CN114014967A - Modified carboxylic styrene-butadiene latex and preparation method thereof - Google Patents
Modified carboxylic styrene-butadiene latex and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract
The invention relates to modified carboxylic styrene-butadiene latex and a preparation method thereof, wherein the modified carboxylic styrene-butadiene latex is prepared from the following raw materials in parts by weight: 100 parts of polymerized monomer, 0.01-3 parts of cross-linking agent, 0.01-1.5 parts of catalyst, 0.01-2.5 parts of emulsifier, 0.01-1 part of organic monomer and 95-110 parts of deionized water. The method uses butadiene and styrene as basic raw materials, acrylic acid aqueous solution is doped as a functional monomer, deionized water, the styrene, the acrylic acid aqueous solution, t-DDM, acrylonitrile, acrylamide, an organic monomer, an emulsifier and the like are mixed firstly, carboxyl is grafted on a SBR macromolecular chain, butadiene, residual materials and a catalyst are added, the temperature is continuously raised for polymerization reaction, the vitrification temperature of latex can be reduced by adding the acrylamide, and the flexibility and the tensile strength of the latex after solidification are enhanced. The modified carboxylic styrene-butadiene latex prepared by the invention has lower glass transition temperature (Tg), excellent bonding strength and flexibility and higher tensile strength.
Description
Technical Field
The invention belongs to the field of polymers, and relates to modified carboxylic styrene-butadiene latex and a preparation method thereof.
Background
Styrene-butadiene latex (SBL) is an aqueous solution with a solid content of 30-50% obtained by emulsion polymerization of butadiene (B) and styrene (S). Is prepared by emulsion polymerization of styrene and butadiene in different proportions. There are various varieties depending on the styrene content, the emulsifier, the polymerization temperature, etc., and the properties and uses thereof are also different. When the emulsion is used as a coating adhesive, the ratio of styrene to butadiene is (60-50) to (40-50), the emulsion is milky white, the solid content is about 45-50%, the emulsion has negative charges, and the pH value is 9.0-10.5. After the styrene-butadiene latex adhesive is coated, the coated paper can obtain the highest pigment bonding strength and wet abrasion resistance, and the smoothness, printing glossiness, dry napping value, CIE whiteness and ISO whiteness of the coated paper are improved. The traditional coating adhesive has large styrene consumption, and usually needs to be mixed with casein, modified starch and the like for use, so that the hardness of the coated paper can be increased, and the coated paper is gradually replaced by styrene-butadiene latex due to poor stability, large particle size and high possibility of being influenced by heavy metal ions, and the styrene-butadiene latex consumption is increased year by year.
The carboxylic styrene-butadiene latex is a milky water dispersion with blue-violet gloss, which is a copolymer generated by emulsion polymerization of butadiene, styrene, a small amount of carboxylic acid and other functional additives as polymerization raw materials. The carboxylic styrene-butadiene latex has the advantages of high cohesive force and conjunctival strength, good mechanical and chemical stability, good fluidity and storage stability, large filling amount and the like, and is widely applied to industries of papermaking, carpets, textile, environment-friendly ornaments, architectural decoration and the like. In recent years, polymers, particularly styrene-butadiene latex, are adopted to modify concrete so as to improve the service performance of the concrete and prolong the service life of the concrete. In the prior art, patent CN106220787A discloses a carboxylated styrene-butadiene latex special for cement, which is prepared by adding carboxylated styrene-butadiene latex into cement, and utilizing the characteristics of high conjunctival strength and binding power of the carboxylated styrene-butadiene latex, the binding power, water-gathering property, wear resistance, fluidity, moldability, mechanical and chemical stability of the whole cement are greatly improved, so that the water loss of the cement is reduced, and the binding power, wear resistance and durability, compressive strength, mechanical and chemical stability of the cement are greatly enhanced.
Therefore, research institutions at home and abroad are continuously dedicated to research and develop a carboxylic styrene-butadiene latex with low glass transition temperature, strong binding force and good flexibility.
Disclosure of Invention
The invention aims to provide modified carboxylic styrene-butadiene latex and a preparation method thereof, which aim to solve the problems of higher glass transition temperature, high hardness or low flexibility and the like in the prior art.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides modified carboxylic styrene-butadiene latex, which comprises the following raw material components in parts by weight: 20-50 parts of butadiene, 30-65 parts of styrene, 0.001-5 parts of an acrylic acid aqueous solution, 0.1-3 parts of tert-dodecyl mercaptan (t-DDM), 0.1-3 parts of acrylonitrile, 0.01-3 parts of a cross-linking agent, 0.01-1.5 parts of a catalyst, 0.01-2.5 parts of an emulsifier, 0.01-1 part of an organic monomer and 95-110 parts of deionized water.
Further, the cross-linking agent is acrylamide.
Further, the catalyst is an ammonium persulfate aqueous solution, and the concentration of the ammonium persulfate aqueous solution is 20-30 wt%.
Further, the emulsifier is at least one of DOWFAX 2A1 (sodium dodecyl diphenyl oxide disulfonate), sodium dodecyl benzene sulfonate and Disponil SLS 103 (sodium alkyl sulfate).
Further, the organic monomer is composed of carboxylic acid A and carboxylic acid B, wherein the carboxylic acid A is acrylic acid, and the carboxylic acid B is one of itaconic acid and fumaric acid. Furthermore, the mass ratio of the added carboxylic acid A to the added carboxylic acid B is 1-5: 1. further, acrylic acid used herein is an aqueous acrylic acid solution having a concentration of 80% by weight.
Further, the conductivity of the deionized water is less than 15 mu S/cm, and bacteria and yeast are removed by filtration.
Further, the modified carboxylic styrene-butadiene latex also comprises a defoaming agent, a bactericide and a pH neutralizing agent.
The second technical scheme of the invention also provides a preparation method of the modified carboxylic styrene-butadiene latex, which comprises the following steps:
(1) adding part of styrene, acrylic acid aqueous solution (80 wt%), t-DDM, deionized water, acrylonitrile, acrylamide, emulsifier A and 1.85g of organic monomers (carboxylic acid A and carboxylic acid B) into a reactor, uniformly stirring, introducing nitrogen, performing vacuum pumping, replacing air for three times, raising the temperature (namely raising the temperature once), and adding catalyst ammonium persulfate aqueous solution to start polymerization;
(2) after reacting for a period of time, continuously adding the rest of styrene, butadiene, deionized water, an ammonium persulfate aqueous solution and t-DDM into the reaction liquid obtained in the step (1), and carrying out secondary heating reaction;
(3) and (3) cooling the reaction liquid obtained in the step (2), adding a pH neutralizer sodium hydroxide solution and the like to adjust the pH value, degassing and filtering to obtain the modified carboxylic styrene-butadiene latex product.
Further, in the step (1), deionized water is added into the mixture in an amount of 30-60% of the total amount of the deionized water; firstly, adding styrene into the mixture by 30-50% of the total amount of the styrene; firstly, adding t-DDM (tert-dodecyl mercaptan) in an amount of 0.01-10% of the total amount; the catalyst is added into the reactor at first, wherein the total amount of the catalyst is 20-30%.
Further, in the step (1), the temperature of the primary heating is 70-105 ℃, and the reaction time is 1-3 hours.
Further, in the step (1), deionized water is heated to 60-70 ℃ during mixing so as to improve the dissolving capacity.
Further, in the step (1), before the uniform mixing, all of the bactericide, the pH neutralizer sodium hydroxide solution and other chemicals are added.
Further, in the step (2), the temperature of the secondary heating reaction is 80-110 ℃ and the time is 2-5 hours.
Further, in the step (2), the pH of the reaction product obtained by the secondary heating reaction is adjusted to 7-9, and then degassing and filtering are carried out to obtain the target product.
Further, adjusting the pH value to 7-9 by using a sodium hydroxide solution.
Further, the concentration of the sodium hydroxide solution is 20 wt%.
Furthermore, in the step (2), the degassing time is 3-4 hours.
Further, in the step (2), the t-DDM in the rest materials is dissolved in the rest deionized water and added in a form of t-DDM aqueous solution, and the concentration of the t-DDM aqueous solution is 70-80 wt%.
By adopting the technical scheme, butadiene and styrene are used as basic raw materials, acrylic acid is doped as a functional monomer, deionized water, styrene, an acrylic acid aqueous solution, t-DDM, acrylonitrile, acrylamide, an organic monomer, an emulsifier and the like are mixed in advance, carboxyl is grafted on a SBR (styrene butadiene rubber) macromolecular chain to improve the mechanical stability and the bonding strength of latex, butadiene, residual materials and a catalyst are added, the temperature is continuously increased for polymerization reaction, the addition of the acrylamide can also improve the conversion rate of the polymerization reaction, reduce the amount of recovered monomers and reduce the vitrification temperature of the latex, so that the hardness of the latex is reduced, and the flexibility and the tensile strength of the latex after curing are enhanced. And finally, degassing in a degassing container to remove residual monomers, further removing the monomers on the premise of not influencing the stability of the styrene-butadiene latex and the product quality, reducing the monomer content, ensuring that the Volatile Organic Compound (VOC) content in the finally prepared product is very low (less than 50ppm), reducing pollution and protecting the environment.
In the invention, if the reaction temperature is too high, the polymerization rate of the reaction is low (less than 90 percent), and a large amount of gel is generated, so that qualified products cannot be obtained; if the reaction temperature is too low, it may result in a low polymerization rate (< 90%) of the reaction, a large amount of coagulant may be produced, and the particle size distribution of the product may be too broad to obtain an acceptable product.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, acrylic acid is used as a functional monomer, and carboxyl is grafted on a SBR macromolecular chain, so that the mechanical stability and the bonding strength of the latex are improved;
(2) according to the invention, acrylamide is introduced into a polymerization system, so that the conversion rate of polymerization reaction is improved, the amount of recovered monomers is reduced, and the glass transition temperature of latex is reduced, thereby reducing the hardness of the latex and enhancing the flexibility and tensile strength of the latex after solidification;
(3) the product is degassed to remove residual monomers, so that the product has little smell and low VOC content, reduces pollution and protects the environment;
(4) the modified carboxylic styrene-butadiene latex prepared by the invention has lower glass transition temperature (Tg), excellent bonding strength and flexibility and higher tensile strength.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments. In the following examples, the starting materials and the treatment steps used are conventional commercial products and conventional techniques, unless otherwise specified.
In the following examples, the carboxylic acid A used is acrylic acid, the carboxylic acid B used is fumaric acid and the emulsifier A used is DOWFAX 2A 1.
Example 1:
this example illustrates modified carboxylated styrene-butadiene latex and a method for preparing the same according to the present invention.
480g of styrene, 60g of an aqueous acrylic acid solution (80 wt%), 1.25g t-DDM, 3100g of deionized water, 1.38g of acrylonitrile, 1.60g of acrylamide, 2.02g of emulsifier A and 1.85g of organic monomers (carboxylic acid A and carboxylic acid B) are added into a reactor, a stirrer is opened, nitrogen is introduced after uniform stirring, vacuum suction is carried out, and air is replaced three times. Then, the temperature was raised to 75 ℃ and 185g of an aqueous ammonium persulfate solution was added as a catalyst to start the polymerization reaction, and the reaction temperature was maintained at 75 ℃ for 1.5 hours. 9380g of styrene and 5380g of butadiene were then added dropwise together with 7000g of deionized water, 150g of an aqueous ammonium persulfate solution (20% by weight) and an aqueous phase of 46.8g t-DDM (70% by weight), and the reaction was continued for 3 hours while warming to 100 ℃. And then keeping the temperature in the reactor at 100 ℃ for continuous heat preservation reaction for 2 hours, wherein the conversion rate of the monomer reaches 99%, reducing the temperature and discharging, adding a pH neutralizer sodium hydroxide solution when the solid content reaches about 50%, regulating the pH value to 8, degassing and filtering to obtain the modified carboxylated styrene-butadiene latex S1.
Example 2:
this example illustrates modified carboxylated styrene-butadiene latex and a method for preparing the same according to the present invention.
552g of styrene, 75g of an aqueous acrylic acid solution (80 wt%), 1.5g t-DDM, 3290g of deionized water, 1.55g of acrylonitrile, 1.92g of acrylamide, 2.53g of emulsifier A and 2.22g of organic monomers (carboxylic acid A and carboxylic acid B) are added into a reactor, a stirrer is opened, nitrogen is introduced after uniform stirring, vacuum suction is carried out, and air is replaced three times. Then, the temperature was raised to 75 ℃ and 185g of an aqueous ammonium persulfate solution was added as a catalyst to start the polymerization reaction, and the reaction temperature was maintained at 75 ℃ for 1.5 hours. 9310g of styrene and 5365g of butadiene were then added dropwise together with 6810g of deionized water, 150g of an aqueous ammonium persulfate solution (20% by weight) and an aqueous phase of 50.0g t-DDM (70% by weight), and the reaction was continued for 3 hours while warming to 100 ℃. And then keeping the temperature in the reactor at 100 ℃ for continuous heat preservation reaction for 2 hours, wherein the conversion rate of the monomer reaches 99%, reducing the temperature and discharging, adding a pH neutralizer sodium hydroxide solution when the solid content reaches about 50%, regulating the pH value to 8, degassing and filtering to obtain the modified carboxylated styrene-butadiene latex S2.
Example 3:
this example illustrates modified carboxylated styrene-butadiene latex and a method for preparing the same according to the present invention.
670g of styrene, 90g of an aqueous acrylic acid solution (80 wt%), 1.8g t-DDM, 3680g of deionized water, 2.12g of acrylonitrile, 2.88g of acrylamide, 3.54g of emulsifier A and 2.45g of organic monomers (carboxylic acid A and carboxylic acid B) are added into a reactor, a stirrer is opened, nitrogen is introduced after uniform stirring, vacuum suction is carried out, and air is replaced for three times. Then, the temperature was raised to 75 ℃ and 185g of an aqueous ammonium persulfate solution was added as a catalyst to start the polymerization reaction, and the reaction temperature was maintained at 75 ℃ for 1.5 hours. 9190g of styrene and 5350g of butadiene, as well as 6420g of deionized water, 150g of aqueous ammonium persulfate solution (20% by weight) and an aqueous phase of 55.0g t-DDM (70% by weight) were then added dropwise, followed by warming to 100 ℃ and continuing the reaction for 3 hours. And then keeping the temperature in the reactor at 100 ℃ for continuous heat preservation reaction for 2 hours, wherein the conversion rate of the monomer reaches 99%, reducing the temperature and discharging, adding a pH neutralizer sodium hydroxide solution when the solid content reaches about 50%, regulating the pH value to 8, degassing and filtering to obtain the modified carboxylated styrene-butadiene latex S3.
Comparative example 1:
this comparative example is illustrative of a reference modified carboxylated styrene-butadiene latex and its method of preparation.
This comparative example 1 is different from example 3 in that acrylamide as a crosslinking agent is added in a mass ratio of 1:2 (comparative example 1: example 3 ═ 1:2), and other preparation conditions are the same as in example 3, to obtain a modified carboxylated styrene-butadiene latex S4.
Comparative example 2:
this comparative example is illustrative of a reference modified carboxylated styrene-butadiene latex and its method of preparation.
The comparative example 2 is different from the example 3 in that the functional monomer acrylic acid is added in a mass ratio of 1:2 (comparative example 2: example 3 ═ 1:2), and other preparation conditions were the same as in example 3, to obtain a modified carboxylated styrene-butadiene latex S5.
Modified carboxylated styrene-butadiene latex was prepared according to the methods of examples 1 to 3 and comparative examples 1 to 2, and the quality and performance of the product were measured according to the following methods:
(1) solid content: carrying out detection according to relevant regulations and detection standards in SH/T1154-1999 determination of total solid content of synthetic rubber latex;
(2) pH value: the detection is carried out according to relevant regulations and detection standards in SH/T1150-1999 determination of pH value of synthetic rubber latex;
(3) tensile strength: carrying out detection according to relevant regulations and detection standards in GB/T3849-2008 'determination of tensile strength and elongation at break' of hard rubber;
(4) viscosity: detection was carried out according to the relevant provisions and detection standards in SH/T1152-1992, determination of the viscosity of synthetic rubber latices;
(5) tg value: detecting according to relevant regulations and detection standards in SH/T1799-2016 (differential scanning calorimetry for measuring glass transition temperature of synthetic rubber latex);
(6) mechanical stability: the measurements were carried out according to the relevant provisions and criteria of examination in SH/T1151-1999 "measurement of high-speed mechanical stability of synthetic latices".
The modified carboxylic styrene-butadiene latex products S1-S5 prepared in the above examples 1-3 and comparative examples 1-2 respectively are subjected to performance detection according to the method, and the result shows that the product S3 prepared in the example 3 has the strongest tensile strength, the lowest glass transition temperature Tg (Tg) of 0 ℃, and has excellent bonding strength and flexibility; comparative example 1 the product S4 prepared in comparative example 1 has a lower tensile strength, an increased glass transition temperature Tg and a lower flexibility due to the addition of the crosslinking agent acrylamide in a mass ratio of 1:2 to example 3 (comparative example 1: example 3: 1: 2); comparative example 2 the product S5 prepared in comparative example 2 was poor in viscosity and reduced in mechanical properties due to the addition of the functional monomer acrylic acid in a mass ratio of 1:2 to example 3 (comparative example 2: example 3 ═ 1: 2).
From the results, the modified carboxylic styrene-butadiene latex prepared by the method provided by the invention not only has higher tensile strength, but also has lower glass transition temperature, and has excellent bonding strength and flexibility.
Example 4:
compared with the example 1, most of the components are the same, except that the formula of each raw material component in the example is correspondingly adjusted as follows: 20 parts of butadiene, 30 parts of styrene, 0.001 part of an acrylic acid aqueous solution, 0.1 part of tert-dodecyl mercaptan, 0.1 part of acrylonitrile, 3 parts of a crosslinking agent, 0.01 part of a catalyst, 0.01 part of an emulsifier, 0.01 part of an organic monomer and 95-110 parts of deionized water. In addition, it should be noted that, in the preparation process, the addition order and the proportion of the components are the same as those in example 1.
Example 5:
compared with the example 1, most of the components are the same, except that the formula of each raw material component in the example is correspondingly adjusted as follows: 50 parts of butadiene, 50 parts of styrene, 2 parts of an acrylic acid aqueous solution, 1.5 parts of tert-dodecyl mercaptan, 1.5 parts of acrylonitrile, 1 part of a cross-linking agent, 1.5 parts of a catalyst, 2.5 parts of an emulsifier, 1 part of an organic monomer and 95 parts of deionized water. In addition, it should be noted that, in the preparation process, the addition order and the proportion of the components are the same as those in example 1.
Example 6:
compared with the example 1, most of the components are the same, except that the formula of each raw material component in the example is correspondingly adjusted as follows: 35 parts of butadiene, 65 parts of styrene, 5 parts of an acrylic acid aqueous solution, 3 parts of tert-dodecyl mercaptan, 3 parts of acrylonitrile, 0.01 part of a cross-linking agent, 0.75 part of a catalyst, 1.5 parts of an emulsifier, 0.5 part of an organic monomer and 100 parts of deionized water. In addition, it should be noted that, in the preparation process, the addition order and the proportion of the components are the same as those in example 1.
Preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The modified carboxylic styrene-butadiene latex is characterized by comprising the following raw materials in parts by weight: 20-50 parts of butadiene, 30-65 parts of styrene, 0.001-5 parts of an acrylic acid aqueous solution, 0.1-3 parts of tert-dodecyl mercaptan, 0.1-3 parts of acrylonitrile, 0.01-3 parts of a cross-linking agent, 0.01-1.5 parts of a catalyst, 0.01-2.5 parts of an emulsifier, 0.01-1 part of an organic monomer and 95-110 parts of deionized water.
2. The modified carboxylated styrene-butadiene latex according to claim 1, wherein said cross-linking agent is acrylamide.
3. The modified carboxylated styrene-butadiene latex according to claim 1, wherein said catalyst is ammonium persulfate.
4. The modified carboxylated styrene-butadiene latex according to claim 1, wherein said emulsifier is at least one of sodium dodecyl diphenyl oxide disulfonate, sodium dodecyl benzene sulfonate or sodium alkyl sulfate.
5. The modified carboxylated styrene-butadiene latex according to claim 1, wherein the organic monomer is composed of carboxylic acid A and carboxylic acid B, wherein carboxylic acid A is acrylic acid, and carboxylic acid B is at least one of itaconic acid and fumaric acid.
6. The modified carboxylated styrene-butadiene latex according to claim 5, wherein the ratio of the added mass of the carboxylic acid A to the added mass of the carboxylic acid B is 1 to 5: 1.
7. The modified carboxylated styrene-butadiene latex according to claim 1, further comprising a defoaming agent, a bactericide and a pH neutralizer.
8. The process for preparing modified carboxylated styrene-butadiene latex according to any of claims 1 to 7, comprising the following steps:
(1) adding part of styrene, an acrylic acid aqueous solution, tert-dodecyl mercaptan, deionized water, acrylonitrile, a cross-linking agent, an emulsifier and an organic monomer into a reactor, uniformly stirring, introducing nitrogen, heating for one time, and adding a catalyst to start a polymerization reaction;
(2) after reacting for a period of time, continuously adding the rest of styrene, butadiene, deionized water, catalyst and tert-dodecyl mercaptan into the reaction solution obtained in the step (1), and heating for reaction for the second time;
(3) and (3) cooling the reaction liquid obtained in the step (2), adjusting the pH value, degassing and filtering to obtain the modified carboxylic styrene-butadiene latex product.
9. The method for preparing modified carboxylated styrene-butadiene latex according to claim 8, wherein in the step (1), deionized water is added to the latex in an amount of 30 to 60 percent of the total amount; firstly, adding styrene into the mixture by 30-50% of the total amount of the styrene; firstly, adding 0.01-10% of catalyst of tert-dodecyl mercaptan into the tert-dodecyl mercaptan, and firstly adding 20-30% of catalyst of tert-dodecyl mercaptan;
the temperature of the primary heating is 70-105 ℃, and the time of the polymerization reaction is 1-3 h.
10. The method for preparing modified carboxylated styrene-butadiene latex according to claim 8, wherein in the step (2), the temperature of the second heating reaction is 80-110 ℃ for 2-5 hours;
and (3) adjusting the pH of the reaction product obtained by the secondary heating reaction to 7-9, degassing and filtering to obtain the target product.
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| CN115894798A (en) * | 2022-12-26 | 2023-04-04 | 杭州龙驹合成材料有限公司 | A kind of carboxylated styrene-butadiene latex, its preparation method and application |
| CN116874694A (en) * | 2023-07-26 | 2023-10-13 | 杭州富阳富翔化工有限公司 | A kind of carboxyl styrene-butadiene latex for cardboard and its preparation method |
| CN116874694B (en) * | 2023-07-26 | 2024-01-05 | 杭州富阳富翔化工有限公司 | A kind of carboxyl styrene-butadiene latex for cardboard and its preparation method |
| CN117364527A (en) * | 2023-09-21 | 2024-01-09 | 江苏博汇纸业有限公司 | High-stability latex for coated paper and preparation method thereof |
| CN118108886A (en) * | 2024-03-04 | 2024-05-31 | 绿能纤材(重庆)科技有限公司 | Preparation method of modified carboxyl styrene-butadiene latex |
| CN118702865A (en) * | 2024-08-27 | 2024-09-27 | 杭州富阳富翔化工有限公司 | Composite carboxyl styrene butadiene latex for coated paper and preparation method thereof |
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