CN-121991263-A - Carboxyl hydrogenated liquid nitrile rubber, preparation method thereof and vulcanized rubber

Abstract

The invention relates to the technical field of hydrogenated nitrile rubber, in particular to carboxyl hydrogenated liquid nitrile rubber, a preparation method thereof and vulcanized rubber. Disclosed is a process for producing a carboxylated hydrogenated liquid nitrile rubber, which comprises subjecting a starting material for providing a carboxylated hydrogenated liquid nitrile rubber to a contact reaction comprising metathesis and hydrogenation in the presence of a solvent, hydrogen and a catalyst, wherein the starting material for providing a carboxylated hydrogenated liquid nitrile rubber is selected from carboxylated nitrile rubbers, or nitrile rubbers and unsaturated carboxylic acids. The preparation method is simple, and has the advantages of mild reaction conditions, high reaction rate and controllable molecular weight of the product.

Inventors

• CHEN FEI
• ZHENG HONGBING
• XIONG FENG
• HAN YAN
• WANG YUCHAO
• WEN JINGBIN
• GONG GUANGBI

Assignees

• 中石油(上海)新材料研究院有限公司
• 中国石油天然气股份有限公司

Dates

Publication Date

20260508

Application Date

20241106

Claims (15)

1. 1. A process for preparing a carboxylated hydrogenated liquid nitrile rubber, characterized in that it comprises providing a starting material of a carboxylated hydrogenated liquid nitrile rubber in the presence of a solvent, hydrogen and a catalyst, and performing a contact reaction comprising metathesis and hydrogenation; Wherein the raw material for providing the carboxyl hydrogenated liquid nitrile rubber is selected from carboxyl nitrile rubber or nitrile rubber and unsaturated carboxylic acid.
2. 2. The preparation method according to claim 1, wherein, The content of bound acrylonitrile in the carboxylated nitrile rubber is 30-35 wt percent, and/or The carboxylated nitrile rubber has a number average molecular weight of 80000-150000, and/or The carboxyl nitrile rubber has carboxyl content of 0.1-6wt% and/or The carboxylated nitrile rubber has a Mooney viscosity of 50 to 59, and/or The molecular weight distribution index of the carboxylated nitrile rubber is 1.5-10.
3. 3. The preparation method according to claim 1, wherein, The content of bound acrylonitrile in the nitrile rubber is 27wt percent to 35wt percent, and/or The nitrile rubber has a number average molecular weight of 80000 to 120000, and/or The nitrile rubber has a Mooney viscosity of 45 to 55, and/or The molecular weight distribution index of the nitrile rubber is 1-8.
4. 4. The process according to any one of claim 1 to 3, wherein, The mass ratio of the carboxylated nitrile rubber or the nitrile rubber to the solvent is 0.01-0.15:1, and/or The mass ratio of the carboxylated nitrile rubber or the nitrile rubber to the catalyst is 1:0.0002-0.003, and/or The mass ratio of the unsaturated carboxylic acid to the nitrile rubber is 0.005-0.06:1.
5. 5. The preparation method according to claim 4, wherein, The mass ratio of the carboxylated nitrile rubber or the nitrile rubber to the catalyst is 1:0.0003-0.001.
6. 6. The process according to any one of claim 1 to 3, wherein, The catalyst is selected from at least one of Grubbs I, grubbs II, grubbs III and Hoveyda-Grubbs II, and/or The solvent is at least one selected from methyl ethyl ketone, toluene ketone, butanone, chloromethane, trichloromethane, ethyl acetate, butyl butyrate, chlorobenzene, stilbene, toluene and xylene, and/or The unsaturated carboxylic acid is selected from unsaturated carboxylic acids of C 3 -C 10 .
7. 7. The preparation method according to claim 6, wherein, The unsaturated carboxylic acid is selected from one of methacrylic acid, acrylic acid, butenoic acid, maleic acid and fumaric acid.
8. 8. The process according to any one of claim 1 to 3, wherein, The hydrogen pressure is 6-12MPa, and/or The conditions of the contact reaction include a temperature of 70-160 ℃ and/or a time of 1-12h.
9. 9. The preparation method according to claim 8, wherein, The conditions of the contact reaction include a temperature of 120-160 ℃ and/or a time of 4-8 hours.
10. 10. A carboxylated hydrogenated liquid nitrile rubber produced by the process of any one of claims 1 to 9.
11. 11. The carboxylated hydrogenated liquid nitrile rubber according to claim 10, wherein, The carboxyl hydrogenated liquid nitrile rubber contains hydrogenated polybutadiene chain segment, polyacrylonitrile chain segment and modified functional group carboxyl, and/or The glass transition temperature of the carboxyl hydrogenated liquid nitrile rubber is not higher than-30 ℃.
12. 12. The carboxylated hydrogenated liquid nitrile rubber according to claim 11, wherein, The glass transition temperature of the carboxyl hydrogenated liquid nitrile rubber is-47 to-30 ℃, and/or The molecular weight distribution index of the carboxyl hydrogenated liquid nitrile rubber is 2.5-6, and/or The number average molecular weight of the carboxyl hydrogenated liquid nitrile rubber is 1500-10000.
13. 13. The carboxylated hydrogenated liquid nitrile rubber according to any one of claims 10-12, wherein, The carboxyl is selected from-R-COOH, R is H or C 1 -C 9 alkenylene and/or alkylene, and/or The hydrogenated polybutadiene block has a degree of hydrogenation of 60wt% to 100wt%.
14. 14. The carboxylated hydrogenated liquid nitrile rubber according to any one of claims 10-12, wherein, Based on the mass of the carboxyl hydrogenated liquid nitrile rubber: the content of the polyacrylonitrile chain segment is 25wt% to 35wt%, and/or The content of the carboxyl is 1.1-4wt%.
15. 15. A vulcanizate, characterized in that it is obtained from a carboxylated hydrogenated liquid nitrile rubber according to any one of claims 10 to 14 under vulcanization conditions.

Description

Carboxyl hydrogenated liquid nitrile rubber, preparation method thereof and vulcanized rubber Technical Field The invention relates to the technical field of hydrogenated nitrile rubber, in particular to carboxyl hydrogenated liquid nitrile rubber, a preparation method thereof and vulcanized rubber. Background Hydrogenated nitrile rubber (HNBR) is produced by hydrogenation of unsaturated double bonds contained in nitrile rubber (NBR) molecules under high temperature and high pressure conditions. HNBR has good heat resistance, good chemical corrosion resistance, such as good resistance to refrigerant, acid and alkali, excellent ozone resistance and higher compression set resistance, and also has the characteristics of high strength, high tearing property, excellent wear resistance and the like, and is one of special rubber with extremely excellent comprehensive properties. Its excellent performance is that of sealing element and medium-resistant pipeline and the like, plays a great role in severe service scenes. Currently, most commercial HNBR is solid HNBR, and the number average molecular weight is usually more than hundreds of thousands. The liquid hydrogenated nitrile rubber (LHNBR) is a special HNBR product, the number average molecular weight of which is usually less than 10000, and which is in a viscous liquid state at normal temperature. The low-molecular liquid toughening agent is a novel low-molecular liquid toughening agent, a plasticizer and a rubber softener, has unique advantages in the field of paint, and can be used as a matrix material of special composite materials such as electromagnetic shielding coating, oil-resistant coating, battery corrosion-resistant coating sealing fittings, damping noise reduction coating and the like. The preparation method of the liquid nitrile rubber is a low-temperature emulsion polymerization method, which is to polymerize a plurality of oil phase monomers in a water phase medium under the action of an emulsifier, and control the molecular weight of the polymer through an initiator and a chain transfer agent (usually mercaptan) to realize the preparation of the liquid NBR. The related documents mainly include CN103626924A, CN1978476A, CN105837754A, CN118108896A and the like. The process route has low conversion rate, generally adopts a mode of prolonging the polymerization time to improve the monomer conversion rate and reduce the production efficiency, is limited by the defect of low conversion rate, needs to reasonably collect and treat unconverted monomers, and has high requirements on post-treatment processes such as tail gas treatment and the like. Hydrogenated carboxylated nitrile rubber (HXNBR) is the carboxyl group incorporated into HNBR and currently the major nitrile rubber manufacturers worldwide are preparing HXNBR by the route of catalytic hydrogenation of NBR rubber copolymerized from ternary emulsions of butadiene, acrylonitrile, unsaturated carboxylic acids or carboxylic esters. The introduction of carboxyl leads the oil resistance to be further enhanced, and simultaneously effectively improves the performances of the rubber material such as tensile strength, elastic modulus, hardness, adhesiveness and the like, in particular improves the tensile strength of HNBR at high temperature. In addition, the carboxyl can also improve the polarity of HNBR molecular chains, increase the compatibility with general resin materials such as polyvinyl chloride, phenolic resin and the like, and widen the application field of HNBR. The preparation method of LHNBR has little research in the published data, and the types of LHNBR products are very limited. Disclosure of Invention The invention aims to solve the problems that the types of hydrogenated liquid nitrile rubber products are very limited and the product performance is to be improved in the prior art, and provides a novel carboxyl liquid nitrile rubber, a preparation method thereof and vulcanized rubber. The method has the advantages of simple preparation method, mild reaction condition, high reaction rate and controllable molecular weight of the product. In order to achieve the above object, a first aspect of the present invention provides a process for producing a carboxylated hydrogenated liquid nitrile rubber, which comprises subjecting a starting material for providing a carboxylated hydrogenated liquid nitrile rubber to a contact reaction comprising metathesis and hydrogenation in the presence of a solvent, hydrogen and a catalyst, wherein the starting material for providing a carboxylated hydrogenated liquid nitrile rubber is selected from carboxylated nitrile rubbers, or nitrile rubbers and unsaturated carboxylic acids. In a second aspect, the invention provides the carboxyl hydrogenated liquid nitrile rubber prepared by the preparation method of the first aspect. In a third aspect, the present invention provides a vulcanizate obtained from the carboxylated hydrogenated liquid nitrile rubber acco