KR-20260065946-A - Liquid Styrene-Butadiene Rubber, Method of Manufacturing the Same, and Applications

KR20260065946AKR 20260065946 AKR20260065946 AKR 20260065946AKR-20260065946-A

Abstract

The present invention discloses a liquid styrene-butadiene rubber, a method for manufacturing the same, and applications. The polymerization monomers of the said liquid styrene-butadiene rubber are butadiene, styrene, and sulfonic acid group-containing ester monomers. The present invention includes sulfonic acid group-containing ester monomers in the manufacture of liquid styrene-butadiene rubber to obtain liquid styrene-butadiene rubber with superior temperature resistance, wear resistance, corrosion resistance, and mechanical performance.

Inventors

치우 관준
왕 용펑
자오 지차오
양 하이롱
샤오 웨이
종 치린
왕 완청
왕 샤오펑
장 화치앙
웨이 쉬링

Assignees

페트로차이나 컴퍼니 리미티드

Dates

Publication Date: 20260511
Application Date: 20241014
Priority Date: 20231024

Claims (19)

As liquid styrene-butadiene rubber, The polymerization monomer of the above liquid styrene-butadiene rubber comprises butadiene, styrene, and a sulfonic acid group-containing ester monomer, and The structural formula of the above sulfonic acid group-containing ester monomer is as follows: liquid styrene-butadiene rubber.
In paragraph 1, A liquid styrene-butadiene rubber in which, when the total weight of the butadiene, styrene, and sulfonic acid group-containing ester monomers is 100 parts, the weight parts of each monomer are 50 to 75 parts of butadiene, 20 to 30 parts of styrene, and 5 to 24 parts of sulfonic acid group-containing ester monomer, respectively.
In paragraph 1, The above liquid styrene-butadiene rubber is a liquid styrene-butadiene rubber prepared using an emulsion copolymerization method with butadiene, styrene, and sulfonic acid group-containing ester monomers.
In paragraph 1, Liquid styrene-butadiene rubber in which the content of the sulfonic acid group-containing ester monomer structure in the above liquid styrene-butadiene rubber is 3 wt% to 18 wt%.
In paragraph 1, A liquid styrene-butadiene rubber having a Mooney viscosity of 40 to 60 Pa·s and a molecular weight Mn range of 3000 to 5000.
A method for manufacturing liquid styrene-butadiene rubber according to any one of claims 1 to 5, wherein the manufacturing method When the total weight of butadiene, styrene, and sulfonic acid group-containing ester monomers is 100 parts, a step of adding 160 to 220 parts of deionized water, 4 to 8 parts of emulsifier, 0.1 to 0.3 parts of reducing agent, 0.1 to 0.4 parts of dispersant, 0.4 to 0.8 parts of electrolyte, 3 to 6 parts of molecular weight regulator, 20 to 30 parts of styrene, 3 to 20 parts of sulfonic acid group-containing ester monomers, and 0.01 to 0.1 parts of oxygen remover to a reaction vessel, and after the addition is completed, adding 50 to 75 parts of butadiene in a protective gas atmosphere and stirring to pre-emulsify, and then adding 0.1 to 0.2 parts of an initiator to carry out a polymerization reaction; A manufacturing method comprising the step of obtaining the liquid styrene-butadiene rubber by adding an emulsifier, an initiator, a molecular weight regulator, and a sulfonic acid group-containing ester monomer, respectively, when three monomers—butadiene, styrene, and a sulfonic acid group-containing ester monomer—reach a certain monomer conversion rate, adding 0.05 to 0.2 parts of a termination agent to terminate the reaction when the monomer conversion rate reaches 82 to 87%, and then performing degassing, flocculation, washing, and drying.
In paragraph 6, When the three monomers of butadiene, styrene, and sulfonic acid group-containing ester monomers mentioned above reach a certain monomer conversion rate, the step of additionally adding an emulsifier, an initiator, a molecular weight regulator, and a sulfonic acid group-containing ester monomer, respectively, is specifically: A manufacturing method comprising: adding 1 to 2 parts of a sulfonic acid group-containing ester monomer when the monomer conversion rate reaches 25% to 30%; adding 0.4 to 0.8 parts of an emulsifier, 0.002 to 0.004 parts of an initiator, and 0.5 to 0.8 parts of a molecular weight regulator when the monomer conversion rate reaches 50% to 55%; and adding 1 to 2 parts of a sulfonic acid group-containing ester monomer when the monomer conversion rate reaches 65% to 70%.
In paragraph 6 or 7, The above emulsifier is an anionic-anionic compound surfactant or anionic-nonionic compound surfactant; wherein the anionic-anionic compound surfactant is a compound of rosin soap and fatty alkyl sulfonate, with a compounding mass ratio of (4-5):1; and the above anionic-nonionic compound surfactant is a compound of rosin soap and polyoxyethylene ether, with a compounding mass ratio of (3-4):1, in a method for manufacturing.
In paragraph 6 or 7, A method for manufacturing the above reducing agent selected from at least one of sodium formaldehyde sulfoxylate, ferrous sulfate, copper sulfate, EDTA iron sodium salt, and EDTA copper sodium salt.
In paragraph 6 or 7, The above-mentioned dispersant is selected from at least one of a sodium β-naphthalenesulfonate formaldehyde condensate, a sodium methylnaphthalenesulfonate formaldehyde condensate, and a benzylnaphthalenesulfonate formaldehyde condensate.
In paragraph 6 or 7, A method for manufacturing the above electrolyte being potassium phosphate or potassium chloride.
In paragraph 6 or 7, The above molecular weight regulator is a method of preparation selected from at least one of dodecyl mercaptan, t-dodecyl mercaptan, and 2,4-diphenyl-4-methyl-1-pentene.
In paragraph 6 or 7, The above oxygen remover is a method of manufacturing selected from at least one of sodium bisulfite, dimethyl ketoxime, and isoascorbic acid.
In paragraph 6 or 7, The above-mentioned initiator is a method of manufacturing selected from at least one of cumene hydroperoxide, diisopropylbenzene hydroperoxide, and t-butylperoxyisopropyl carbonate.
In paragraph 6 or 7, The above-mentioned termination agent is a method of preparation selected from at least one of hydroxylamine sulfate, diethyl hydroxylamine, and isopropyl hydroxylamine.
In paragraph 6, The above sulfonic acid group-containing ester monomer is, A manufacturing method comprising the steps of: introducing acrylic acid, sodium hydroxyethylsulfonate, a dehydrating agent, and a catalyst into a reaction vessel; performing an esterification reaction by raising the temperature in a protective gas atmosphere; continuously distilling and discharging the generated water and dehydrating agent during the reaction process; refluxing the dehydrating agent back into the reaction vessel after separation to continue the reaction; stopping the reaction when the amount of water being separated no longer increases and reaches the theoretical calculated amount; filtering the reaction system to obtain a filter cake; and obtaining the sulfonic acid group-containing ester monomer by vacuum distillation of the filter cake.
In Paragraph 16, A method for manufacturing in which the molar ratio of sodium hydroxyethylsulfonate to acrylic acid is 1: (1 to 1.5).
In Paragraph 16, A method for manufacturing in which the dehydrating agent is selected from at least one of toluene, ethylbenzene, and p-toluene; and the catalyst is selected from at least one of methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and 2-naphthalenesulfonic acid.
Application of liquid styrene-butadiene rubber in tires or epoxy resin toughening agents according to any one of claims 1 to 5.

Description

Liquid Styrene-Butadiene Rubber, Method of Manufacturing the Same, and Applications This application claims priority to the Chinese patent application filed with the Chinese Intellectual Property Office on October 24, 2023, application number 202311382441.8, with the invention title “Liquid styrene-butadiene rubber and method of manufacturing and application thereof,” all of which are incorporated into this application by reference. The present invention relates to the field of liquid styrene-butadiene rubber, specifically to liquid styrene-butadiene rubber and its manufacturing method and application. Liquid rubber is a viscous oligomeric liquid with a relative molecular weight between 500 and 50,000 and constant fluidity at room temperature, and its viscosity varies depending on the molecular weight and molecular configuration. Liquid rubber comes in various types, such as liquid styrene-butadiene rubber, liquid nitrile butadiene rubber, and liquid ethylene-propylene rubber. Compared to solid rubber, liquid rubber has advantages such as excellent fluidity, ease of processing, and low energy consumption, so it is widely applied in fields such as sealing materials, adhesives, and tires. Liquid styrene-butadiene rubber is a diene copolymer-based liquid rubber produced by radical or anionic polymerization of butadiene and styrene. Radical emulsion polymerization is currently the most commonly used manufacturing method because it is easy to operate, allows for easy control of reaction temperature, and has a fast polymerization rate. Compared to natural rubber, liquid styrene-butadiene rubber possesses certain adhesive, temperature, wear, and mechanical properties, and also has good compatibility with some general-purpose rubbers, so it is widely applied in fields such as adhesives, fillers, and tires. However, in some relatively extreme environments, the performance of conventional liquid styrene-butadiene rubber is no longer sufficient to meet material requirements, so there is a need for further development of liquid styrene-butadiene rubber with superior temperature, wear, corrosion resistance, and mechanical properties. CN103539912A discloses a method for producing high-performance butadiene-styrene liquid rubber by dissolving a terpene resin at 80 to 110°C and grafting it onto a styrene-butadiene latex by emulsion polymerization to obtain terpene resin-modified liquid styrene-butadiene rubber, but the essence of the said method is the modification of styrene-butadiene rubber, which is not related to the polymerization process of styrene-butadiene rubber, and belongs to the subsequent polymerization modification of liquid styrene-butadiene rubber. CN115124663A discloses a modified styrene-butadiene rubber comprising a styrene-butadiene rubber matrix and a modified polymer bonded to at least a portion of the surface of the styrene-butadiene rubber matrix, wherein the modified polymer comprises a polymerization segment of a first monomer and a polymerization segment of a second monomer; wherein the first monomer is selected from acrylamide compounds, (meth)acrylate compounds, polyene compounds, and combinations thereof; and wherein the second monomer is selected from an ethylenically unsaturated group-containing azo initiator. The modified styrene-butadiene rubber of the present application has a high graft rate and, during the manufacturing process of asphalt waterproofing coil materials, the polymerization segment of the second monomer in the modified styrene-butadiene rubber continuously promotes a cross-linking reaction between the functional groups on the polymerization segment of the first monomer and other ethylenically unsaturated group-containing modifiers, thereby imparting good anti-aging performance. The present invention involves using styrene-butadiene rubber as a substrate to perform radical solution polymerization based thereon, and ternary copolymerization using an ester-containing monomer and an azo initiator, and is not related to the polymerization of styrene-butadiene rubber but belongs to the subsequent polymerization modification of styrene-butadiene rubber. CN1468877A discloses a method for synthesizing terminal hydroxyl group styrene-butadiene liquid rubber, wherein butadiene and styrene are used as monomers and an organic peroxide is used as an initiator to produce terminal hydroxyl group polybutadiene-styrene liquid rubber by radical solution polymerization. CN111560096A discloses a method for manufacturing styrene-butadiene rubber, wherein styrene-butadiene rubber is obtained by performing an emulsion polymerization reaction using styrene, butadiene, water, an emulsifier, an electrolyte, a reducing agent, an environmentally friendly molecular weight regulator, and an initiator as raw materials, under conditions of a polymerization reaction temperature ≤ 5°C and nitrogen gas protection. However, the said method replaces the conventional styrene-butadiene rubber regulator and does n