CN110483674B - Butadiene-styrene copolymer latex for paper coating and preparation method and application thereof - Google Patents
Butadiene-styrene copolymer latex for paper coating and preparation method and application thereof Download PDFInfo
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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Abstract
The invention relates to butadiene-styrene copolymer latex for paper coating, a preparation method and application thereof. The copolymer latex includes: soft and hard two-phase copolymer and water, at least one phase is formed by emulsion polymerization of butadiene, styrene, functional monomer and unsaturated carboxylic acid monomer; the weight of the monomer mixture of the soft phase copolymer accounts for 20-50 wt% of the total weight of the monomer mixture; the weight of the monomer mixture of the hard phase copolymer accounts for 50-80 wt% of the total weight of the monomer mixture; the preparation method comprises a prepolymerization stage, a polymerization stage and a degassing stage; and application in the field of paper coating. The invention has the advantages that: the latex has stable performance, strong compatibility with coating, strong controllability of particle size and glass transition temperature, higher dry-wet napping strength, better adhesion, glossiness and smoothness and capability of meeting the requirement of high-speed coating of a paper machine.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of emulsion polymerization copolymer latex, in particular to butadiene-styrene copolymer latex for paper coating and a preparation method and application thereof.
[ background of the invention ]
In recent years, with the improvement of the cultural living standard of people, the demand of various types of coated paper and high-grade paper coated paper for publishing printing and commercial printing is rapidly increased, and the demand of styrene-butadiene latex as one of the main raw materials for paper coating is increased more and more, and the quality requirement is also increased more and more. The current trend of styrene-butadiene latex is toward multi-function and high-functionalization. The most excellent properties of the highly functionalized latex are: the film forming temperature is low, the performance is good, and the stress is higher at normal temperature, so that the stiffness and the gloss of the coated paper, the printing gloss and the surface strength are in optimal balance.
The Chinese patent application with the application number of CN201810174129.2 discloses a preparation method of modified styrene-butadiene latex with a core-shell structure, wherein an inner core of the modified styrene-butadiene latex consists of butadiene, styrene, alkenyl carboxylic acid, nitrile monomer and organic silicon monomer, and an outer shell of the modified styrene-butadiene latex consists of alkyl methacrylate, alkyl acrylate, alkenyl carboxylic acid, a cross-linking agent and an adhesive force monomer.
The Chinese patent with the application number of CN201510354361.0 discloses a starch-based biological latex with a core-shell structure and a preparation method thereof. The latex has a core-shell two-layer structure, wherein the core layer is a cross-linked copolymer mainly comprising starch derivatives and alkene hard monomers; the shell layer is a copolymer mainly comprising vinyl soft monomers. The preparation method comprises the following steps: (1) firstly, stirring starch derivatives and water uniformly, and heating and gelatinizing to prepare starch slurry; (2) adding partial monomers, an initiator, an emulsifier and a crosslinking monomer into the starch slurry to prepare a core-layer polymer; (3) continuously adding the rest monomers, the emulsifier and the initiator, and coating the shell layer polymer on the core layer polymer; (4) and filtering the reaction product to obtain the starch-based biological latex with the core-shell structure. Compared with the traditional starch-based biological latex, the latex can improve the performance of the biological latex without increasing the cost, and partially or completely replaces the conventional carboxylic styrene-butadiene latex or styrene-acrylic latex in the papermaking field.
The above patents all disclose processes for the preparation of latexes for coated paper. However, it is difficult to achieve the desired water-resistant printing strength and ink receptivity, and the surface strength, printing gloss, and blister resistance cannot meet the requirements for high-speed coating on a paper machine. This requires a certain molecular and particle design of the SBR latex to achieve a balance of properties.
Based on the above technical situation, the present inventors have proposed the following technical solutions.
[ summary of the invention ]
The first technical problem to be solved by the invention is to overcome the defects of the prior art and provide butadiene-styrene copolymer latex for paper coating, which has stable performance, strong compatibility with coating, strong controllability of particle size and glass transition temperature, higher dry-wet napping strength, better adhesion, glossiness and smoothness for paper and can meet the requirement of high-speed coating of a paper machine.
The second technical problem to be solved by the present invention is to provide a method for preparing butadiene-styrene copolymer latex for paper coating.
The third technical problem to be solved by the present invention is to propose an application of butadiene-styrene copolymer latex for paper coating.
In order to solve the first technical problem, the invention adopts the following technical scheme: the copolymer latex includes: soft and hard two-phase copolymer and water, at least one phase is formed by emulsion polymerization of butadiene, styrene, functional monomer and unsaturated carboxylic acid monomer; the weight of the monomer mixture of the soft phase copolymer accounts for 20-50 wt% of the total weight of the monomer mixture; the weight of the monomer mixture of the hard phase copolymer accounts for 50-80 wt% of the total weight of the monomer mixture; the copolymer latex has a particle size of 100-200 nm; the potential is-10 to-30 mv, the gel content is 70 to 90 percent, the glass transition temperature is-5 to 5 ℃ and 7 to 15 DEG C
Further, in the above technical solution, the soft phase copolymer composition includes: butadiene monomer: 39-44%; styrene monomer: 54-58%; unsaturated carboxylic acid: 2-4%; the hard phase copolymer latex comprises the following components: butadiene monomer: 33 to 38 percent; styrene monomer: 56-61%; unsaturated carboxylic acid: 2.0-5.0%; functional monomer: 2.0 to 5.0 percent.
Further, in the above technical scheme, the unsaturated carboxylic acid is any one or a mixture of acrylic acid, itaconic acid, methacrylic acid, fumaric acid and maleic acid, and preferably, the soft phase and the hard phase are a mixture of acrylic acid and itaconic acid in a weight ratio of 1: 1-3: 1.
In the technical scheme, the functional monomer is any one or a mixture of acrylonitrile, methyl methacrylate, acrylamide and hydroxymethyl acrylamide, and preferably a mixture of acrylonitrile and hydroxymethyl acrylamide in a mass ratio of 3: 1-1: 1.
In order to solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the butadiene-styrene copolymer latex with the heterogeneous structure comprises the following specific steps:
(1) prepolymerization stage
Dissolving the seed latex, the emulsifier accounting for 0.10-0.25 wt% of the total weight, the electrolyte and the chelating agent by using deionized water to prepare a water solution, adding the water solution into a reaction kettle, stirring and heating to 75-95 ℃. Beginning to dropwise add 11.5-12.8 wt% of butadiene monomer, 15.8-17 wt% of styrene monomer, 0.7-0.8 wt% of unsaturated carboxylic acid, 0.10-0.25 wt% of emulsifier and 0.20-0.24 wt% of initiator, wherein the dropwise adding time is 0.5-1.5 hours;
(2) polymerisation stage
After the pre-reaction in the step (1) is finished, continuously dripping 0.30-0.42 wt% of emulsifier, 0.4-0.5 wt% of initiator, 13.3-14.9 wt% of butadiene monomer, 22.3-23.9 wt% of styrene monomer, 0.8-1 wt% of unsaturated carboxylic acid, 0.8-1 wt% of functional monomer and molecular weight regulator into a reaction kettle; continuously adding other materials except the initiator solution for 2.0-3.0 hours, and keeping the reaction temperature at 75-95 ℃; the initiator solution is continuously added for 3.5-4.5 hours; after the continuous dropwise adding is finished, preserving the heat for 1-3 hours at the temperature of 80-100 ℃;
(3) degassing stage
After the reaction is finished, the product is subjected to flash evaporation and steam stripping steps, and then the degassing stage is finished;
feeding the latex for 1.5-3 hours in a flash evaporation process, wherein the vacuum degree is-0.05-0.095 MPa, and the temperature is 60-90 ℃; in the stripping process, adding a redox initiator accounting for 0.05-0.075% of the total amount of the latex or a thermal initiator accounting for 0.05-0.1%, wherein the steam flow is 1-3 tons/hour, the stripping time is 2.5-4.5 hours, the vacuum degree is-0.65-0.085 MPa, and the temperature is 65-85 ℃;
and finally cooling, adding alkali to neutralize until the pH value is neutral, and filtering to obtain the butadiene-styrene copolymer latex with a heterogeneous structure.
Further, in the technical scheme of the preparation method of the copolymer latex, in the degassing stage, the redox initiator is hydrogen peroxide and sodium bisulfite, dicumyl peroxide and sodium bisulfite, or hydrogen peroxide pair in a mass ratio of 1: 1-1: 1.5
Alkane and sodium bisulfite, and the thermal initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate.
Further, in the technical scheme of the preparation method of the copolymer latex, the emulsifier is an anionic emulsifier; the electrolyte is potassium chloride, sodium chloride or sodium carbonate; the chelating agent is ethylenediamine tetraacetic acid and disodium salt thereof; the molecular weight regulator is tert-dodecyl mercaptan or n-dodecyl mercaptan or the mixture of the tert-dodecyl mercaptan and the n-dodecyl mercaptan.
Further, in the technical scheme of the preparation method of the copolymer latex, the feeding of the latex is carried out for 1.5-3 hours in the flash evaporation process, the vacuum degree is-0.05-0.095 MPa, and the temperature is 60-90 ℃; in the stripping process, a redox initiator accounting for 0.05-0.075% of the total amount of the latex or a thermal initiator accounting for 0.05-0.1% of the total amount of the latex is added, the steam flow is 1-3 tons/hour, the stripping time is 2.5-4.5 hours, the vacuum degree is-0.65-0.085 MPa, and the temperature is 65-85 ℃.
In order to solve the third technical problem, the invention adopts the following technical scheme: the copolymer latex is applied to paper coating, and when the paper coating is carried out, the copolymer latex is mixed with calcium carbonate, a dispersing agent, a thickening agent and a water repellent agent to prepare a complex for use, wherein the complex comprises the following components in percentage by mass: 8-10% of latex, 0.1-0.2% of dispersant, 0.05-0.15% of thickener and 0.25-0.35% of water repellent agent; calcium carbonate: the rest is obtained; the dispersing agent is inorganic phosphate or polyacrylate, the thickening agent is acrylic acid copolymer, and the water-resistant agent is any one of glyoxal, polyamine polyurea, melamine formaldehyde resin and ammonium carbonate.
The invention has the beneficial effects that: the butadiene-styrene copolymer latex with the heterogeneous structure is a soft core and a middle hard shell, has strong controllability on the particle size and the glass transition temperature of the latex, and can adjust the particle size and the glass transition temperature of a product according to specific requirements. The use of the anionic emulsifier enables a hydration layer and an adsorption layer to be formed between the soft phase and the hard phase of the polymer, and the product has stronger stability and better compatibility with the coating through physical adsorption and chemical bond combination. The latex can endow paper with higher dry and wet napping strength, better cohesive force, glossiness and smoothness, meet the quality requirements of various types of coated paper, high-grade paper and coated paper, and particularly meet the requirements of water-resistant printing strength, ink acceptance and blistering resistance under the conditions of high coating speed and development of a flat printing technology.
[ detailed description ] embodiments
The invention discloses butadiene-styrene copolymer latex for paper coating and a preparation method and application thereof. The copolymer latex consists of a soft-hard two-phase copolymer and water, and at least one phase is formed by emulsion polymerization of butadiene, styrene, a functional monomer and an unsaturated carboxylic acid monomer.
Wherein the soft phase copolymer composition comprises:
butadiene monomer: 39-44%;
styrene monomer: 54-58%;
unsaturated carboxylic acid: 2-4%;
the hard phase copolymer latex composition comprises:
butadiene monomer: 33 to 38 percent;
styrene monomer: 56-61%;
unsaturated carboxylic acid: 2.0-5.0%;
functional monomer: 2.0 to 5.0 percent.
The unsaturated carboxylic acid is one or a mixture of more of acrylic acid, itaconic acid, methacrylic acid, fumaric acid and maleic acid, and preferably the mixture of acrylic acid and itaconic acid is used for the soft phase and the hard phase in a weight ratio of 1: 1-3: 1.
The functional monomer is one or a mixture of several of acrylonitrile, methyl methacrylate, acrylamide and hydroxymethyl acrylamide, and the mixture of the acrylamide and the hydroxymethyl acrylamide in a mass ratio of 3: 1-1: 1 is preferred.
The copolymer latex has a particle size of 100-200 nm; the potential is-10 to-30 mv, the gel content is 70 to 90 percent, and the glass transition temperature is-5 to 5 ℃ and 7 to 15 ℃.
The preparation method of the copolymer latex comprises the following steps:
(1) prepolymerization stage
Dissolving the seed latex, the emulsifier accounting for 0.10-0.25 wt% of the total weight, the electrolyte and the chelating agent by using deionized water to prepare a water solution, adding the water solution into a reaction kettle, stirring and heating to 75-95 ℃. Beginning to dropwise add 11.5-12.8 wt% of butadiene monomer, 15.8-17 wt% of styrene monomer, 0.7-0.8 wt% of unsaturated carboxylic acid, 0.10-0.25 wt% of emulsifier and 0.20-0.24 wt% of initiator, wherein the dropwise adding time is 0.5-1.5 hours;
(2) polymerisation stage
After the pre-reaction in the step (1) is finished, continuously dripping 0.30-0.42 wt% of emulsifier, 0.4-0.5 wt% of initiator, 13.3-14.9 wt% of butadiene monomer, 22.3-23.9 wt% of styrene monomer, 0.8-1 wt% of unsaturated carboxylic acid, 0.8-1 wt% of functional monomer and molecular weight regulator into a reaction kettle; continuously adding other materials except the initiator solution for 2.0-3.0 hours, and keeping the reaction temperature at 75-95 ℃; the initiator solution is continuously added for 3.5-4.5 hours; after the continuous dropwise adding is finished, preserving the heat for 1-3 hours at the temperature of 80-100 ℃;
(3) degassing stage
After the reaction is finished, the product is subjected to flash evaporation and steam stripping steps, and then the degassing stage is finished;
feeding the latex for 1.5-3 hours in a flash evaporation process, wherein the vacuum degree is-0.05-0.095 MPa, and the temperature is 60-90 ℃; in the stripping process, adding a redox initiator accounting for 0.05-0.075% of the total amount of the latex or a thermal initiator accounting for 0.05-0.1%, wherein the steam flow is 1-3 tons/hour, the stripping time is 2.5-4.5 hours, the vacuum degree is-0.65-0.085 MPa, and the temperature is 65-85 ℃;
and finally cooling, adding alkali to neutralize until the pH value is neutral, and filtering to obtain the butadiene-styrene copolymer latex with a heterogeneous structure.
In the degassing stage, the redox initiator is hydrogen peroxide and sodium bisulfite, or dicumyl peroxide and sodium bisulfite, or hydrogen peroxide pair with the mass ratio of 1: 1-1: 1.5
Alkane and sodium bisulfite, and the thermal initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate.
The emulsifier is an anionic emulsifier and comprises: any one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alkyl alcohol ether sulfate, sulfonated succinate and alkyl ether sulfonated succinate.
The electrolyte is potassium chloride, sodium chloride or sodium carbonate and the like.
The chelating agent is ethylenediamine tetraacetic acid and disodium salt thereof, EDTA is abbreviated.
The molecular weight regulator is tert-dodecyl mercaptan, n-dodecyl mercaptan or their mixture.
Further, in the technical scheme of the preparation method of the copolymer latex, the feeding of the latex is carried out for 1.5-3 hours in the flash evaporation process, the vacuum degree is-0.05-0.095 MPa, and the temperature is 60-90 ℃; in the stripping process, a redox initiator accounting for 0.05-0.075% of the total amount of the latex or a thermal initiator accounting for 0.05-0.1% of the total amount of the latex is added, the steam flow is 1-3 tons/hour, the stripping time is 2.5-4.5 hours, the vacuum degree is-0.65-0.085 MPa, and the temperature is 65-85 ℃.
In the preparation process, in the emulsion polymerization, various additives such as electrolyte, chelating agent, buffering agent, dispersing agent and the like can be added into a polymerization reaction system according to needs; these substances are generally used in conventional amounts.
In the emulsion polymerization of the invention, a specified amount of water, the unsaturated carboxylic acid, the emulsifier, various auxiliary agent solutions, the monomer and the molecular weight regulator are added into a reactor, the initiator solution is added when the temperature is raised to the reaction temperature, and the rest of the monomer, the emulsifier, various auxiliary agent solutions, the unsaturated carboxylic acid, the molecular weight regulator and the like are continuously added in the polymerization process; the reaction was terminated when the polymerization conversion was greater than 99% and the final latex solids content was 50. + -. 1%.
The butadiene-styrene copolymer latex having a heterogeneous structure prepared by the present invention can be applied to the field of papermaking, i.e., used for paper coating. When paper is coated, the copolymer latex is required to be mixed with calcium carbonate, a dispersing agent, a thickening agent and a water-resisting agent to prepare a complex for use, and the complex comprises the following components in percentage by mass: 8 to 10 percent of latex, 0.1 to 0.2 percent of dispersant, 0.05 to 0.15 percent of thickener and 0.25 to 0.35 percent of water repellent agent; calcium carbonate: the rest is obtained;
the dispersant is inorganic phosphate or polyacrylate;
the thickening agent is acrylic acid copolymer;
the water repellent agent is any one of glyoxal, polyamine polyurea, melamine formaldehyde resin and ammonium methyl carbonate.
The following provides specific embodiments of the butadiene-styrene copolymer latex having a heterogeneous structure and the method for preparing the same, and the present invention will be further described with reference to comparative examples.
In the examples and comparative examples, all materials are in mass fraction.
The emulsion polymerization was carried out in a 10 liter stainless steel autoclave, purged with nitrogen, equipped with a stirrer, and controlled in temperature.
Example 1
In a 10L stainless steel autoclave, deionized water in an amount of 29.01 wt%, seed latex in an amount of 0.72 wt%, sodium dodecylbenzenesulfonate in an amount of 0.2 wt%, and EDTA in an amount of 0.02 wt% were added, dissolved by stirring, and heated to 80 ℃. Then, 11.5 wt% of butadiene monomer, 17wt% of styrene monomer, 0.8wt% of acrylic acid, 0.15 wt% of sodium dodecylbenzenesulfonate, 0.2 wt% of ammonium persulfate and 0.14 wt% of t-dodecyl mercaptan were continuously added dropwise to the total weight, and polymerization was carried out for 1.5 hours. Then, continuously dropwise adding a monomer mixture consisting of 13.3 wt% of butadiene monomer, 23.9wt% of styrene monomer, 1.0 wt% of acrylic acid and itaconic acid mixture, 1.0 wt% of acrylonitrile, 0.3 wt% of sodium dodecyl benzene sulfonate and 0.26 wt% of tertiary-dodecyl mercaptan into the reaction kettle, and continuously adding for 2.5 hours; simultaneously, an initiator solution consisting of 0.50 weight percent of ammonium persulfate is dropwise added for 4.5 hours, and the reaction temperature is kept at 85 ℃ for reaction. After the continuous dropwise addition, the mixture was kept at 95 ℃ for 3 hours.
After the reaction is finished, the product is cooled after flash evaporation and stripping steps, sodium hydroxide solution is added for neutralization until the pH value is neutral, and then filtration is carried out, so that the butadiene-styrene copolymer latex with the solid content of 50.5%, the gel content of 76.2% and the glass transition temperature of 5 ℃ and 15 ℃ is obtained.
Examples 2 to 10
The reaction processes of the examples 2 to 10 are the same as those of the example 1, and the change of each composition and reaction parameter is shown in Table 1;
the properties of the resulting butadiene-styrene copolymer latex are shown in Table 2.
TABLE 1 reaction parameters of the examples
TABLE 2 data for the physical Properties of the latices of the examples
The butadiene-styrene copolymer latex products having a heterogeneous structure prepared in examples 1 to 10 were used in coating experiments for paper, the coating formulation is shown in Table 3, and the printing properties of the coated paper are shown in Table 4.
TABLE 3 coating composition ratios
| Components | Ratio/%) | Stirring speed/rpm, time/min |
| Calcium carbonate | 100 | 1200/10 |
| Butadiene-styrene copolymer latex | 9.0 | 800/5 |
| Thickening agent | 0.10 | 800/2 |
| Dispersing agent | 0.15 | 1200/10 |
| Water repellent agent | 0.30 | 800/2 |
TABLE 4 printed Properties of the coated paper
Through paper coating experiments, the butadiene-styrene copolymer latex product with the heterogeneous structure has strong stability and good compatibility with coating, and the coated paper has higher dry and wet napping strength, better cohesive force, whiteness, glossiness and smoothness, and can meet the requirements of water-resistant printing strength, ink acceptance and blistering resistance particularly under the conditions of high coating speed and the advancement of a flat printing technology.
It should be understood that the above description is only exemplary of the present invention, and is not intended to limit the scope of the present invention, which is defined by the appended claims.
Claims (6)
1. A butadiene-styrene copolymer latex for paper coating, characterized in that the copolymer latex comprises: soft and hard two-phase copolymer and water, at least one phase is formed by polymerizing butadiene, styrene, functional monomer and unsaturated carboxylic acid monomer;
the weight of the monomer mixture of the soft phase copolymer accounts for 20-50 wt% of the total weight of the monomer mixture;
the weight of the monomer mixture of the hard phase copolymer accounts for 50-80 wt% of the total weight of the monomer mixture;
the copolymer latex has a particle size of 100-200 nm; the potential is-10 to-30 mv, the gel content is 70 to 90 percent, and the glass transition temperature is-5 to 5 ℃ and 7 to 15 ℃;
the soft phase copolymer composition comprises:
butadiene monomer: 39-44%;
styrene monomer: 54-58%;
unsaturated carboxylic acid: 2-4%;
the hard phase copolymer latex composition comprises:
butadiene monomer: 33 to 38 percent;
styrene monomer: 56-61%;
unsaturated carboxylic acid: 2.0-5.0%;
functional monomer: 2.0-5.0%;
the preparation method of the copolymer latex comprises the following steps:
(1) prepolymerization stage
Dissolving seed latex, an emulsifier accounting for 0.10-0.25 wt% of the total weight, an electrolyte and a chelating agent by deionized water to prepare an aqueous solution, adding the aqueous solution into a reaction kettle, stirring and heating to 75-95 ℃, starting to dropwise add a butadiene monomer accounting for 11.5-12.8 wt% of the total weight, a styrene monomer accounting for 15.8-17 wt%, an unsaturated carboxylic acid accounting for 0.7-0.8 wt%, an emulsifier accounting for 0.10-0.25 wt% and an initiator accounting for 0.20-0.24 wt% of the total weight, wherein the dropwise adding time is 0.5-1.5 hours;
(2) polymerisation stage
After the pre-reaction in the step (1) is finished, continuously dripping 0.30-0.42 wt% of emulsifier, 0.4-0.5 wt% of initiator, 13.3-14.9 wt% of butadiene monomer, 22.3-23.9 wt% of styrene monomer, 0.8-1 wt% of unsaturated carboxylic acid, 0.8-1 wt% of functional monomer and molecular weight regulator into a reaction kettle; continuously adding other materials except the initiator solution for 2.0-3.0 hours, and keeping the reaction temperature at 75-95 ℃; the initiator solution is continuously added for 3.5-4.5 hours; after the continuous dripping is finished, preserving the heat for 1 to 3 hours at the temperature of 80 to 100 ℃, wherein the components of each reaction substance are in mass fraction;
(3) degassing stage
After the reaction is finished, the product is subjected to flash evaporation and steam stripping steps, and then the degassing stage is finished;
feeding the latex for 1.5-3 hours in a flash evaporation process, wherein the vacuum degree is-0.05-0.095 MPa, and the temperature is 60-90 ℃; in the stripping process, adding a redox initiator accounting for 0.05-0.075% of the total amount of the latex or a thermal initiator accounting for 0.05-0.1%, wherein the steam flow is 1-3 tons/hour, the stripping time is 2.5-4.5 hours, the vacuum degree is-0.65-0.085 MPa, and the temperature is 65-85 ℃;
and finally cooling, adding alkali to neutralize until the pH value is neutral, and filtering to obtain the butadiene-styrene copolymer latex with a heterogeneous structure.
2. The butadiene-styrene copolymer latex for paper coating according to claim 1, wherein said unsaturated carboxylic acid is any one or a mixture of acrylic acid, itaconic acid, methacrylic acid, fumaric acid and maleic acid.
3. The butadiene-styrene copolymer latex for paper coating according to claim 1, wherein said functional monomer is any one or mixture of acrylonitrile, methyl methacrylate, acrylamide and methylol acrylamide.
4. The butadiene-styrene copolymer latex for paper coating as claimed in claim 1, wherein in the degassing step, the redox initiator is hydrogen peroxide and sodium bisulfite, dicumyl peroxide and sodium bisulfite, or hydrogen peroxide p-alkane and sodium bisulfite in a mass ratio of 1:1 to 1:1.5, and the thermal initiator is any one of ammonium persulfate, potassium persulfate and sodium persulfate.
5. The butadiene-styrene copolymer latex for paper coating according to claim 1, wherein said emulsifier is an anionic emulsifier; the electrolyte is potassium chloride, sodium chloride or sodium carbonate; the chelating agent is ethylenediamine tetraacetic acid and disodium salt thereof; the molecular weight regulator is tert-dodecyl mercaptan or n-dodecyl mercaptan or the mixture of the tert-dodecyl mercaptan and the n-dodecyl mercaptan.
6. The butadiene-styrene copolymer latex for paper coating according to any one of claims 1 to 5, wherein: the copolymer latex obtained by the preparation method is applied to paper coating, and when the paper coating is carried out, the copolymer latex needs to be mixed with calcium carbonate, a dispersing agent, a thickening agent and a water repellent agent to prepare a complex for use, wherein the complex comprises the following components in percentage by mass:
8 to 10 percent of latex, 0.1 to 0.2 percent of dispersant, 0.05 to 0.15 percent of thickener and 0.25 to 0.35 percent of water repellent agent; calcium carbonate: the rest is obtained;
the dispersant is inorganic phosphate or polyacrylate;
the thickening agent is acrylic acid copolymer;
the water repellent agent is any one of glyoxal, polyamine polyurea, melamine formaldehyde resin and ammonium zirconium carbonate.
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| US8674000B2 (en) * | 2006-10-24 | 2014-03-18 | Lg Chem, Ltd. | Multi-layered paper coating latex having high swelling and contraction property, method for preparing the same, and paper coating composition containing the same |
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