Comb-like polyurethane and methods for preparing and using the same

Patent metadata

Field	Value
Publication number	US-9631044-B2
Application number	US-201514880306-A
Country	US
Kind code	B2
Filing date	Oct 12, 2015
Priority date	Apr 10, 2013
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

A method for preparing a comb-like polyurethane, including: 1) adding a diol to a reaction vessel, stirring, heating, vacuum dehydrating, and cooling the diol; adding a diisocyanate to the diol, and pre-polymerizing the diisocyanate and the diol under vacuum to yield a polyurethane prepolymer; 2) dissolving lysine in a mixture of water and an organic solvent to yield a first solution, adding the first solution to the polyurethane prepolymer to yield a first reaction mixture; stopping stirring and allowing the first reaction mixture to stand for between 10 and 12 hrs, pouring the first reaction mixture into water, and drying a precipitate to yield a polyurethane elastomer containing carboxyl groups; 3) dissolving the polyurethane elastomer in an organic solvent to yield a second solution; adding an epoxy-terminated polyethylene glycol to the second solution, and stirring a resulting mixture at between 110 and 130° C.

First claim

The invention claimed is:

1. A method for preparing a polyurethane, the method comprising:
1) adding 1 part by mole of a diol having a number-average molecular weight of between 500 and 4000 to a reaction vessel, stirring and heating the diol to a temperature of between 100 and 120° C., vacuum dehydrating the diol for between 90 and 240 minutes, and cooling the diol to a temperature of between 50 and 80° C.; adding between 1.58 and 7.10 parts by mole of a diisocyanate to the diol, and pre-polymerizing the diisocyanate and the diol under vacuum at the temperature of between 50 and 80° C. for between 1 and 4 hrs to yield a polyurethane prepolymer;
2) dissolving between 0.5 and 6 parts by mole of lysine in a first solvent to yield a first solution, adding the first solution to the polyurethane prepolymer and stirring for between 10 and 30 min to yield a first reaction mixture; stopping stirring and allowing the first reaction mixture to stand for between 10 and 12 hrs, pouring the first reaction mixture into water, and drying a resulting precipitate at room temperature to yield a polyurethane elastomer containing carboxyl groups;
3) dissolving the polyurethane elastomer containing between 0.5 and 2 parts by mole of the carboxyl groups in a second solvent to yield a second solution; adding dicyclohexylcarbodiimide and N-hydroxysuccinimide which are equimolar and are at least 1.2 times the parts by mole of the carboxyl groups in the polyurethane elastomer, and between 0.5 and 2 parts by mole of an amine-terminated polyethylene glycol in sequence to the second solution, and stirring a resulting mixture for between 20 and 30 hrs at room temperature to yield a reaction solution; and
4) adding 0.1 M hydrochloric acid which is between 1 and 3 wt. % of the second solvent to the reaction solution for reaction for between 3 and 6 hrs; filtering a resulting mixture to remove a precipitate from a first filtrate, and dropping the first filtrate into distilled water under stirring to form a uniformly dispersed colloid; filtering the uniformly dispersed colloid to yield a second filtrate; transferring the second filtrate to a dialysis bag having a molecular weight cutoff of between 8000 and 14000, dialyzing the second filtrate in distilled water, changing the distilled water every 4 to 6 hrs, and taking out the dialysis bag after between 5 and 7 days; vacuum freeze drying a colloid in the dialysis bag to yield a functional polyurethane comprising a side chain of amino-terminated polyethylene glycol;
or
1) adding 1 part by mole of a diol having a number-average molecular weight of between 500 and 4000 to a reaction vessel, stirring and heating the diol to a temperature of between 100 and 120° C., vacuum dehydrating the diol for between 90 and 240 minutes, and cooling the diol to the temperature of between 50 and 80° C.; adding between 1.58 and 7.10 parts by mole of a diisocyanate to the diol, and pre-polymerizing the diisocyanate and the diol under vacuum at the temperature of between 50 and 80° C. for between 1 and 4 hrs to yield a polyurethane prepolymer;
2) dissolving between 0.5 and 6 parts by mole of lysine in a first solvent to yield a first solution, adding the first solution to the polyurethane prepolymer and stirring for between 10 and 30 min to yield a first reaction mixture; stopping stirring and allowing the first reaction mixture to stand for between 10 and 12 hrs, pouring the first reaction mixture into water, and drying a resulting precipitate at room temperature to yield a polyurethane elastomer containing carboxyl groups; and
3) dissolving the polyurethane elastomer containing between 1 and 4 parts by mole of the carboxyl groups in a second solvent to yield a second solution, adding between 1 and 4 parts by mole of an epoxy-terminated polyethylene glycol to the second solution to obtain a second reaction mixture, heating the second mixture to the temperature of between 110 and 130° C. under nitrogen protection, stirring for between 20 and 30 hrs; transferring the second reaction mixture to a dialysis bag having a molecular weight cutoff of between 8000 and 14000, dialyzing the second reaction mixture in distilled water, changing the distilled water every 4 to 6 hrs, and taking out the dialysis bag after between 5 and 7 days; vacuum freeze drying a solution in the dialysis bag to yield a functional polyurethane comprising a side chain of epoxy-terminated polyethylene glycol; wherein
a dosage of the first solvent satisfies that a solid content of the first reaction mixture is between 26 and 39 wt. %;
a dosage of the second solvent satisfies that polyurethane elastomer containing the carboxyl groups is between 2 and 10 wt. % of the second solution;
the first solvent is a mixed solvent of water and one selected from the group consisting of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, and a dosage of water accounts for between 10 and 30 wt. % of the mixed solvent;
the second solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide; and
the number-average molecular weight of the amine-terminated polyethylene glycol or the epoxy-terminated polyethylene glycol is between 200 and 8000.

2. A method for preparing a polyurethane, the method comprising:
a) adding 1 part by mole of a diol having a number-average molecular weight of between 500 and 4000 to a reaction vessel, stirring and heating the diol to a temperature of between 100 and 120° C., vacuum dehydrating the diol for between 90 and 240 minutes, and cooling the diol to the temperature of between 50 and 80° C.; adding between 2.2 and 7.08 parts by mole of a diisocyanate to the diol, and pre-polymerizing the diisocyanate and the diol under vacuum at the temperature of between 50 and 80° C. for between 1 and 4 hrs to yield a polyurethane prepolymer; and
b) dissolving between 0.15 and 2.10 parts by mole of a diamine chain extender containing a side chain of polyethylene glycol in tetrahydrofuran or in a second solvent, adding a resulting solution to the polyurethane prepolymer while stirring to yield a reaction system; stopping heating, allowing to react for between 10 and 15 min; dissolving between 0.5 and 4.5 part by mole of lysine in water to form a lysine solution, and adding the lysine solution to the reaction system for chain extension for between 10 and 30 min; stopping stirring and allowing a reaction mixture to stand for between 10 and 12 hrs; transferring the reaction mixture to a dialysis bag having a molecular weight cutoff of between 8000 and 14000, dialyzing the reaction mixture in distilled water, changing the distilled water every 4 to 6 hrs, and taking out the dialysis bag after between 5 and 7 days; and vacuum freeze drying a solution in the dialysis bag to yield a functional polyurethane comprising a side chain of carboxyl-terminated polyethylene glycol;
wherein
a dosage of tetrahydrofuran or the second solvent satisfies that a total weight of added reactants thereto is between 30 and 50 wt. % of the resulting solution;
the content of water is between 10 and 30 wt. % of the weight of the second solvent;
the second solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide; and
the diamine chain extender containing the side chain of polyethylene glycol is represented by the following formula:

wherein n represents a positive integer ranging from 4 to 180.

3. A polyurethane prepared by the method of claim 1 , comprising the side chain of polyethylene glycol having a functional end group; wherein the functional end group is an amino group or an epoxy group; and a peak of the polyethylene glycol appears on a 1 H-NMR spectrum at a chemical shift of 3.50 ppm and on an infrared

Assignees

• Univ Sichuan
• Univ Laval

Inventors

• Xie Xingyi
• Zhang Ze
• Wu Xiangyang
• Fu Qiang
• Zhong Yinping

Classifications

• C12N2533/30

  Synthetic polymers · CPC title

• C08G18/10 Primary

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08G18/34

  Carboxylic acids; Esters thereof with monohydroxyl compounds · CPC title

• C12N2501/165

  Vascular endothelial growth factor [VEGF] · CPC title

• C12N5/0691

  Vascular smooth muscle cells; 3D culture thereof, e.g. models of blood vessels · CPC title