Amphoteric shape-memory polyurethane and method for preparing the same

Patent metadata

Field	Value
Publication number	US-10329376-B2
Application number	US-201615387589-A
Country	US
Kind code	B2
Filing date	Dec 21, 2016
Priority date	Dec 2, 2014
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

A method for preparing an amphoteric shape-memory polyurethane and an amphoteric shape-memory polyurethane prepared by the method, the method including: 1) polymerizing monomer A and monomer B to synthesize a polyurethane; and 2) contacting monomer D and the polyurethane to conduct a ring-opening reaction on a nitrogen group of the polyurethane, to yield an amphoteric shape-memory polyurethane. The monomer A is a N-alkyl dialkanolamine having a formula I. The monomer B is a polyisocyanate, and the monomer D is an alkyl sulfonate.

First claim

The invention claimed is:

1. A method for preparing an amphoteric shape-memory polyurethane, comprising:
1) polymerizing monomer A and monomer B to synthesize a polyurethane; and
2) contacting monomer D and the polyurethane to conduct a ring-opening reaction on a nitrogen group of the polyurethane, to synthesize an amphoteric shape-memory polyurethane;

wherein
the monomer A is a N-alkyl dialkanolamine having a formula I:

in which,
R represents —C n H m ,
n is an integer between 1 and 18,
m ≤ 2 n +1,
R′ represents C x H 2x , and
x is an integer between 1 and 5;

the monomer B is a polyisocyanate; and
the monomer D is an alkyl sultone;
wherein in 1), following the polymerization of the monomer A and the monomer B, monomer C is added, and the monomer C is a polyhydric alcohol.

2. The method of claim 1 , wherein:
a dosage of the monomer A and a dosage of the monomer C satisfy the following relation: a molar ratio q =[C]/([C] +[A]) involving a molar number [A] of the monomer A and a molar number [C] of the monomer C is between 0 and 0.5;
the dosage of the monomer A, a dosage of the monomer B, and the dosage of the monomer C satisfy that a molar ratio r =[NCO]/[OH] involving a molar number [OH] of a hydroxyl group in the monomer A or a sum of hydroxyl groups in the monomer A and the monomer C and a molar number of [NCO] of an isocyanate group of the monomer B is between 0.95 and 1.05; and
a dosage of the monomer D satisfies that a molar ratio p =[D]/[A] involving the molar number [A] of the monomer A and a molar number [D] of the monomer D is between 0.2 and 1.2.

3. The method of claim 1 , wherein in 1), synthesis of the polyurethane comprises: stirring the monomer A, the monomer B, an organic solvent, and dibutyl tin dilaurate as a catalyst in the presence of nitrogen gas for reaction at a temperature of between 70 and 90° C. for between 2 and 5 hrs; adding the monomer C to a resulting mixture for further reaction for between 2 and 5 hrs to yield a polyurethane prepolymer solution; and adding the organic solvent to the polyurethane prepolymer solution to adjusting a weight concentration of the polyurethane prepolymer solution to account for between 10 and 30 percent by weight of a total weight of a resulting mixed solution.

4. The method of claim 3 , wherein in 2), synthesis of the amphoteric shape-memory polyurethane comprises: mixing the polyurethane prepolymer solution, the monomer D, and the organic solvent in the presence of nitrogen gas to yield a mixed solution, controlling a weight concentration of the mixed solution to be between 5 and 20 percent by weight; sealing the mixed solution for reaction at a temperature of between 30 and 50° C. for between 8 and 24 hrs to yield a solution comprising the amphoteric shape-memory polyurethane.

5. The method of claim 4 , further comprising: evaporating the organic solvent from the solution comprising the amphoteric shape-memory polyurethane at a temperature of between 80 and 100° C.

6. The method of claim 5 , wherein the solution comprising the amphoteric shape-memory polyurethane is dried in a blast oven and a vacuum oven at the temperature of between 80 and 100° C. respectively to evaporate the organic solvent.

7. The method of claim 3 , wherein:
the organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, or tetrahydrofuran;
the monomer B is an aliphatic polyisocyanate acid or an aromatic polyisocyanate acid; and
the monomer C is a dihydric alcohol, a trihydric alcohol, or a tetrahydric alcohol.

8. The method of claim 4 , wherein:
the organic solvent is N, N-dimethylformamide, N, N-dimethylacetamide, or tetrahydrofuran;
the monomer B is an aliphatic polyisocyanate acid or an aromatic polyisocyanate acid; and
the monomer C is a dihydric alcohol, a trihydric alcohol, or a tetrahydric alcohol.

9. The method of claim 1 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

10. The method of claim 2 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

11. The method of claim 3 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

12. The method of claim 4 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

13. The method of claim 5 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

14. The method of claim 6 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

15. The method of claim 7 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

16. The method of claim 8 , wherein:
the N-alkyl dialkanolamine is N-methyldiethanolamine, N-octadecyldiethanolamine, or N-methyldimethanolamine;
the monomer B is hexamethylene diisocyanate, diphenylmethane diisocyanate, or isophorone diisocyanate;
the monomer C is 1,4-butanediol or 1,4-ethanediol; and
the monomer D is 1,3-propanesultone or 1,4-butane sultone.

17. An amphoteric shape-memory polyurethane prepared by the method of claim 1 .

Assignees

• Univ Shenzhen

Inventors

• Chen Shaojun
• Yang Yan
• Mo Funian
• Ren Huanhuan
• Ge Zaochuan

Classifications

• C08G18/73

  acyclic · CPC title

• C08G18/87 Primary

  by sulfur · CPC title

• C08G18/8041 Primary

  with compounds of C08G18/3271 · CPC title

• C08G18/0833 Primary

  containing cationic or cationogenic groups together with anionic or anionogenic groups · CPC title

• C08G18/288

  Compounds containing at least one heteroatom other than oxygen or nitrogen · CPC title