Modified non-hydrogenated styrene elastomer material and preparation method thereof

Abstract

The invention discloses a modified non-hydrogenated styrene elastomer material and a preparation method thereof, relates to the technical field of high polymer material synthesis and modification, and provides a structural formula of the modified non-hydrogenated styrene elastomer material. The modified non-hydrogenated styrene elastomer material is prepared by condensation polymerization of a high-molecular polymer of a single-end functionalized or double-end functionalized non-hydrogenated styrene elastomer, isocyanate with a structural general formula of OCN-R-NCO and an amino silane compound in an organic solvent. The elastomer material disclosed by the invention is a multi-block copolymer which takes a non-hydrogenated styrene elastomer material as a main component, so that the surface performance of the styrene elastomer is remarkably improved, and the problems of poor stain resistance and oil resistance of styrene thermoplastic elastomers can be effectively solved.

Description

Technical Field

[0001] This invention relates to the field of polymer material synthesis and modification technology, specifically to a modified non-hydrogenated styrene elastomer material and its preparation method. Background Technology

[0002] Styrene-based thermoplastic elastomers are block polymers formed by the polymerization of styrene with butadiene or isoprene, and their hydrogenated derivatives. They combine the high elasticity of rubber with the hot processing properties of plastics, making them polymer materials that fall between traditional vulcanized rubber and plastics. Styrene-based thermoplastic elastomers possess excellent thermal stability, low-temperature flexibility, resilience, impact resistance, and biocompatibility, and are widely used in plastic impact modifiers, asphalt modifiers, cable insulation sheaths, sealants, adhesives, medical devices, waterproof membranes, coatings, and footwear manufacturing.

[0003] However, the poor stain and oil resistance of styrene-based thermoplastic elastomers has become a bottleneck restricting their development, especially in the automotive, consumer electronics, smart wearable devices, and medical device industries. Compared with typical organic compounds, siloxane molecular chains are generally considered to possess dual "organic-inorganic" properties. Polydimethylsiloxane, in particular, exhibits extremely low glass transition temperature (Tg = -123℃), very low surface tension and surface energy, surface hydrophobicity, low solubility parameters and low dielectric constant, oxidation stability against atomic oxygen and plasma, high permeability to various gases, surface activity, and chemical and physiological inertness. Introducing siloxane bonds into polymers can enable organic polymers to acquire the various properties possessed by organosilicon. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a modified non-hydrogenated styrene elastomer material and its preparation method. This elastomer material is a multi-block copolymer with non-hydrogenated styrene elastomer material as the main component, which significantly improves the surface properties of styrene elastomers and can effectively solve the problems of poor stain resistance and oil resistance of styrene thermoplastic elastomers.

[0005] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A modified non-hydrogenated styrene elastomer material is provided, the structural formula of which is:

[0006]

[0007] Where X is styrene;

[0008] Y is at least one of polybutadiene and polyisoprene;

[0009] A is

[0010] S is an isocyanate with the general structural formula OCN-R-NCO;

[0011] G is

[0012] R is at least one of methyl, ethyl, vinyl, propyl, trifluoropropyl, and phenyl;

[0013] m is a positive integer between 10 and 1000;

[0014] n is a positive integer between 20 and 3000;

[0015] j is a positive integer between 0 and 1000;

[0016] k is a positive integer between 0 and 1000;

[0017] p is a positive integer between 10 and 1000;

[0018] q is a positive integer between 4 and 200.

[0019] Furthermore, Y is at least one of 1,2-polybutadiene, 1,4-polybutadiene, 1,2-polyisoprene, and 1,4-polyisoprene.

[0020] Further, S is one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoflurone diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, terephthalene diisocyanate, 1,4-cyclohexane diisocyanate, phenylmethylene diisocyanate, cyclohexane dimethyl diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl-isophenylmethylene diisocyanate, norbornene diisocyanate, dimethyl biphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyl diphenylmethane diisocyanate, and lysine diisocyanate.

[0021] The above-mentioned modified non-hydrogenated styrene elastomer material is prepared by condensation polymerization of a single- or double-functionalized non-hydrogenated styrene elastomer polymer, an isocyanate with the general structural formula OCN-R-NCO, and an aminosilane compound in an organic solvent.

[0022] Furthermore, the preparation method of the modified non-hydrogenated styrene elastomer material includes the following steps:

[0023] At a temperature of 20-80℃, the polymer of a single- or double-functionalized non-hydrogenated styrene elastomer is dissolved in an organic solvent, and then an excess of isocyanate with the general formula OCN-R-NCO is added. The reaction is carried out for 1-2 hours, and an excess of glacial ethanol is added to obtain a precipitate. The precipitate is then dissolved in an organic solvent, followed by the addition of an aminosilane compound. The reaction is carried out for 1-2 hours, and an excess of glacial ethanol is added to obtain a precipitate. The precipitate is then dried to obtain a modified non-hydrogenated styrene elastomer material.

[0024] Furthermore, the single- or double-functionalized non-hydrogenated styrene elastomer is first reacted with an isocyanate having the general structural formula OCN-R-NCO, and then reacted with an aminosilane compound to obtain a modified non-hydrogenated styrene elastomer material.

[0025] Furthermore, the mass ratio of the single- or double-functionalized non-hydrogenated styrene elastomer polymer, the isocyanate with the general structural formula OCN-R-NCO, and the aminosilane compound is 1:0.01-0.5:0.01-1.

[0026] Furthermore, the aminosilane compound is one of monoaminosilane, diaminosilane, triaminosilane, and polyaminosilane.

[0027] Furthermore, the organic solvent is at least one selected from toluene, xylene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0028] Furthermore, condensation polymerization is carried out at temperatures of 20-80℃.

[0029] The present invention has the following beneficial effects:

[0030] 1. This invention involves the condensation polymerization of a single- or double-functionalized non-hydrogenated styrene elastomer, an isocyanate with the general structural formula OCN-R-NCO, and an aminosilane in a solution system to prepare a multi-block copolymer with non-hydrogenated styrene elastomer as the main component. This significantly improves the surface properties of styrene elastomers and can effectively solve the problems of poor stain resistance and oil resistance of styrene thermoplastic elastomers.

[0031] 2. This invention introduces siloxane bonds into non-hydrogenated styrene elastomers. This modified non-hydrogenated styrene elastomer can not only maintain its excellent elasticity, but also improve its stain resistance and oil resistance, achieving technical effects that are completely unexpected by those skilled in the art. It has very good economic benefits and is very suitable for industrial applications.

[0032] 3. The preparation method of the present invention prepares modified non-hydrogenated styrene elastomer through a simple condensation polymerization reaction. The reaction is carried out at 20-80℃, the process is easy to control, and there are no harsh reaction conditions.

[0033] 4. The modified non-hydrogenated styrene elastomer material obtained by this invention has excellent stain resistance and oil resistance, which can expand the application of hydrogenated styrene elastomers in the automotive, consumer electronics, smart wearable devices and medical device industries. Detailed Implementation

[0034] The principles and features of this invention are described below. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0035] Example 1

[0036] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0037] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess toluene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Monoaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0038] Example 2

[0039] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0040] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess diphenylmethane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Monoaminosilane was then added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain another precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0041] Example 3

[0042] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0043] In a reactor at 35°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then hexamethylene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Monoaminosilane was then added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0044] Example 4

[0045] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0046] In a reactor at 45°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess isoflurane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of monoaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0047] Example 5

[0048] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0049] In a reactor at 65°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of monoaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0050] Example 6

[0051] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0052] In a reactor at 75°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess 1,4-cyclohexane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of monoaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0053] Example 7

[0054] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0055] In a reactor at 25°C, a single-hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess toluene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0056] Example 8

[0057] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0058] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess diphenylmethane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0059] Example 9

[0060] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0061] In a reactor at 35°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess hexamethylene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0062] Example 10

[0063] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0064] In a reactor at 45°C, a single-hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess isoflurane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of diaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0065] Example 11

[0066] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0067] In a reactor at 65°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of diaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0068] Example 12

[0069] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0070] In a reactor at 75°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess 1,4-cyclohexane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0071] Example 13

[0072] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0073] In a reactor at 25°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess toluene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0074] Example 14

[0075] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0076] In a reactor at 25°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess diphenylmethane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0077] Example 15

[0078] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0079] In a reactor at 35°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess hexamethylene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0080] Example 16

[0081] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0082] In a reactor at 45°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess isoflurane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0083] Example 17

[0084] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0085] In a reactor at 65°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of polyaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0086] Example 18

[0087] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0088] In a reactor at 75°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess 1,4-cyclohexane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of polyaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0089] Example 19

[0090] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0091] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess toluene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Monoaminosilane was then added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0092] Example 20

[0093] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0094] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess diphenylmethane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Monoaminosilane was then added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0095] Example 21

[0096] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0097] In a reactor at 35°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess hexamethylene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Monoaminosilane was then added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0098] Example 22

[0099] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0100] In a reactor at 45°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess isoflurane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of monoaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0101] Example 23

[0102] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0103] In a reactor at 65°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of monoaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0104] Example 24

[0105] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0106] In a reactor at 75°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess 1,4-cyclohexane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Monoaminosilane was then added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain another precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0107] Example 25

[0108] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0109] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess toluene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0110] Example 26

[0111] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0112] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess diphenylmethane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0113] Example 27

[0114] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0115] In a reactor at 35°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess hexamethylene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0116] Example 28

[0117] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0118] In a reactor at 45°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, then excess isoflurane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, diaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0119] Example 29

[0120] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0121] In a reactor at 65°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of diaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0122] Example 30

[0123] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0124] In a reactor at 75°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess 1,4-cyclohexane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of diaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0125] Example 31

[0126] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0127] In a reactor at 25°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess toluene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0128] Example 32

[0129] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0130] In a reactor at 25°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess diphenylmethane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0131] Example 33

[0132] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0133] In a reactor at 35°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess hexamethylene diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0134] Example 34

[0135] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0136] In a reactor at 45°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, then excess isoflurane diisocyanate was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dissolved in tetrahydrofuran. Next, polyaminosilane was added, and the reaction was carried out for 1 hour. Excess glacial ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0137] Example 35

[0138] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0139] In a reactor at 65°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of polyaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0140] Example 36

[0141] A modified non-hydrogenated styrene elastomer material, the preparation method of which includes the following steps:

[0142] In a reactor at 75°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, and then excess 1,4-cyclohexane diisocyanate was added. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was then dissolved in tetrahydrofuran, followed by the addition of polyaminosilane. The reaction was carried out for 1 hour, and then excess glacial ethanol was added to obtain a precipitate. The precipitate was dried at 60°C to obtain a modified non-hydrogenated styrene elastomer material.

[0143] Comparative Example 1

[0144] An elastomer material, the preparation method of which includes the following steps:

[0145] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer was dissolved in tetrahydrofuran, and then an excess of dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and an excess of icy ethanol was added to obtain a precipitate. The precipitate was then dried at 60°C to obtain the elastomer material.

[0146] Comparative Example 2

[0147] An elastomer material, the preparation method of which includes the following steps:

[0148] In a reactor at 25°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, and then polyaminosilane was added. After reacting for 1 hour, excess icy ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain the elastomer material.

[0149] Comparative Example 3

[0150] An elastomer material, the preparation method of which includes the following steps:

[0151] In a reactor at 25°C, a hydroxyl-terminated styrene-butadiene-styrene elastomer material was dissolved in tetrahydrofuran, and then an excess of dicyclohexylmethane diisocyanate was added. The reaction was carried out for 1 hour, and an excess of icy ethanol was added to obtain a precipitate. The precipitate was then dried at 60°C to obtain the elastomer material.

[0152] Comparative Example 4

[0153] An elastomer material, the preparation method of which includes the following steps:

[0154] In a reactor at 25°C, a hydroxyl-terminated styrene-isoprene-styrene elastomer material was dissolved in tetrahydrofuran, and then polyaminosilane was added. After reacting for 1 hour, excess icy ethanol was added to obtain a precipitate, which was then dried at 60°C to obtain the elastomer material.

[0155] Experimental Example

[0156] In a reactor at 25°C, styrene-butadiene-styrene elastomer material with single or double hydroxyl ends was dissolved in tetrahydrofuran. Then, excess diisocyanate was added, and after reacting for 1 hour, excess glacial ethanol was added to obtain a precipitate. The precipitate was dissolved in tetrahydrofuran, and then mono-amino, di-amino, or polyamino silanes were added. After reacting for 1 hour, excess glacial ethanol was added to obtain a precipitate. The precipitate was thoroughly dried at 60°C to obtain a modified non-hydrogenated styrene elastomer. The stain resistance of the modified non-hydrogenated styrene elastomer was tested according to QB / T5070-2017 "Test Methods for Stain Resistance of Artificial Leather and Synthetic Leather". The test results are shown in Table 1.

[0157] Table 1. Experimental Results

[0158]

[0159]

[0160] As shown in Table 1, this invention provides a modified non-hydrogenated styrene elastomer material and its preparation method. This material is a multi-block copolymer with non-hydrogenated styrene elastomer as the main component. It is prepared by condensation polymerization of a single- or double-ended functionalized non-hydrogenated styrene elastomer, an isocyanate with the general formula OCN-R-NCO, and an aminosilane in a solution system. The modified non-hydrogenated styrene elastomer prepared by this invention not only maintains its excellent elasticity but also improves its stain resistance and oil resistance, achieving technical effects that are completely unexpected by those skilled in the art. It has excellent economic benefits and is very suitable for industrial applications.

[0161] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A modified non-hydrogenated styrene elastomer material, characterized in that, Its structural formula is: Where X is styrene; Y is at least one of polybutadiene and polyisoprene; A is S is an isocyanate with the general structural formula OCN-R-NCO; G is R is at least one of methyl, ethyl, vinyl, propyl, trifluoropropyl, and phenyl; m is a positive integer between 10 and 1000; n is a positive integer between 20 and 3000; j is a positive integer between 0 and 1000; k is a positive integer between 0 and 1000; p is a positive integer between 10 and 1000; q is a positive integer between 4 and 200.

2. The modified non-hydrogenated styrene elastomer material as described in claim 1, characterized in that, The Y is at least one of 1,2-polybutadiene, 1,4-polybutadiene, 1,2-polyisoprene, and 1,4-polyisoprene.

3. The modified non-hydrogenated styrene elastomer material as described in claim 1, characterized in that, The S is one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoflurone diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, terephthalic diisocyanate, 1,4-cyclohexane diisocyanate, phenylmethylene diisocyanate, cyclohexane dimethyl diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl-methylene diisocyanate, norbornene diisocyanate, dimethyl biphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyl diphenylmethane diisocyanate, and lysine diisocyanate.

4. The method for preparing the modified non-hydrogenated styrene elastomer material according to any one of claims 1-3, characterized in that, The modified non-hydrogenated styrene elastomer material is prepared by condensation polymerization of a single- or double-functionalized non-hydrogenated styrene elastomer polymer, an isocyanate with the general structural formula OCN-R-NCO, and an aminosilane compound in an organic solvent.

5. The method for preparing the modified non-hydrogenated styrene elastomer material as described in claim 4, characterized in that, Includes the following steps: At a temperature of 20-80℃, the polymer of a single- or double-functionalized non-hydrogenated styrene elastomer is dissolved in an organic solvent, and then an excess of isocyanate with the general formula OCN-R-NCO is added. The reaction is carried out for 1-2 hours, and an excess of glacial ethanol is added to obtain a precipitate. The precipitate is then dissolved in an organic solvent, followed by the addition of an aminosilane compound. The reaction is carried out for 1-2 hours, and an excess of glacial ethanol is added to obtain a precipitate. The precipitate is then dried to obtain a modified non-hydrogenated styrene elastomer material.

6. The method for preparing the modified non-hydrogenated styrene elastomer material as described in claim 4 or 5, characterized in that, The polymer of the single- or double-functionalized non-hydrogenated styrene elastomer, the isocyanate with the general structural formula OCN-R-NCO, and the aminosilane compound are in a mass ratio of 1:0.01-0.5:0.01-1.

7. The method for preparing the modified non-hydrogenated styrene elastomer material as described in claim 4 or 5, characterized in that, The aminosilane compound is one of monoaminosilane, diaminosilane, triaminosilane, and polyaminosilane.

8. The method for preparing the modified non-hydrogenated styrene elastomer material as described in claim 4 or 5, characterized in that, The organic solvent is at least one selected from toluene, xylene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide, and N,N-dimethylacetamide.

9. The method for preparing the modified non-hydrogenated styrene elastomer material as described in claim 4, characterized in that, Condensation polymerization occurs at temperatures ranging from 20 to 80°C.

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