阅读说明：本技术 氢化苯乙烯/共轭二烯烃共聚物及其发泡材料和应用 (Hydrogenated styrene/conjugated diene copolymer, and foaming material and application thereof ) 是由 梁红文 莫笑君 李望明 刘朝周 杨帆 康铮 王旭 佘振银 于 2019-10-29 设计创作，主要内容包括：公开了一种氢化苯乙烯/共轭二烯烃共聚物及其发泡材料和应用,该共聚物含有苯乙烯类结构单元、氢化共轭二烯烃类结构单元；以共聚物的总量为基准,苯乙烯类结构单元的含量为15-50wt％优选18-45重量％,氢化共轭二烯烃类结构单元中1,2-聚合结构单元的含量为8-32％优选10-30％更优选12-25％,苯乙烯类结构单元在所述氢化共轭二烯烃类结构单元中的无规度为30-80％优选为35-75％,所述共聚物中共轭二烯烃的氢化度为85-100％优选95-100％。该氢化苯乙烯/共轭二烯烃共聚物的扯断拉伸强度为30-60MPa、扯断伸长率300-600％、硬度(邵氏A)为70-98,并且可以采用超临界二氧化碳发泡工艺制作反弹大于60％,压缩变形小于30％的性能优异的发泡体。(Disclosed is a hydrogenated styrene/conjugated diene copolymer, its foaming material and application, wherein the copolymer contains styrene structural unit, hydrogenated conjugated diene structural unit; the content of the styrenic structural unit is 15 to 50% by weight, preferably 18 to 45% by weight, the content of the 1, 2-polymerized structural unit in the hydrogenated conjugated diene structural unit is 8 to 32% by weight, preferably 10 to 30% by weight, more preferably 12 to 25% by weight, the randomness of the styrenic structural unit in the hydrogenated conjugated diene structural unit is 30 to 80% by weight, preferably 35 to 75% by weight, and the degree of hydrogenation of the conjugated diene in the copolymer is 85 to 100% by weight, preferably 95 to 100% by weight, based on the total amount of the copolymer. The hydrogenated styrene/conjugated diene copolymer has tensile strength at break of 30-60MPa, elongation at break of 300-600% and hardness (Shore A) of 70-98, and can be prepared into foam with excellent performance, wherein the rebound is more than 60% and the compression deformation is less than 30% by adopting a supercritical carbon dioxide foaming process.)

A hydrogenated styrene/conjugated diene copolymer comprising a styrene-based structural unit represented by the formula 1, a conjugated diene-based structural unit represented by the formula 2 and a conjugated diene-based structural unit represented by the formula 3,

wherein R is₁、R ₂、R ₃、R ₄、R ₅、R ₆、R ₇、R ₈、R ₉Each is H, C1-C3 alkyl, R₁₀Is H or C1-C4 alkyl; the content of the styrenic structural unit is 15 to 50% by weight, preferably 18 to 45% by weight, based on the total amount of the copolymer, the content of the hydrogenated conjugated diene structural unit represented by formula 3 is 8 to 32% by weight, based on the total amount of the hydrogenated conjugated diene structural unit represented by formula 2 and the hydrogenated conjugated diene structural unit represented by formula 3, the randomness of the styrenic structural unit in the conjugated diene structural unit is 30 to 80%, and the hydrogenation degree of the conjugated diene in the copolymer is 85 to 100%.

The hydrogenated styrene/conjugated diene copolymer according to claim 1, wherein the content of the styrenic structural unit is from 25 to 35% by weight based on the total amount of the copolymer, the content of the hydrogenated conjugated diene structural unit represented by formula 3 is from 10 to 30% by weight, preferably from 12 to 25% by weight based on the total amount of the hydrogenated conjugated diene structural unit represented by formula 2 and the hydrogenated conjugated diene structural unit represented by formula 3, the randomness of the styrenic structural unit in the conjugated diene structural unit is from 35 to 70%, and the degree of hydrogenation of the conjugated diene in the copolymer is from 95 to 100%.

The hydrogenated styrene/conjugated diene copolymer according to claim 1 or 2, wherein the crystallization temperature of the hydrogenated styrene/conjugated diene copolymer as measured by DSC is 18 ℃ or more, preferably 18 to 70 ℃, and the enthalpy is not less than 1.7J/g, preferably 2 to 25J/g.

The hydrogenated styrene/conjugated diene copolymer according to any one of claims 1 to 3, wherein the domains formed by the styrenic structural unit represented by formula 1 and the domains formed by the hydrogenated conjugated diene structural unit represented by formula 2 and the hydrogenated conjugated diene structural unit represented by formula 3 coexist in a columnar/spherical and lamellar distribution.

The hydrogenated styrene/conjugated diene copolymer according to any one of claims 1 to 4, wherein the styrenic structural unit represented by formula 1, the hydrogenated conjugated diene structural unit represented by formula 2 and the hydrogenated conjugated diene structural unit represented by formula 3 are a structural unit represented by the following formula 1 to 1, a structural unit represented by the following formula 2 to 1 and a structural unit represented by the following formula 3 to 1, respectively

The hydrogenated styrene/conjugated diene copolymer according to any one of claims 1 to 5, wherein the copolymer has a number average molecular weight of 3 to 50 ten thousand, preferably 4 to 20 ten thousand, more preferably 5 to 8 ten thousand, as measured by gel chromatography.

The hydrogenated styrene/conjugated diene copolymer according to any one of claims 1 to 6, wherein the copolymer has a 300% tensile strength at break of 8MPa or more, preferably 10 to 20MPa, a tensile strength at break of 30MPa or more, preferably 30 to 60MPa, an elongation at break of 300-600%, preferably 350-500%, a hardness (Shore A) of 80 or more, preferably 80-98, and a melt index (200 ℃,5kg) of 0 to 8g/10min, preferably 1 to 2g/10 min.

A foamed material obtained by foaming, preferably physically foaming, the hydrogenated styrene/conjugated diene copolymer according to any one of claims 1 to 7.

The foam material according to claim 8, wherein the rebound of the foam measured according to ASTM-D2632 is from 58 to 65%, and the compression set of the foam measured according to GB/T6669-2008 is from 20 to 28%.

The foamed material of claim 8 or 9, wherein the foaming is supercritical carbon dioxide foaming or supercritical nitrogen foaming.

Use of the foam material according to any one of claims 8 to 10 for the preparation of foamed shoe soles.

Use of a hydrogenated styrene/conjugated diene copolymer according to any one of claims 1 to 7 for the preparation of foamed shoe soles.