugging into along nearly bar block and connect, and makes function fixture and transducer assemblies tightly
It is connected as one.It is provided with to organize naturally in the function fixture intracavitary that function fixture is constituted and constitutes lock ring snare, make function fixture
It can press from both sides and be adjacent to the function fixture chamber for receiving inner cylinder 8 described in ultrasound wave irradiation, and can very be bonded in consistent manner.Function fixture
It is that forceps-shaped ultrasonic processor skill upgrading breaks through important component, its material selection is preferably to be adjusted by material processing
The metal or alloy or other rigids of hardness and toughness assemble ultrasonic energy to reach resonance, and unobstructed irradiation is straight
Finger receives in inner cylinder 8 described in ultrasound wave irradiation, obviously can significantly promote the purpose of ultrasound functions effect.
The construction of the assisted reaction kettle is identical as the reaction kettle, and volume is only 1 to five/10ths points of reaction kettle
One of between.
The preparation system of carboxylic styrene butadiene latex of the present invention can effectively improve production efficiency, and can ensure carboxyl
The various excellent physical and chemical performances of styrene-butadiene latex.
The preferred embodiment of the present invention has been described in detail above, it should be understood that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
According to present inventive concept by logic analysis, reasoning or according to the limited available technology of experiment in prior art basis
Scheme, should be among the protection domain determined by the claims.
Claims (4)
1. the method for preparing carboxylic styrene butadiene latex in the preparation system of carboxylic styrene butadiene latex, which is characterized in that carboxy styrene-butadiene rubber
The preparation system of breast, including assisted reaction kettle, reaction kettle and degassing kettle, the material of the assisted reaction kettle and the reaction kettle into
Mouth connection, the material outlet of the reaction kettle are connect with the feeding mouth of the degassing kettle, and the reaction kettle includes inner cylinder and envelope
End socket mounted in inner cylinder both ends, is arranged jacket cylinder outside the inner cylinder, at several ultrasonic waves of inner cylinder side wall array
Device is managed, ultrasonic treatment unit is to carrying out ultrasonic irradiation in inner cylinder；
The degassing kettle includes cylinder and is encapsulated in the end socket at cylinder both ends, and the cylinder includes large cylinder and small cylinder, described
It is connected by conical ring between large cylinder and small cylinder；Agitating shaft is set in the cylinder, several use are installed on the agitating shaft
In the blade of stirring homogeneous, the output axis connection of the one end of the mixing shaft and stirring motor, the other end of the agitating shaft is placed in
It is fixed on the bearing on low head, ultrasonic treatment unit is installed in the large cylinder and small cylinder outer surface；
The method for preparing carboxylic styrene butadiene latex, includes the following steps：
(1) 40~80% water in composition of raw materials, 20~40% emulsifier, 20~40% propylene are put into respectively in reaction kettle
Acid, sodium pyrophosphate, function monomer, seed glue and chelating agent；
(2) after being warming up to 83~94 DEG C, be at the uniform velocity added dropwise in 2~4 hours butadiene and styrene, mercaptan, remaining acrylic acid,
70~80% ammonium persulfate, 5~8% caustic soda and remaining emulsifier in composition of raw materials；
(3) after monomer dropping, reaction temperature is improved to 93~98 DEG C, the reaction was continued 2~3 hours；When monomer participates in polymerizeing
Total conversion when reaching 98.0% of monomer gross mass or more, be cooled to 65~75 DEG C, turn material to degassing kettle, be added remaining
50~70% caustic soda in ammonium persulfate and composition of raw materials, control degassing kettle vacuum degree is -0.07~-0.09MPa, vacuum flashing
Degassing 3.5~4.5 hours then proceedes to remaining caustic soda pH value to 7~9, cool to 35~45 DEG C；
The carboxylic styrene butadiene latex, by including that following parts by weight component is made：
The seed glue is carboxylic styrene butadiene latex seed emulsion, and the carboxylic styrene butadiene latex seed emulsion is by following parts by weight array
Divide and is made：
The function monomer is acrylamide or N hydroxymethyl acrylamide or the function monomer is acrylonitrile, acrylamide
With N hydroxymethyl acrylamide composition, wherein the mass ratio of the acrylonitrile, acrylamide and N hydroxymethyl acrylamide is
1：3-6:2-3.
2. the method described in accordance with the claim 1 for preparing carboxylic styrene butadiene latex, which is characterized in that the side wall of the reaction kettle is set
Ultrasonic irradiation device is set, in reaction, power 600-1000W, ultrasonic frequency is 60~80khz, the power of sound wave
Density is 2~5w/cm2。
3. the method for preparing carboxylic styrene butadiene latex according to claim 2, which is characterized in that the ultrasonic irradiation device
Ultrasonic irradiation is carried out to the reaction kettle for pulsed, often irradiates 3-6 minutes and closes 3 minutes.
4. according to the method according to claim 2 or 3 for preparing carboxylic styrene butadiene latex, which is characterized in that the emulsifier is by the moon
Ionic emulsifying agent and nonionic emulsifier are with (3~4)：1 mass ratio is combined；The anion emulsifier is C8~C18
It is one or more in sodium alkyl benzene sulfonate, C8~C18 sodium alkyl sulfates, two phenolic ether sodium disulfonate of C8~C18 alkyl；It is described non-
Ionic emulsifying agent be ethoxymer distribution be 5~20 C8~C12 alkyl phenol polyoxyethylene ether, ethoxymer distribution 5
C4~C8 fatty alcohol polyoxypropylenes that~20 C8~C12 fatty alcohol polyoxyethylene ether and expoxy propane adduct numbers is 2~10
It is one or more in ether.
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| EP4043498A4 (en) * | 2020-04-24 | 2023-01-11 | LG Chem, Ltd. | Post-treatment device |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104592447B (en) * | 2015-01-12 | 2017-04-19 | 浙江天晨胶业股份有限公司 | Preparation method of carboxylic butadiene-styrene latex |
| CN105413248B (en) * | 2015-12-29 | 2017-10-31 | 浙江天晨胶业股份有限公司 | A kind of carboxylic styrene butadiene latex degassing method |
| CN105498294A (en) * | 2015-12-29 | 2016-04-20 | 浙江天晨胶业股份有限公司 | Degassing equipment |
| CN107774213A (en) * | 2016-08-30 | 2018-03-09 | 南通鸿志化工有限公司 | A kind of telescopic sodium borohydride agitating device |
| CN106478883A (en) * | 2016-11-30 | 2017-03-08 | 黄河三角洲京博化工研究院有限公司 | A kind of styrene-butadiene latex and preparation method thereof |
| CN112724846B (en) * | 2021-01-14 | 2022-08-26 | 中科华宇(福建)科技发展有限公司 | Label adhesive and preparation equipment thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2507555Y (en) * | 2001-11-07 | 2002-08-28 | 成都市九洲机电工程研究所 | Ultrasonic reactor |
| CN102786620A (en) * | 2012-07-18 | 2012-11-21 | 杭州蓝诚实业有限公司 | Small-particle-size carboxylic styrene-butadiene latex and its preparation method |
| CN203021488U (en) * | 2013-01-04 | 2013-06-26 | 珠海金鸡化工有限公司 | Preparation system of carboxy styrene-butadiene latex |
| CN203043635U (en) * | 2013-01-04 | 2013-07-10 | 珠海金鸡化工有限公司 | Degasser for producing carboxylic styrene butadiene latex |
| CN103396717A (en) * | 2013-07-25 | 2013-11-20 | 佛山市三水灏诚合成树脂有限公司 | Wallpaper water-based paint, preparation method thereof and wallpaper |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100409076B1 (en) * | 2000-12-20 | 2003-12-11 | 주식회사 엘지화학 | Method for preparing latex in use paper coating |
| EP2456837A1 (en) * | 2009-07-22 | 2012-05-30 | Basf Se | Use of film-forming polymers and organic hollow particles for coating agents |
-
2014
- 2014-09-17 CN CN201410475370.0A patent/CN104231173B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2507555Y (en) * | 2001-11-07 | 2002-08-28 | 成都市九洲机电工程研究所 | Ultrasonic reactor |
| CN102786620A (en) * | 2012-07-18 | 2012-11-21 | 杭州蓝诚实业有限公司 | Small-particle-size carboxylic styrene-butadiene latex and its preparation method |
| CN203021488U (en) * | 2013-01-04 | 2013-06-26 | 珠海金鸡化工有限公司 | Preparation system of carboxy styrene-butadiene latex |
| CN203043635U (en) * | 2013-01-04 | 2013-07-10 | 珠海金鸡化工有限公司 | Degasser for producing carboxylic styrene butadiene latex |
| CN103396717A (en) * | 2013-07-25 | 2013-11-20 | 佛山市三水灏诚合成树脂有限公司 | Wallpaper water-based paint, preparation method thereof and wallpaper |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4043498A4 (en) * | 2020-04-24 | 2023-01-11 | LG Chem, Ltd. | Post-treatment device |
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