Preparation method of shape memory polyurethane

Patent metadata

Field	Value
Publication number	US-11091583-B2
Application number	US-201916452517-A
Country	US
Kind code	B2
Filing date	Jun 25, 2019
Priority date	Jul 5, 2017
Publication date	Aug 17, 2021
Grant date	Aug 17, 2021

Abstract

The present disclosure provides a preparation method of a shape memory polyurethane, which comprising: reacting 1,3,5,7-tetrahydroxyadamantane, ε-caprolactone, a catalyst and a solvent for 20-50 hours under the conditions of inert gas and 70° C. to 130° C. to obtain adamantyl star poly(ε-caprolactone), wherein the mole ratio of the 1,3,5,7-tetrahydroxyadamantane to the ε-caprolactone is 1:(40-240); mixing the adamantyl star poly(ε-caprolactone) with long-chain diol and diisocyanate, adding the catalyst and the solvent, and reacting for 3-9 hours at 50-100° C. to obtain an isocyanate-terminated polyurethane prepolymer, wherein the mass ratio of the adamantyl star poly(ε-caprolactone) to the long-chain diol is 9:1-1:9; and adding a linking agent in the polyurethane prepolymer so that the linking agent reacts with isocyanate in the polyurethane prepolymer to obtain an adamantyl cross-linked shape memory polyurethane.

First claim

The invention claimed is:

1. A method for preparing a shape memory polyurethane comprising:
reacting 1,3,5,7-tetrahydroxyadamantane, ε-caprolactone, a first catalyst and a first solvent for 20-50 hours under the conditions of inert gas and a temperature of 70° C. to 130° C. to obtain adamantyl star poly(ε-caprolactone), wherein the mole ratio of the 1,3,5,7-tetrahydroxyadamantane to the ε-caprolactone is 1:40-1:240;
mixing the adamantyl star poly(ε-caprolactone) with long-chain diol and diisocyanate, adding a second catalyst and a second solvent, and reacting for 3-9 hours at 50-100° C. to obtain a solution of isocyanate-terminated polyurethane prepolymer, wherein the mass ratio of the adamantyl star poly(ε-caprolactone) to the long-chain diol is 9:1-1:9; and
adding a linking agent in the solution of isocyanate-terminated polyurethane prepolymer so that the linking agent reacts with isocyanate in the polyurethane prepolymer to obtain an adamantyl cross-linked shape memory polyurethane,
wherein the long-chain diol is one or more selected from the group consisting of poly(ε-caprolactone) diol, poly(diethylene glycol adipate) diol, polyethylene adipate diol, poly(1,4-butanediol adipate) diol and polyglycol ether diol;
the first catalyst is the same as the second catalyst, and the first solvent is the same as the second solvent.

2. The method of claim 1 , wherein the mole ratio of the 1,3,5,7-tetrahydroxyadamantane to the ε-caprolactone is 1:180-1:240.

3. The method of claim 1 , wherein the mass ratio of the adamantyl star poly(ε-caprolactone) to the long-chain diol is 9:1.

4. The method of claim 1 , wherein the isocyanate is one selected from the group consisting of 2,4-toluene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate biphenyl, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenyldiisocyanate, 1,6-hexamethylene diisocyanate, trans-1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and 3-isocyanate methylene-3,5,5-trimethylcyclohexyl isocyanate.

5. The method of claim 1 , wherein the solvent is one or more selected from the group consisting of toluene, N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl pyrrolidone, dimethylsulfoxide and butyl acetate.

6. The method of claim 1 , wherein the linking agent is one or more selected from the group consisting of 1, 2-ethylene glycol, 1, 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexyl dimethanol, diethylene glycol, 1,4-cyclohexanediol, 1,6-hexanediol, 1, 2-ethylenediamine, 1,3-propane diamine, 1,4-butanediamine, and 1,6-hexamethylenediamine.

7. The method of claim 1 , wherein the catalyst is stannous isooctanate and/or dibutyltin dilaurate.

Assignees

• Univ Shenzhen

Inventors

• Chen Shaojun
• Fu Shuqin

Classifications

• C08G18/12 Primary

  using two or more compounds having active hydrogen in the first polymerisation step · CPC title

• C08G18/73

  acyclic · CPC title

• C08G63/08

  Lactones or lactides · CPC title

• C08G18/4286 Primary

  prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds · CPC title

• C08G18/4277

  Caprolactone and/or substituted caprolactone · CPC title