CN110407983A - Carboxylic styrene butadiene latex and its preparation method and application - Google Patents
Carboxylic styrene butadiene latex and its preparation method and application Download PDFInfo
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- CN110407983A CN110407983A CN201810384802.5A CN201810384802A CN110407983A CN 110407983 A CN110407983 A CN 110407983A CN 201810384802 A CN201810384802 A CN 201810384802A CN 110407983 A CN110407983 A CN 110407983A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to polymer arts, and in particular, to a kind of carboxylic styrene butadiene latex and its preparation method and application.The method of carboxylic styrene butadiene latex is prepared the following steps are included: the mixed system containing butadiene, styrene, acrylic acid, retarder, molecular weight regulator, water, pH buffer, chelating agent and emulsifier is successively carried out polymerization reaction at 55-60 DEG C and 68-72 DEG C 1) in the presence of initiator；2) polymeric reaction product is mixed with the oil phase containing acrylic acid, styrene and butadiene and the water phase containing water, initiator, emulsifier and molecular weight regulator, and gained mixture is successively subjected to polymerization reaction at 68-72 DEG C and 80-85 DEG C.Not only partial size is small for the carboxylic styrene butadiene latex being prepared using method provided by the invention, but also has excellent stability and high adhesion strength, and when being used as cathode of lithium battery with slurry, the high and low temperature discharge performance of lithium battery is more excellent.
Description
Technical field
The present invention relates to polymer arts, and in particular, to carboxylic styrene butadiene latex and its preparation method and application.
Background technique
Carboxylic styrene butadiene latex is to add a small amount of carboxylic acid and other auxiliary agents with butadiene, styrene, is generated by emulsion polymerization
Copolymer is a kind of milky aqueous dispersion, causes the influence to ray refractive index according to its partial size difference, liquid can be with not
Same gloss.Carboxylic styrene butadiene latex cohesive force with higher and conjunctiva intensity, mechanical and chemical stability is good, mobility, storage
The advantages that stability is good, and loading is big.It is widely used in the industries such as papermaking, carpet, weaving, ornaments environmental protection, building decoration.
However, the preparation method for the carboxylic styrene butadiene latex that patent and document are related at present, particle size distribution range is greatly simultaneously
And molecular weight is uneven, and cause mechanical performance not ideal enough.For example CN101125902A discloses a kind of carpet back coating carboxylic
Base styrene-butadiene latex preparation method, polymerized monomer are used using butadiene, styrene as main monomer, are aided with function monomer, auxiliary monomer
A, auxiliary monomer B, emulsifier are used in combination using anion emulsifier and nonionic emulsifier, and initiator uses potassium peroxydisulfate water
The heat decomposition types persulfuric acid salt such as solution or ammonium persulfate aqueous solution, molecular weight regulator uses dodecyl mercaptan carbon, and uses
Electrolyte, chelating agent, pH buffer needed for polymerization.It is fed intake using intermittent fed batch or dropwise addition mode, and using decompression
Flash liberation synthesizes a kind of environment-protection ground blanket back painting carboxylic styrene butadiene latex.
For another example, CN1891728A discloses a kind of technology of preparing of novel carboxylic styrene-butadiene latex, with aliphatic conjugated diene
Hydrocarbon, aromatic ethenyl compound are main monomer, and C is added3-C5Vinyl unsaturated carboxylic acid, vinyl esters of unsaturated carboxylic acids,
Vinyl unsaturated carboxylic acid amide and vinyl unsaturated nitrile monomer are modified；Emulsifier includes alkyl phenol polyoxyethylene ether
The anion emulsifiers such as sulfate and alkyl aryl polyoxyethylene ether class nonionic emulsifier, anion emulsifier at least select alkane
A certain kind in base aryl polyoxyethylene ether sulfate or alkyl diphenyl ether disulfonate；Persulfate is initiator, alkyl sulfide
Alcohols is molecular weight regulator, using electrolyte, chelating agent needed for emulsion polymerization, pH buffer.
But the latex particle size of above scheme synthesis is larger and is not adjustable, so that particle diameter distribution of latex is concentrated, influences glue
The good mobility of cream, mechanical stability and chemical stability, thus lithium electricity when influencing to be used as cathode of lithium battery with slurry
The high and low temperature discharge performance in pond.
Summary of the invention
The purpose of the invention is to overcoming the partial size for the butadiene-styrene latex being prepared using existing method larger and
The defect of stability difference provides a kind of carboxylic styrene butadiene latex and its preparation method and application.
To achieve the goals above, the present invention provides a kind of method for preparing carboxylic styrene butadiene latex, this method include with
Lower step:
(1) in the presence of initiator, will containing butadiene, styrene, acrylic acid, retarder, molecular weight regulator,
Water, pH buffer, chelating agent and emulsifier mixed system the first polymerization reaction is successively carried out at 55-60 DEG C and in 68-72
The second polymerization reaction is carried out at DEG C；
(2) by the second polymeric reaction product with containing acrylic acid, styrene and butadiene oil mutually and containing water, cause
The water phase of agent, emulsifier and molecular weight regulator is mixed, and gained mixture is successively carried out third at 68-72 DEG C and is gathered
It closes reaction and carries out the 4th polymerization reaction at 80-85 DEG C.
The present invention also provides carboxylic styrene butadiene latexs prepared by the above method.In addition, the present invention further provides
Carboxylic styrene butadiene latex as described above is preparing the application in lithium battery.
The present invention prepares carboxylic styrene butadiene latex using the special process for gradually heating up, gradually feeding, obtained Carboxy
Not only partial size is smaller for latex, but also has excellent mobility and stability and high adhesion strength, as lithium electricity
The high and low temperature discharge performance of lithium battery is more excellent when pond negative paste ingredient uses.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The method provided by the invention for preparing carboxylic styrene butadiene latex the following steps are included:
(1) in the presence of initiator, will containing butadiene, styrene, acrylic acid, retarder, molecular weight regulator,
Water, pH buffer, chelating agent and emulsifier mixed system the first polymerization reaction is successively carried out at 55-60 DEG C and in 68-72
The second polymerization reaction is carried out at DEG C；
(2) by the second polymeric reaction product with contain (in addition) acrylic acid, (in addition) styrene and (in addition) fourth
The oil phase of diene and the water for containing water, (in addition) initiator, (in addition) emulsifier and (in addition) molecular weight regulator
It is mutually mixed, and gained mixture is successively carried out at 68-72 DEG C to third polymerization reaction and the progress the 4th at 80-85 DEG C
Polymerization reaction.
The present invention is not particularly limited the dosage of each substance in the mixed system, it is preferable that relative to 100 weight
The dosage of the butadiene of part and the total weight of styrene, the acrylic acid is 1-5 parts by weight, and the dosage of the retarder is
0.001-0.05 parts by weight, the dosage of the molecular weight regulator are 0.01-1 parts by weight, and the dosage of the water is 10-500 weight
Part is measured, the dosage of the pH buffer is 0.03-1 parts by weight, and the dosage of the chelating agent is 0.05-1 parts by weight, the emulsification
The dosage of agent is 1-10 parts by weight, and the weight ratio of butadiene and styrene is 0.3-3:1 in the mixed system.More preferably
Ground, relative to the butadiene of 100 parts by weight and the total weight of styrene, the dosage of the acrylic acid is 2-5 parts by weight, described slow
The dosage of poly- agent is 0.01-0.03 parts by weight, and the dosage of the molecular weight regulator is 0.05-0.5 parts by weight, the use of the water
Amount is 200-400 parts by weight, and the dosage of the pH buffer is 0.05-0.3 parts by weight, and the dosage of the chelating agent is 0.07-
0.1 parts by weight, the dosage of the emulsifier are 4-8 parts by weight, and in the mixed system butadiene and styrene weight ratio
For 0.5-2:1.
The preparation method of the carboxylic styrene butadiene latex provided according to the present invention there is not the amount of initiator used in step (1)
There is special requirement, for example, the total weight relative to butadiene and styrene in the mixed system of 100 parts by weight, in step (1)
The amount of the initiator used is 0.2-0.5 parts by weight.
The present invention is not particularly limited the dosage of each substance in the oily phase, it is preferable that relative to 100 parts by weight
The total weight of butadiene and styrene in the mixed system, it is described oil phase in acrylic acid dosage be 5-20 parts by weight,
The dosage of the styrene is 500-1000 parts by weight, and the dosage of the butadiene is 200-500 parts by weight.It is highly preferred that phase
For the total weight of butadiene and styrene in the mixed system of 100 parts by weight, the use of the acrylic acid in the oil phase
Amount is 10-15 parts by weight, and the dosage of the styrene is 620-720 parts by weight, and the dosage of the butadiene is 300-450 weight
Part.
The present invention is not particularly limited the dosage of each substance in the water phase, it is preferable that relative to 100 parts by weight
The total weight of butadiene and styrene in the mixed system, the dosage of water is 100-1000 parts by weight, institute in the water phase
The dosage for stating initiator is 0.1-1.5 parts by weight, and the dosage of the emulsifier is 50-500 parts by weight, the molecular weight regulator
Dosage be 0.1-10 parts by weight.It is highly preferred that relative to butadiene and styrene in the mixed system of 100 parts by weight
Total weight, the dosage of water is 400-800 parts by weight in the water phase, and the dosage of the initiator is 0.2-1 parts by weight, described
The dosage of emulsifier is 80-120 parts by weight, and the dosage of the molecular weight regulator is 2-4 parts by weight.
The preparation method of the carboxylic styrene butadiene latex provided according to the present invention, in initiator and step (2) used in step (1)
Initiator used may be the same or different, and can be each independently and existing various can cause styrene, fourth
Diene, acrylic acid carry out the substance of polymerization reaction, are preferably each independently selected from potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate
At least one.
The preparation method of the carboxylic styrene butadiene latex provided according to the present invention, emulsifier and the water in the mixed system
Emulsifier in phase may be the same or different, and can be each independently and existing various can play emulsification
Substance, be preferably each independently selected from neopelex, dodecyl sodium sulfate, sodium cetanesulfonate and oleic acid
At least one of sodium, the compound emulsifying agent being more preferably made of at least two in mentioned emulsifier.
The present invention is not particularly limited the type of the retarder, for example, sodium nitrite can be selected from, to nitroxyl chloride
At least one of benzene ortho-sulfonic acid, 2,6- dichloro paranitroanilinum and 4-Nitrobenzenesulfonyl chloride.Delay used in step (1) poly-
Agent can be identical or different with the retarder being added in the 4th polymeric reaction product.
The pH buffer can for it is existing it is various prevent pH value in system from the substance to fluctuate widely occur, it is specific
Example includes but is not limited at least one of sodium bicarbonate, saleratus, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate and ammonium carbonate.
From raw material it is ready availability from the point of view of, the pH buffer is preferably at least one in sodium bicarbonate, sodium carbonate and ammonium hydrogen carbonate
Kind.
The present invention is not particularly limited the type of the chelating agent, can selected from disodium EDTA and/
Or sodium iron ethylene diamine tetra acetate.
The preparation method of the carboxylic styrene butadiene latex provided according to the present invention, molecular weight regulator and step used in step (1)
Suddenly molecular weight regulator used in (2) may be the same or different, and can be each independently existing various can adjust
The substance for saving polymer molecular weight, for example, tert-dodecyl mercaptan, dodecyl mercaptan carbon and uncle 18 can be each independently selected from
At least one of carbon mercaptan.From raw material it is ready availability from the point of view of, molecular weight regulator used in step (1) and step (2)
Molecular weight regulator used is particularly preferably tert-dodecyl mercaptan.
The preparation method of the carboxylic styrene butadiene latex provided according to the present invention, it is preferable that the time of first polymerization reaction
It is 2-4 hours, the time of second polymerization reaction is 3-6 hours, and the time of the third polymerization reaction is 3-6 hours, institute
The time for stating the 4th polymerization reaction makes 95% or more the conversion ratio (for example, 2-4 hours) for obtaining monomer.
The preparation method of carboxylic styrene butadiene latex provided by the invention usually carries out in an inert atmosphere, to avoid air institute band
The inhibition come and chain transfer reaction.The inert atmosphere refer to do not chemically reacted with reactants and products it is any one
Kind gas or admixture of gas, such as one or more of nitrogen and periodic table of elements zero group gas.Keep the side of inert atmosphere
Method can be that above-mentioned any one gas or gas not chemically reacted with reactants and products is passed through into reaction system
Mixture.
A kind of specific embodiment according to the present invention, the preparation method of the carboxylic styrene butadiene latex include: (a) by fourth two
Alkene, styrene, acrylic acid, retarder, molecular weight regulator, water, pH buffer, chelating agent and emulsifier are added to reaction kettle
In, stirring is then started, each substance is stirred evenly in the case where revolving speed is 100-200rmp, is subsequently passed nitrogen, vacuum suction is set
It ventilates；(b) system temperature is increased at 55-60 DEG C, and the aqueous solution of initiator is added, later maintain reaction temperature
It is reacted at 55-60 DEG C 2-4 hours, then temperature is risen at 68-72 DEG C and is reacted 3-6 hours；(c) continuous into aforesaid reaction vessel
The oil phase containing acrylic acid, styrene and butadiene and the water containing water, initiator, emulsifier and molecular weight regulator is added dropwise
Temperature is risen to after being added dropwise and reacts 3-6 hours at 68-72 DEG C by phase, and temperature is then risen to 80-85 DEG C the reaction was continued 2-4
Hour.
The preparation method of carboxylic styrene butadiene latex provided by the invention, it is preferable that this method further includes toward the 4th polymerization reaction
Retarder is added in product, later cooling discharge, and steams moisture using Rotary Evaporators, when solid content reaches 40-50 weight
The pH value of system is adjusted to 8-10 when measuring %, the carboxylic styrene butadiene latex of the ultra-small grain size of high solids content can be obtained in this way.
As previously mentioned, the present invention is to the type and dosage of the retarder being added into the 4th polymeric reaction product without spy
It does not limit.For example, the retarder can be selected from sodium nitrite, paranitrochlorobenzene ortho-sulfonic acid, 2,6- dichloro paranitroanilinum
At least one of with 4-Nitrobenzenesulfonyl chloride, preferably sodium nitrite.Relative in the mixed system of 100 parts by weight
The dosage of the total weight of butadiene and styrene, the retarder being added into the 4th polymeric reaction product can be 0.2-100 weight
Measure part, preferably 0.4-5 parts by weight.
It will be appreciated to those of skill in the art that in order to avoid the influence of various ion pair polymerizations reaction, institute of the present invention
The water used is usually deionized water.
The present invention also provides carboxylic styrene butadiene latexs prepared by the above method.Present invention Carboxy obtained
The solid content of latex can be 30-70 weight %, preferably 35-65 weight %, more preferably 40-50 weight %.
In addition, the present invention also provides foregoing carboxylic styrene butadiene latexs to prepare the application in lithium battery.The present invention
Carboxylic styrene-butadiene rubber as cathode of lithium battery slurry in use, lithium battery obtained simultaneously high and low temperature with higher
Discharge performance.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example:
The average grain diameter of latex is measured by being commercially available from the ZS90 dynamic laser particle size analyzer of Malvern company, is
Volume average particle size.
The microstructure of polymer uses Switzerland Bruker company AVANCE DRX 400MHz nmr determination, surveys
Surely room temperature is used, method is hydrogen nuclear magnetic resonance spectroscopy, and solvent is deuterated chloroform.
Number-average molecular weight uses the gel permeation chromatograph of the model ALLIANCE2690 purchased from U.S. WATERS company
(GPC) it measures, wherein using THF as mobile phase, using Narrow distribution polystyrene as standard specimen, test temperature is 25 DEG C.
Embodiment 1
The embodiment is for illustrating carboxylic styrene butadiene latex provided by the invention and preparation method thereof.
(1) by 560g butadiene, 320g styrene, 40g acrylic acid, 0.09g paranitrochlorobenzene ortho-sulfonic acid, uncle 0.84g ten
Two carbon mercaptan, 2100g deionized water, 0.92g sodium bicarbonate, 0.65g disodium EDTA, 24.4g detergent alkylate
Sodium sulfonate and 16.3g dodecyl sodium sulfate are added in reaction kettle, start stirring, and revolving speed 120rmp leads to after mixing evenly
Enter nitrogen, vacuum suction, displaced air 3 times.Temperature is increased to 57 DEG C, imports the potassium peroxydisulfate water that 124g concentration is 2 weight %
Solution starts polymerization reaction, and maintaining reaction temperature is reacted 2 hours at 57 DEG C.Then being warming up to 70 DEG C, the reaction was continued 3 hours.
(2) oil of the acrylic acid containing 102.4g, 6280g styrene and 3588g butadiene is then added dropwise mutually and contains
4716g deionized water, 104.3g concentration be the persulfate aqueous solution of 2 weight %, 317.2g neopelex and
The water phase of 634.3g sodium cetanesulfonate and 31.2g tert-dodecyl mercaptan, being warming up to 72 DEG C, the reaction was continued 3 hours.Then it rises
The reaction was continued 2 hours to 85 DEG C for temperature, and the conversion ratio of monomer reaches 95% at this time, and retarder sodium nitrite 4.36g is added, cools down out
Material, takes Rotary Evaporators to steam moisture, and ammonium hydroxide is added when solid content reaches 45 weight % and adjusts pH value to 8, obtains carboxyl
Butadiene-styrene latex Q1, average grain diameter are shown in Table 1.
Embodiment 2
The embodiment is for illustrating carboxylic styrene butadiene latex provided by the invention and preparation method thereof.
(1) by 320g butadiene, 560g styrene, 18g acrylic acid, the 2,6- dichloro paranitroanilinum of 0.25g, uncle 1.5g
DDM dodecyl mercaptan, 2100g deionized water, 0.92g sodium bicarbonate, 0.88g iron edta sodium salt, 24.4g dodecyl
Benzene sulfonic acid sodium salt and 43.8g dodecyl sodium sulfate are added in reaction kettle, start stirring, revolving speed 120rmp, after mixing evenly
It is passed through nitrogen, vacuum suction, displaced air 3 times.Temperature is increased to 55 DEG C, imports the potassium peroxydisulfate that 200g concentration is 2 weight %
Aqueous solution starts polymerization reaction, and maintaining reaction temperature is reacted 3 hours at 55 DEG C.Then being warming up to 70 DEG C, the reaction was continued 3 hours.
(2) oil of the acrylic acid containing 120g, 5500g styrene and 2860g butadiene is then added dropwise mutually and contains
3620g deionized water, 260.9g concentration be the persulfate aqueous solution of 2 weight %, 363.4g neopelex and
The water phase of 390.7g enuatrol and 18.4g tert-dodecyl mercaptan, being warming up to 70 DEG C, the reaction was continued 3 hours.Then 80 DEG C are warming up to
The reaction was continued 3 hours, and the conversion ratio of monomer reaches 95% at this time, and retarder sodium nitrite 26.4g is added, and cooling discharge is taken
Rotary Evaporators steam moisture, and ammonium hydroxide is added when solid content reaches 45 weight % and adjusts pH value to 10, obtains Carboxy cream
Glue Q2, average grain diameter are shown in Table 1.
Embodiment 3
The embodiment is for illustrating carboxylic styrene butadiene latex provided by the invention and preparation method thereof.
(1) by 560g butadiene, 320g styrene, 40g acrylic acid, the 4-Nitrobenzenesulfonyl chloride of 0.12g, uncle 0.84g ten
Eight carbon mercaptan, 2100g deionized water, 0.92g sodium bicarbonate, 0.68g disodium EDTA, 24.4g detergent alkylate
Sodium sulfonate and 43.8g dodecyl sodium sulfate are added in reaction kettle, start stirring, and revolving speed 120rmp leads to after mixing evenly
Enter nitrogen, vacuum suction, displaced air 3 times.Temperature is increased to 57 DEG C, imports the potassium peroxydisulfate water that 124g concentration is 2 weight %
Solution starts polymerization reaction, and maintaining reaction temperature is reacted 2 hours at 57 DEG C.Then being warming up to 70 DEG C, the reaction was continued 3 hours.
(2) oil containing 102.4g acrylic acid, 6280g styrene and 3588g butadiene is then added dropwise mutually and contains
4716g deionized water, persulfate aqueous solution, 317.2g enuatrol and the 634.3g hexadecane that 104.3g concentration is 2 weight %
The water phase of 18 carbon mercaptan of base sodium sulfonate and uncle 31.2g, being warming up to 68 DEG C, the reaction was continued 3 hours.Then 85 DEG C of continuation are warming up to
Reaction 2 hours, the conversion ratio of monomer reaches 95% at this time, and retarder sodium nitrite 4.36g is added, and cooling discharge takes rotation
Evaporimeter steams moisture, and ammonium hydroxide is added when solid content reaches 45 weight % and adjusts pH value to 9, obtains carboxylic styrene butadiene latex Q3,
Its average grain diameter is shown in Table 1.
Comparative example 1
The comparative example is for illustrating carboxylic styrene butadiene latex of reference and preparation method thereof.
Carboxylic styrene butadiene latex is prepared according to the method for embodiment 1, unlike, all raw materials are added simultaneously, it is specific to walk
It is rapid as follows:
(1) by 560g butadiene, 320g styrene, 40g acrylic acid, 0.09g paranitrochlorobenzene ortho-sulfonic acid, uncle 0.84g ten
Two carbon mercaptan, 2100g deionized water, 0.92g sodium bicarbonate, 0.65g disodium EDTA, 24.4g detergent alkylate
Sodium sulfonate and 16.3g dodecyl sodium sulfate are added in reaction kettle, start stirring, and revolving speed 120rmp leads to after mixing evenly
Enter nitrogen, vacuum suction, displaced air 3 times.
(2) oil of the acrylic acid containing 102.4g, 6280g styrene and 3588g butadiene is then added dropwise mutually and contains
4716g deionized water, 104.3g concentration be the persulfate aqueous solution of 2 weight %, 317.2g neopelex and
The water phase of 634.3g sodium cetanesulfonate and 31.2g tert-dodecyl mercaptan.After being added dropwise, temperature is increased to 57 DEG C, is imported
124g concentration is that the persulfate aqueous solution of 2 weight % starts polymerization reaction, and successively it is small to react 2 at 57 DEG C for maintaining reaction temperature
When, it reacts 3 hours at 70 DEG C, is reacted 3 hours at 72 DEG C, reacted 2 hours at 85 DEG C, the conversion ratio of monomer reaches at this time
95%, retarder sodium nitrite 4.36g is added, cooling discharge takes Rotary Evaporators to steam moisture, when solid content reaches 45 weights
Ammonium hydroxide is added when measuring % and adjusts pH value to 8, obtains reference carboxylic styrene butadiene latex DQ1, average grain diameter is shown in Table 1.
Comparative example 2
The comparative example is for illustrating carboxylic styrene butadiene latex of reference and preparation method thereof.
Carboxylic styrene butadiene latex is prepared according to the method for embodiment 1, unlike, do not take four step temperature programmings to polymerize, tool
Steps are as follows for body:
(1) by 560g butadiene, 320g styrene, 40g acrylic acid, 0.09g paranitrochlorobenzene ortho-sulfonic acid, uncle 0.84g ten
Two carbon mercaptan, 2100g deionized water, 0.92g sodium bicarbonate, 0.65g disodium EDTA, 24.4g detergent alkylate
Sodium sulfonate and 16.3g dodecyl sodium sulfate are added in reaction kettle, start stirring, and revolving speed 120rmp leads to after mixing evenly
Enter nitrogen, vacuum suction, displaced air 3 times.Temperature is increased to 65 DEG C, imports the potassium peroxydisulfate water that 124g concentration is 2 weight %
Solution starts polymerization reaction, and maintaining reaction temperature is reacted 5 hours at 65 DEG C.
(2) oil containing 102.4g acrylic acid, 6280g styrene and 3588g butadiene is then added dropwise mutually and contains
4716g deionized water, 104.3g concentration be the persulfate aqueous solution of 2 weight %, 317.2g neopelex and
The water phase of 634.3g sodium cetanesulfonate and 31.2g tert-dodecyl mercaptan, being warming up to 80 DEG C, the reaction was continued 5 hours, single at this time
The conversion ratio of body reaches 95%, and retarder sodium nitrite 4.36g is added, and cooling discharge takes Rotary Evaporators to steam moisture, when
Solid content is added ammonium hydroxide and adjusts pH value to 8 when reaching 45 weight %, obtain reference carboxylic styrene butadiene latex DQ2, average grain diameter is shown in
Table 1.
Comparative example 3
The comparative example is for illustrating carboxylic styrene butadiene latex of reference and preparation method thereof.
Carboxylic styrene butadiene latex is prepared according to the method for embodiment 1, unlike, step (2) is added without acrylic acid, is joined
Than carboxylic styrene butadiene latex DQ3, average grain diameter is shown in Table 1.
Comparative example 4
The comparative example is for illustrating carboxylic styrene butadiene latex of reference and preparation method thereof.
Carboxylic styrene butadiene latex is prepared according to the method for embodiment 1, unlike, the acrylic acid being added in step (2) is replaced
For " acrylamide " of equivalent, reference carboxylic styrene butadiene latex DQ4 is obtained, average grain diameter is shown in Table 1.
Test case 1
Test case is used to illustrate the test of carboxylic styrene butadiene latex performance.
(1) test of peel strength:
Under room temperature (25 DEG C or so), 1.5g sodium carboxymethylcellulose (is purchased from Guangzhou Qun De trade Co., Ltd, board
Number be 30000A, number-average molecular weight 650000), 94.5g deionized water, 1.0g conductive black (be purchased from Quanzhou City Fengze District section
Fine horse chemical industry has company, Co., Ltd, trade mark XC-200), 90g natural graphite (purchased from Qingdao day and reach graphite Co., Ltd, board
Number be KS-75) and 2g carboxylic styrene butadiene latex be stirred in double-planet dispersion machine with the revolving speed of 60rmp, sample after half an hour
Product dispersion is uniform, obtains lithium battery graphite cathode slurry J1-J3 and reference lithium battery graphite cathode slurry DJ1-DJ4.
Respectively by lithium battery graphite cathode slurry J1-J3 and reference lithium battery graphite cathode slurry DJ1-DJ4 in copper foil
The film that upper coating thickness is 10 microns is good in Guangzhou section after film is dry and carries out removing by force on KJ-1065A adhesive strength tester
Degree test, the results are shown in Table 1.
(2) test of mechanical stability:
Respectively by carboxylic styrene butadiene latex Q1-Q3 and reference carboxylic styrene butadiene latex DQ1-DQ4 be placed in high-speed mixer with
The revolving speed of 2000rmp stirs half an hour, products therefrom is then crossed 300 mesh screens, and resulting solid product is dry, used
The weight ratio of desciccate and former latex measures the mechanical stability of latex, wherein weight ratio is smaller to illustrate that mechanical stability is got over
It is good.The results are shown in Table 1.
Table 1
| Number | Average grain diameter (nm) | Peel strength (mN/mm) | Mechanical stability (%) |
| Embodiment 1 | 80.8 | 0.81269 | 5.4 |
| Embodiment 2 | 86.3 | 0.82616 | 4.8 |
| Embodiment 3 | 84.5 | 0.81038 | 5.2 |
| Comparative example 1 | 126.5 | 0.54886 | 8.3 |
| Comparative example 2 | 158.3 | 0.57597 | 8.7 |
| Comparative example 3 | 143.7 | 0.60981 | 6.9 |
| Comparative example 4 | 119.9 | 0.63823 | 7.1 |
As can be seen from the above results, the carboxylic styrene butadiene latex being prepared using method provided by the invention not only partial size
It is small, but also have excellent stability and high adhesion strength.
Test case 2
Using lithium battery graphite cathode slurry J1-J3 obtained in test case 1 and reference lithium battery graphite cathode slurry
DJ1-DJ4 prepares lithium battery, and the specific method is as follows:
(1) positive preparation
2.5kg LiFePO 4,0.025kg adhesive polyvinylidene fluoride (PVDF) and 0.1kg conductive agent carbon black is mixed
It closes, method particularly includes: first using N-Methyl pyrrolidone as solvent, adhesive PVDF dissolution is configured to the solution of 6 weight %, and
LiFePO 4, conductive agent carbon black are mixed with the solution of above-mentioned PVDF respectively under stiring, stirring later forms uniform slurry
Material.
The slurry is uniformly coated on aluminium foil, then drying, roll-in at 100 DEG C, cut be made having a size of 120mm ×
The anode of 160mm, wherein the quality of positive electrode active materials LiFePO 4 is about 320g/m on pole piece2。
(2) preparation of cathode
Slurry J1-J3 and DJ1-DJ4 are uniformly coated in carbon coated aluminum foil respectively, then at 90 DEG C drying, roll-in,
It cuts and the cathode having a size of 125mm × 165mm is made, wherein the quality of negative electrode active material graphite is about 170g/m on pole piece2。
(3) assembly of battery
Above-mentioned positive and negative electrode and polypropylene screen are built up to the battery core component of a square soft bag lithium ionic cell, then will
LiPF6Nonaqueous electrolytic solution is formed by the in the mixed solvent that the concentration of 1 mol/L is dissolved in EC/DMC=1:1 (volume ratio), by this
Electrolyte is in the amount injection battery case of 5g/Ah, 20Ah soft-package battery is made in sealing.
(4) high temperature discharge performance test
1) constant-voltage charge is turned to 4.2V, cut-off current 0.02C with 0.5C constant current at room temperature, stands 10min, then with
0.5C is discharged to 3.0V；10min is stood, initial capacity, platform are recorded.
2) mesuring battary 0.5C is fully charged, test and record full piezoelectric voltage and internal resistance, thickness or diameter.
3) battery is put into constant temperature 2h in 55 ± 2 DEG C of high-temperature cabinet, then with 0.2C current discharge to 3.0V；Record is remaining
Capacity.Battery is taken out after the test and shelves 2h under the conditions of 23 ± 2 DEG C of environment temperature by this, then estimates battery appearance (no
It explodes and indeformable is determined as OK).Test result is as shown in table 2.Wherein, two parallel laboratory tests are arranged in each sample, though do not show
Out, the high temperature discharge performance of the battery of the carboxylic styrene butadiene latex preparation obtained by embodiment 2 and 3 is close with embodiment 1, determines knot
Fruit is " OK ".
(5) low temperature performance is tested
1) constant-voltage charge is turned to 4.2V, cut-off current 0.02C with 0.5C constant current at room temperature, stands 10min, then with
0.5C is discharged to 3.0V；10min is stood, initial capacity, platform are recorded.
2) mesuring battary 0.5C is fully charged, test and record full piezoelectric voltage and internal resistance, thickness.
3) battery is put into constant temperature 4h in -10 ± 2 DEG C of cryogenic box, then with 0.2C current discharge to 3.0V；(record is put
Capacitance).Battery is taken out after the test and shelves 2h under conditions of meeting above 23 ± 2 DEG C of test environment, then mesh by this
Survey battery appearance.Test result is as shown in table 2.Wherein, two parallel laboratory tests are arranged in each sample, though it is not shown, by embodiment 2
The low temperature performance of the battery of the carboxylic styrene butadiene latex preparation obtained with 3 is close with embodiment 1, determines that result is " OK ".
Table 2
It can be seen that carboxylic styrene butadiene latex made from the method for the present invention with good high and low from the result of the test case
Warm discharge performance, and it is better than comparative example.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for preparing carboxylic styrene butadiene latex, which is characterized in that method includes the following steps:
(1) in the presence of initiator, butadiene, styrene, acrylic acid, retarder, molecular weight regulator, water, pH will be contained
The mixed system of buffer, chelating agent and emulsifier successively carried out at 55-60 DEG C the first polymerization reaction and at 68-72 DEG C into
The second polymerization reaction of row；
(2) by the second polymeric reaction product with containing acrylic acid, styrene and butadiene oil mutually and containing water, initiator,
The water phase of emulsifier and molecular weight regulator is mixed, and gained mixture is successively carried out third polymerization at 68-72 DEG C
Reaction and the 4th polymerization reaction of progress at 80-85 DEG C.
2. according to the method described in claim 1, wherein, in the mixed system, relative to 100 parts by weight butadiene and
The total weight of styrene, the dosage of the acrylic acid are 1-5 parts by weight, and the dosage of the retarder is 0.001-0.05 weight
Part, the dosage of the molecular weight regulator is 0.01-1 parts by weight, and the dosage of the water is 10-500 parts by weight, the pH buffering
The dosage of agent is 0.03-1 parts by weight, and the dosage of the chelating agent is 0.05-1 parts by weight, and the dosage of the emulsifier is 1-10
Parts by weight, and the weight ratio of butadiene and styrene is 0.3-3:1 in the mixed system.
3. according to the method described in claim 1, wherein, relative in the mixed system of 100 parts by weight butadiene and
The dosage of the total weight of styrene, the acrylic acid in the oil phase is 5-20 parts by weight, and the dosage of the styrene is 500-
1000 parts by weight, the dosage of the butadiene are 200-500 parts by weight.
4. according to the method described in claim 1, wherein, relative in the mixed system of 100 parts by weight butadiene and
The total weight of styrene, the dosage of water is 100-1000 parts by weight in the water phase, and the dosage of the initiator is that 0.1-1.5 is weighed
Part is measured, the dosage of the emulsifier is 50-500 parts by weight, and the dosage of the molecular weight regulator is 0.1-10 parts by weight.
5. method described in any one of -4 according to claim 1, wherein initiator used in step (1) and step (2) institute
Initiator is each independently selected from least one of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate；
And/or the emulsifier in the mixed system and the emulsifier in the water phase are each independently selected from detergent alkylate
At least two in sodium sulfonate, dodecyl sodium sulfate, sodium cetanesulfonate and enuatrol；
And/or the retarder is selected from sodium nitrite, paranitrochlorobenzene ortho-sulfonic acid, 2,6- dichloro paranitroanilinum and to nitro
At least one of benzene sulfonyl chloride；
And/or the pH buffer is in sodium bicarbonate, saleratus, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate and ammonium carbonate
At least one；
And/or the chelating agent is selected from disodium EDTA and/or sodium iron ethylene diamine tetra acetate；
And/or molecular weight regulator used in step (1) is each independently selected from molecular weight regulator used in step (2)
At least one of 18 carbon mercaptan of tert-dodecyl mercaptan, dodecyl mercaptan carbon and uncle.
6. method described in any one of -4 according to claim 1, wherein the time of first polymerization reaction is that 2-4 is small
When, the time of second polymerization reaction is 3-6 hours, and the time of the third polymerization reaction is 3-6 hours, and the described 4th is poly-
The time for closing reaction makes 95% or more the conversion ratio for obtaining monomer.
7. method described in any one of -4 according to claim 1, wherein this method further includes toward the 4th polymeric reaction product
Middle addition retarder, cooling discharge later, and moisture is steamed using Rotary Evaporators, when solid content reaches 40-50 weight %
The pH value of system is adjusted to 8-10.
8. according to the method described in claim 7, wherein, relative in the mixed system of 100 parts by weight butadiene and
The total weight of styrene, the dosage for the retarder being added into the 4th polymeric reaction product are 0.2-100 parts by weight.
9. the carboxylic styrene butadiene latex that the method as described in any one of claim 1-8 is prepared.
10. carboxylic styrene butadiene latex as claimed in claim 9 is preparing the application in lithium battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112321761A (en) * | 2020-11-04 | 2021-02-05 | 深圳港池科技有限公司 | Preparation method of adhesive for lithium ion battery |
| CN112436183A (en) * | 2020-11-25 | 2021-03-02 | 上海空间电源研究所 | Semi-gelled electrolyte battery and preparation method thereof |
| CN117004344A (en) * | 2023-10-07 | 2023-11-07 | 淄博奥固特科技有限公司 | Carboxyl styrene-butadiene latex for lithium battery cathode and preparation method thereof |
| CN118027850A (en) * | 2024-03-01 | 2024-05-14 | 绿能纤材(重庆)科技有限公司 | Preparation method of binder for lithium battery |
| CN118108885A (en) * | 2024-03-01 | 2024-05-31 | 绿能纤材(重庆)科技有限公司 | Preparation method and application of carboxylated styrene-butadiene latex |
| CN118448635A (en) * | 2024-07-08 | 2024-08-06 | 深圳好电科技有限公司 | Negative electrode binder, negative electrode composition, negative electrode sheet and lithium ion battery |
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| CN112321761A (en) * | 2020-11-04 | 2021-02-05 | 深圳港池科技有限公司 | Preparation method of adhesive for lithium ion battery |
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| CN118027850A (en) * | 2024-03-01 | 2024-05-14 | 绿能纤材(重庆)科技有限公司 | Preparation method of binder for lithium battery |
| CN118108885A (en) * | 2024-03-01 | 2024-05-31 | 绿能纤材(重庆)科技有限公司 | Preparation method and application of carboxylated styrene-butadiene latex |
| CN118027850B (en) * | 2024-03-01 | 2024-08-02 | 绿能纤材(重庆)科技有限公司 | Preparation method of binder for lithium battery |
| CN118448635A (en) * | 2024-07-08 | 2024-08-06 | 深圳好电科技有限公司 | Negative electrode binder, negative electrode composition, negative electrode sheet and lithium ion battery |
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