Hydrogenated block copolymer and preparation method and application thereof

Abstract

The invention relates to the field of copolymer hydrogenation, and discloses a hydrogenated block copolymer as well as a preparation method and application thereof. The hydrogenated block copolymer isobtained by hydrogenating a styrene-butadiene block copolymer, in the styrene-butadiene block copolymer, the content of a styrene segment is 10-90wt%, and the content of a butadiene segment is 90-10wt%; wherein the content of unsaturated C6 rings in the hydrogenated block copolymer is not more than 5wt%, and the content of straight-chain double bonds in the hydrogenated block copolymer is not more than 5wt%. A benzene ring and a butadiene segment in the styrene-butadiene block copolymer have an extremely high hydrogenation degree and excellent comprehensive performance. When the hydrogenatedblock copolymer is used as an optical material, the material is light, thin, transparent and bright; when the hydrogenated block copolymer is used as a medical material, the material is transparent, pure, safe and reliable; and when the hydrogenated block copolymer is used for preparing a food container, the food container is extremely clean.

Description

technical field

[0001] The invention relates to the field of copolymer hydrogenation, in particular to a hydrogenated styrene-butadiene block copolymer and its preparation method and application. The block copolymer can be widely used in heat resistance, high temperature resistance, high transparency, High impact areas. Background technique

[0002] Styrene-butadiene block copolymers can be widely used in plastic modification, asphalt modification, shoe materials, adhesives, etc. due to their properties as thermoplastic elastomers. However, since the polybutadiene segment in the styrene-butadiene block copolymer contains double bonds, its aging resistance and weather resistance are greatly limited, and the copolymer has poor compatibility with plastics and the like. The usual way to improve the properties of styrene-butadiene block copolymers is to hydrogenate and saturate the polybutadiene segment, so that its aging resistance and weather resistance are significantly impro...

Examples

preparation example Construction

[0085] For the catalyst-I, the present invention also provides a preparation method, comprising:

[0086] Scheme-A: Component a and component b are mixed and aged for the first time to obtain a uniform mixed solution-I, and then component c and mixed solution-I are subjected to second mixed and aged to obtain a uniform hydrogenation catalyst ;

[0087] Wherein, the first mixed aging time is 5-120min, the first mixed aging temperature is -20°C to 25°C; preferably the first mixed aging time is 10-60min, and the first mixed aging temperature is -10°C to 10°C;

[0088] The second mixing aging time is 2-90min, the second mixing aging temperature is -20°C to 25°C; preferably the second mixing aging time is 5-60min, and the second mixing aging temperature is -10°C to 10°C ;or

[0089] Scheme-B: The third mixed aging of component a and component c to obtain a uniform mixed solution-II, and then the fourth mixed aging of component b and mixed solution-II to obtain a uniform hydrogen...

Embodiment approach

[0101] The present invention provides another specific embodiment, the hydrogenation catalyst is Catalyst-II prepared by aging reaction of component a, component b, component c and component d. Preferably, the molar ratio of component a:component b:component c:component d=1:(2-6):(0.05-0.6):(0.05-0.15). Preferentially preparing water, alcohol and components a and b as a homogeneous hydrogenation catalyst is beneficial to the hydrogenation of unsaturated double bonds in styrene-butadiene block copolymers, especially increasing the degree of hydrogenation saturation of benzene rings, Thereby improving the transparency, purity and impact resistance of the obtained material. Wherein, the added amount of alcohol and water is controlled within the above-mentioned range with that of component a, and the purpose of hydrogenation reaction can be well realized. Wherein the molar weights of components a and b are calculated based on the metal elements in the components.

[0102] Accord...

Embodiment 1-1

[0149] The preparation of a styrene-butadiene block copolymer is illustrated.

[0150] In a 5L stainless steel stirred tank under the protection of high-purity nitrogen, add 2457g of refined cyclohexane and 109.2g of styrene after impurity removal, and add a solution of n-butyllithium cyclohexane with a concentration of 0.2M under the condition of stirring and 50°C 27.3mL initiated reaction for 100min;

[0151] After the polymerization is complete, add 163.8g of refined butadiene and continue to react at 50°C for 90min;

[0152] After the reaction is completed, add 1,2-dichloroethane and a cyclohexane solution of silicon tetrachloride to continue the reaction for 30 minutes, wherein the molar ratio of 1,2-dichloroethane to n-butyllithium is 0.15:1, tetrachloro The molar ratio of silicon oxide to n-butyllithium is 0.15:1, and then the terminator isopropanol is added to terminate the reaction, wherein the molar ratio of isopropanol to n-butyllithium is 1:1.

[0153] Obtain the...

technical field

[0001] The invention relates to the field of copolymer hydrogenation, in particular to a hydrogenated styrene-butadiene block copolymer and its preparation method and application. The block copolymer can be widely used in heat resistance, high temperature resistance, high transparency, High impact areas. Background technique

[0002] Styrene-butadiene block copolymers can be widely used in plastic modification, asphalt modification, shoe materials, adhesives, etc. due to their properties as thermoplastic elastomers. However, since the polybutadiene segment in the styrene-butadiene block copolymer contains double bonds, its aging resistance and weather resistance are greatly limited, and the copolymer has poor compatibility with plastics and the like. The usual way to improve the properties of styrene-butadiene block copolymers is to hydrogenate and saturate the polybutadiene segment, so that its aging resistance and weather resistance are significantly impro...

Examples

preparation example Construction

[0085] For the catalyst-I, the present invention also provides a preparation method, comprising:

[0086] Scheme-A: Component a and component b are mixed and aged for the first time to obtain a uniform mixed solution-I, and then component c and mixed solution-I are subjected to second mixed and aged to obtain a uniform hydrogenation catalyst ;

[0087] Wherein, the first mixed aging time is 5-120min, the first mixed aging temperature is -20°C to 25°C; preferably the first mixed aging time is 10-60min, and the first mixed aging temperature is -10°C to 10°C;

[0088] The second mixing aging time is 2-90min, the second mixing aging temperature is -20°C to 25°C; preferably the second mixing aging time is 5-60min, and the second mixing aging temperature is -10°C to 10°C ;or

[0089] Scheme-B: The third mixed aging of component a and component c to obtain a uniform mixed solution-II, and then the fourth mixed aging of component b and mixed solution-II to obtain a uniform hydrogen...

Embodiment approach

[0101] The present invention provides another specific embodiment, the hydrogenation catalyst is Catalyst-II prepared by aging reaction of component a, component b, component c and component d. Preferably, the molar ratio of component a:component b:component c:component d=1:(2-6):(0.05-0.6):(0.05-0.15). Preferentially preparing water, alcohol and components a and b as a homogeneous hydrogenation catalyst is beneficial to the hydrogenation of unsaturated double bonds in styrene-butadiene block copolymers, especially increasing the degree of hydrogenation saturation of benzene rings, Thereby improving the transparency, purity and impact resistance of the obtained material. Wherein, the added amount of alcohol and water is controlled within the above-mentioned range with that of component a, and the purpose of hydrogenation reaction can be well realized. Wherein the molar weights of components a and b are calculated based on the metal elements in the components.

[0102] Accord...

Embodiment 1-1

[0149] The preparation of a styrene-butadiene block copolymer is illustrated.

[0150] In a 5L stainless steel stirred tank under the protection of high-purity nitrogen, add 2457g of refined cyclohexane and 109.2g of styrene after impurity removal, and add a solution of n-butyllithium cyclohexane with a concentration of 0.2M under the condition of stirring and 50°C 27.3mL initiated reaction for 100min;

[0151] After the polymerization is complete, add 163.8g of refined butadiene and continue to react at 50°C for 90min;

[0152] After the reaction is completed, add 1,2-dichloroethane and a cyclohexane solution of silicon tetrachloride to continue the reaction for 30 minutes, wherein the molar ratio of 1,2-dichloroethane to n-butyllithium is 0.15:1, tetrachloro The molar ratio of silicon oxide to n-butyllithium is 0.15:1, and then the terminator isopropanol is added to terminate the reaction, wherein the molar ratio of isopropanol to n-butyllithium is 1:1.

[0153] Obtain the...

Images