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Method for preparing functional polyurethane material with surface modified by poly(vinyl methyl ether)

A technology of polymethyl vinyl ether and functional materials, applied in catheters, coatings, medical science, etc., can solve the problems of rare research and increased reaction rate, and achieve the effect of simple production process and excellent mechanical properties

Inactive Publication Date: 2010-07-07
SOUTHEAST UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, for the azido group (-N 3 ) and ethynyl (-C≡CH) Huisgen 1,3-dipolar cycloaddition reaction is the most widely studied. This is because of the high efficiency of this addition reaction, versatility and inert to other functional groups. In Catalyzed by Cu(I), the azide-alkyne reaction rate can be increased by about 10 6 times, almost quantitatively generate 1,4-substituted 1,2,3-triazoles selectively, and the reaction can be carried out in various solvents, even in pure water. In the azido group ( -N 3 ) and ethynyl (-C≡CH) Huisgen 1,3-dipolar cycloaddition reaction. Since Hawker and Sharpless first reported the application of "click" chemical technology in polymer synthesis in 2004, through " Click” technology to construct complex polymers and precisely control the structure of polymers has become a rapidly growing research field. Recently, Qin and DPrez have reported examples of using “click” chemical technology to construct polyurethanes with special structures. At present, Research in this area is still rare.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] 1) Preparation of polymethyl vinyl ether (Init-PMVE-N) whose end group is an azide group 3 ): Under nitrogen protection, mix 0.2079g (7.0mmoL) 2-bromo-2-methylpropanoic acid-3,3-diethoxypropyl (BrDEP) and 1.2mL (8.2mmol) trimethylsilyl iodide (TMSI) was added to a two-necked round-bottomed flask containing 150 mL of dry toluene at a temperature of -40°C. After 10 minutes, first feed 1.0g (0.017moL) of methyl vinyl ether, and then add ZnI 2 (mg, mmol, dissolved in 4mL of anhydrous ether in advance), while continuing to introduce methyl vinyl ether monomer, the introduction rate is 50g h -1 , the molar ratio of monomer to initiator was 37 until 15 g (0.26 mol) of monomer was introduced. After two hours, the reaction was quenched by adding dry methanol and triethylamine. With 10% sodium thiosulfate (Na 2 S 2 o 3 ) aqueous solution to wash the above-mentioned polymer solution three times, then washed three times with deionized water, and finally dried with anhydrous m...

Embodiment 2

[0034] 1) Preparation of polymethyl vinyl ether (Init-PMVE-N) whose end group is an azide group 3 ): Under nitrogen protection, mix 0.2079g (7.0mmoL) 2-bromo-2-methylpropanoic acid-3,3-diethoxypropyl (BrDEP) and 1.2mL (8.2mmol) trimethylsilyl iodide (TMSI) was added to a two-necked round-bottomed flask containing 150 mL of dry toluene at a temperature of -40°C. After 10 minutes, first feed 1.0g (0.017moL) of methyl vinyl ether, and then add ZnI 2 (mg, mmol, dissolved in 4mL of anhydrous ether in advance), while continuing to introduce methyl vinyl ether monomer, the introduction rate is 50g h -1 , the molar ratio of monomer to initiator was 37 until 15 g (0.26 mol) of monomer was introduced. Two hours later, 4.4 mL of isobutyl vinyl ether IBVE (3.38 g, 33.8 mmol) was added and an appropriate amount of ZnI was added. 2 (10 mg, 0.031 mmol), after one hour, the reaction was quenched by adding anhydrous methanol and triethylamine. With 10% sodium thiosulfate (Na 2 S 2 o 3 )...

Embodiment 3

[0038] 1) Preparation of polymethyl vinyl ether (Init-PMVE-N) whose end group is an azide group 3 ): Under nitrogen protection, mix 0.2079g (7.0mmoL) 2-bromo-2-methylpropionic acid-3,3-diethoxypropyl (BrDEP) and 1.2mL (8.2mmol) trimethyl iodide Silane (TMSI) was added to a two-necked round bottom flask containing 150 mL of dry toluene at -40 °C. After 10 minutes, first feed 1.0g (0.017moL) of methyl vinyl ether, and then add ZnI 2 (mg, mmol, dissolved in 4mL of anhydrous ether in advance), while continuing to introduce methyl vinyl ether monomer, the introduction rate is 50g h -1 , the molar ratio of monomer to initiator was 37 until 15 g (0.26 mol) of monomer was introduced. Two hours later, 4.4 mL of isobutyl vinyl ether IBVE (3.38 g, 33.8 mmol) was added and an appropriate amount of ZnI was added. 2 (10 mg, 0.031 mmol), after one hour, the reaction was quenched by adding anhydrous methanol and triethylamine. With 10% sodium thiosulfate (Na 2 S 2 o 3 ) aqueous solutio...

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PUM

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Abstract

The invention relates to a polyurethane material which is obtained by comprehensively utilizing a method combining semi-continuous living cationic polymerization and 'click' chemistry technology and has adjustable surface hydrophilicity, concretely speaking, poly(vinyl methyl ether) or methyl vinyl ether and a copolymer of other monomers are grafted on the surface of the polyurethane material to obtain the surface functionalized polyurethane material. The invention aims to provide a simple and practicable method to modify the surface of polyurethane so as to obtain the required surface with controllable hydrophilicity. By the method, the functional polyurethane material with adjustable surface hydrophilicity and excellent mechanical property can be obtained, and the problem of combining PMVE and polyurethane can be solved, thus forming the novel functional polyurethane material which is simple in technology, economical and practical.

Description

technical field [0001] The invention belongs to the field of surface functionalization of medical polymer materials, and specifically relates to the preparation of a highly stable hydrophilic and adjustable coating on the surface of medical polyurethane materials such as high-end medical catheters, guide wires and cardiovascular stents. method. Background technique [0002] Polyurethanes (PU) are mainly obtained by polyaddition of diisocyanates and diols or polyols as basic raw materials. It was first synthesized by Bayer in 1947 and has a development history of more than 60 years. The main chain structure of PU is diverse. The nature determines its rich and unique physical and chemical properties. The surface functionalized PU has been widely used as biomedical materials. Alcohol (PEG) or heparin can enhance the hydrophilic lubricity of the catheter surface, anticoagulation and anti-protein deposition, and can be applied to the blood vessels of patients. One of the prerequ...

Claims

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Application Information

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IPC IPC(8): C08G81/02C08G18/83C08G18/67C08F16/18C08F8/30A61L29/08A61L29/06A61L31/10A61L31/06
Inventor 张天柱薛云燕江筱莉周雪锋王北琼刘丽石全顾宁
Owner SOUTHEAST UNIV
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