CN109354706A - A kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified - Google Patents
A kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified Download PDFInfo
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- CN109354706A CN109354706A CN201811189217.6A CN201811189217A CN109354706A CN 109354706 A CN109354706 A CN 109354706A CN 201811189217 A CN201811189217 A CN 201811189217A CN 109354706 A CN109354706 A CN 109354706A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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- General Chemical & Material Sciences (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention provides a kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified, is that the multifunctional polyurethane pre-polymer solution is coated on medical catheter surface, after baking and curing, chemical graft or be adhered on medical catheter surface；The wherein polyglycol chain in the multifunctional polyurethane prepolymer structure, can assign the hydrophily and biocompatibility on the medical catheter surface；Furthermore it is quaternary ammonium cation, the medical catheter surface disinfection antibacterial functions and hydrophily can be assigned.
Description
Technical field
The present invention relates to a kind of application of polyurethane prepolymer in medical catheter surface is modified, in particular to molecular structure
In the multifunctional polyurethane prepolymer containing quaternary ammonium cation and polyglycol chain in the sterilization of medical catheter surface hydrophilic is modified
Application, belong to functional polymer material field.
Technical background
Polyurethane (Polyurethanes, PUs) is to contain the one of carbamate (- NHCOO-) repetitive unit on main chain
The general name of class macromolecule polyalcohol usually occurs sudden reaction by polyalcohol and polyisocyanates and generates, and belongs to typical embedding
Section copolymer；Compared with other high molecular materials, polyurethane material is with molecular structure easily designs, performance is controllable, processability
The characteristics such as energy is good, processing method is various, mechanical performance is excellent.By carrying out functional modification to polyurethane material, thus protecting
While holding polyurethane excellent performance, and its unique biology, photoelectromagnetic heat and other physicochemical properties are assigned, these
Functional polyurethane materials have applied multiple fields.
Medical catheter be refer to connection organism inside and outside, drain, blood-transmitted, auxiliary import other medical apparatus and
Pass through used a kind of tubular body during situation in sensing element detection organism etc..It can be used as the material kind of conduit
Class is various, includes mainly polyvinyl chloride (PVC), silicon rubber, polyurethane or natural rubber, and these materials are hydrophobicity mostly
's.Currently, polymer material catheter outer surface hydrophilic lubrication modification mode can be divided into physical modification, chemical modification, plasma
It is simple and easy to have the low in cost of physical modification, technology only for modification, Modification of Photo-grafting Copolymerization etc..Physical modification is i.e. in conduit table
Face directly coats hydrophilic polymer.Common hydrophilic polymer has polyvinyl alcohol (PVA), polyacrylamide (PAM), poly- second
Glycol (PEG), polyethylene glycol oxide (PEO), polyvinylpyrrolidone (PVP) or its copolymer or its blend etc..By hydrophily
It is the easiest that polymer-coated in catheter surface is modified technology, but hydrophilic polymer adhesive force is weaker, and coating is easy to fall off.
In use, another big problem is Endophytic bacteria in supravasal adherency and proliferation to medical catheter, and it is all in turn result in infection
More problems not only increase disease incidence and case fatality rate in hospital, while also increasing the cost of health care.Therefore exploitation water
While lubricating medical catheter, it can be improved its bacteriostasis property and be of great significance.Conjugated polymer material conduit outer surface parent
While water lubrication is modified, the main method that the surface that antibiotic bactericide is current medical catheter is modified is introduced.On this basis,
The present inventor develops more containing quaternary ammonium cation and polyglycol chain in a kind of molecular structure by MOLECULE DESIGN and research
Function polyurethane prepolymer can be applied to the hydrophilic lubrication of surface of polymer material and sterilize antibacterial modified.
Summary of the invention
The present invention provides a kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified, more function
Energy polyurethane prepolymer refers to the polyurethane prepolymer described in molecular structure containing quaternary ammonium cation and polyglycol chain.Institute
The high-hydrophilic on medical catheter surface, strong antibiotic and sterilizing function can be assigned by stating multifunctional polyurethane prepolymer.
A kind of application technology scheme of the multifunctional polyurethane prepolymer of the present invention in medical catheter surface bacterium is modified
It is: will be uniformly impregnated in the multifunctional polyurethane pre-polymer solution by the medical catheter cleaned up；It takes out
The medical catheter of the completely described multifunctional polyurethane pre-polymer solution is dipped in, baking oven of the temperature between 20~80 DEG C is placed in
In, it is dried 2~72 hours, the modified medical catheter of the multifunctional polyurethane pre-polymer surface is made；
Wherein the medical catheter refers to medical made of polyvinyl chloride, polyurethane, silicon rubber or natural rubber lead
Pipe；
The multifunctional polyurethane pre-polymer solution includes component as described below: multifunctional polyurethane prepolymer 10~100
Part, 0~30 part of chain extender, 0~10 part of trimethylamine, 0~3.0 part of organotin catalysts, 50~500 parts of solvent.
The multifunctional polyurethane prepolymer has structure shown in general formula (A):
R in its formula of (A)1、R2And R3It is respectively selected from C1~C18One of alkyl；M in 1,2 or 3 one
Kind；WithSelected from C1~C18Alkylene orOne of, wherein n is selected between 1~20000
Natural number；X-Selected from Cl-Or Br-。
The chain extender is selected from ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, trimethylolpropane, diethylene glycol (DEG), three sweet
One of alcohol, 1,4- cyclohexanediol, triethanolamine, N methyldiethanol amine.
The trimethylamine is selected from triethylamine, tri-n-butylamine, N, N- dimethyl benzylamine, N,N-dimethylformamide, triethylene
Diamines, dialkylpiperazines, alkyl imidazole, 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0], triethylene diamine carboxylate, two
One of alkyl piperazine carboxylate or alkyl imidazole carboxylate.
The organotin catalysts are selected from dibutyltin dilaurate, stannous octoate, stannous oxalate, two Malaysia of dialkyl group
Sour tin, two (dodecyl sulphur) one of dibutyl tins or dibutyltin diacetate.
The solvent be selected from tetrahydrofuran, 1,4- dioxane, chlorine benzene,toluene,xylene, chloroform, 1,2- dichloroethanes,
Hexane, hexamethylene, decahydronaphthalene, ethyl acetate, N-Methyl pyrrolidone, acetone, butanone, cyclohexanone, n,N-Dimethylaniline, neighbour
Rutgers, diethyl phthalate, dibutyl phthalate, N,N-dimethylformamide, N, N- dimethyl
One or more of acetamide or dimethyl sulfoxide.
Functional group there are three types of in general formula (A) multifunctional polyurethane prepolymer molecule structure of the present invention, the first
Functional group is isocyanate group (- NCO), be it with the amide groups of the polyurethane, polyamide or cellulosic material surface (-
CONH the function base) or after hydroxyl (- OH) progress chemically reacted, while being also to realize that multifunctional polyurethane is pre- with chain extender reaction
The curing functional groups of polymers；Followed by polyglycol chain (poly (ethylene glycol) chain, PEG chain), energy
Enough assign the hydrophily and biocompatibility of the surface of polymer material；It furthermore is quaternary ammonium cation (quaternary
Ammonium cations, QACs), the surface of polymer material sterilization antibacterial and hydrophily can be assigned.
The preparation method of general formula (A) multifunctional polyurethane prepolymer of the present invention, concrete operations are as follows: at room temperature, will
Alkylating reagent, hydroxylamine base polyethylene glycol and polyisocyanates are dissolved in organic solvent respectively, and after stirring and dissolving, alkane is made respectively
Base reagent solution, alkanolamine solution and polyisocyanate solution；Alkylating reagent solution is added in the alkanolamine solution, control
10~120 DEG C of reaction temperature, after being stirred to react 0.5~15 hour, the polyisocyanate solution is added, adjusts reaction temperature
To 20~80 DEG C, continue to be stirred to react 0.5~15 hour, the multifunctional polyurethane prepolymer of structure shown in general formula (A) is made
Solution；
Wherein alkylating reagent is selected from benzyl chloride, 4- methoxy-benzyl chlorine, 4- ethoxy benzyl chlorine, 4- dodecyloxy benzyl
Base chlorine, benzyl bromide, dodecyl bromide, 1- bromobutane, 1- bromooctane, 5- chloromethyl salicylaldehyde, 4,4 '-dichloromethyl diphenyl ether,
3- chloromethane yl diphenyl ether, 2- chloroethyl ethyl ether, 2- bromoethyl ethylether, to benzyl dichloride, 4,4 '-biphenyl-benzyl dichlorides or 1,4- bis-
One of bromobutane；
The hydroxylamine base polyethylene glycol has structure shown in general formula (B):
R in its formula of (B)1And R2Hydrogen or alkyl are not chosen or are respectively selected from C1~C18One of alkyl；M is selected from
1, one of 2 or 3；Selected from C1~C18Alkylene orOne of, wherein n be selected from 1~
Natural number between 20000；
The polyisocyanates has structure shown in general formula (C):
P in its formula of (C) is selected from 1~5 positive integer,Selected from C1~C18Alkylene orOne of, n therein is selected from the natural number between 1~20000；
The mole dosage of the polyisocyanates and the alkylating reagent is the hydroxylamine base polyethylene glycol mole respectively
1.1~3.5 times of dosage and 1.0~6.0 times；
The organic solvent is selected from tetrahydrofuran, 1,4- dioxane, chlorine benzene,toluene,xylene, chloroform, 1,2- dichloro
Ethane, hexane, hexamethylene, decahydronaphthalene, ethyl acetate, N-Methyl pyrrolidone, acetone, butanone, cyclohexanone, N, N- dimethyl benzene
Amine, repefral, diethyl phthalate, dibutyl phthalate, N,N-dimethylformamide, N, N- bis-
One or more of methylacetamide or dimethyl sulfoxide；The quality dosage of the solvent is general formula (B) polyisocyanates
0.5~500 times of quality dosage.
Specific embodiment
In order to be explained to it by way of example to the further understanding of present invention work, its object is to
More fully understand the contents of the present invention.Therefore, the multifunctional polyurethane prepolymer unlisted in embodiment is in medical catheter
Application during surface hydrophilic sterilization is modified, is not construed as limiting the scope of the invention.
Embodiment 1
Weigh 65 grams of formula (b1) shown in structure N, N- dimethyl amido polyethylene glycol -600 is dissolved in 40 grams of N, N- bis-
In methylformamide, N, the n,N-Dimethylformamide solution of N- dimethyl amido polyethylene glycol -600 is made；Weigh 4- methoxy
20 grams of base benzyl chloride are dissolved in 20 grams of ethyl acetate, and the ethyl acetate solution of 4- methoxy-benzyl chlorine is made；Weigh toluene two
30 grams and 0.01 gram of dibutyltin dilaurate of isocyanates are dissolved in 26 grams of Isosorbide-5-Nitrae-dioxane, and toluene diisocyanate is made
The dioxane of acid esters；The ethyl acetate solution is added in the n,N-Dimethylformamide solution, control reaction
20~25 DEG C of temperature, after being stirred to react 2 hours, then by dioxane addition reaction system, adjust reaction temperature 60
~65 DEG C, continue after being stirred to react 2 hours, formula (a is made1) multifunctional polyurethane prepolymer solution；
Formula (a1) the isocyanate group mass percentage in multifunctional polyurethane pre-polymer solution is using GB/T
29493.6-2013 prescriptive procedure detects, sampling analysis detects formula (a1) isocyanates in multifunctional polyurethane pre-polymer solution
The mass percentage of base is 3.88%；
Be 3mm outer diameter by internal diameter it is that the polyurethane catheter that 4.8mm length is 360mm is placed in ethyl alcohol, is cleaned by ultrasonic 30 points
It takes out and dries after clock, be placed in 40 milliliters of formula (a1) 5 seconds in multifunctional polyurethane pre-polymer solution, take out in merging baking oven
60~62 DEG C dry 2 hours, and the modified polyurethane catheter in surface is made.Polyurethane catheter weight after weighing surface before modified
Amount difference is 0.8837 gram, rate of body weight gain 4.3324%, is impregnated 10 seconds in deionized water, takes out and weighs 4.6341 grams of weight gain again.
The water contact angle of polyurethane catheter surface is respectively 78.5 ° and 32.8 ° after before modified, and its is heavy after immersion for a long time in water
Amount does not change, and illustrates that polyurethane catheter surface coating does not fall off, surface lubrication persistence is stablized.
Embodiment 2
According to the method and operating procedure of embodiment 1, by the formula (c in embodiment 11) shown in structure N, N- dimethyl amine
It is formula (c that base polyethylene glycol -600, which changes,2) shown in structure N, N- dimethyl amido Polyethylene glycol-2000,4- methoxy-benzyl
It is 4- dodecyloxy benzyl chloride that chlorine, which changes, and formula (A is made2) multifunctional polyurethane pre-polymer solution.Using the method for embodiment 1
Measurement formula (A2) multifunctional polyurethane pre-polymer solution isocyanate group mass percentage be 3.28%.
Be 3mm outer diameter by internal diameter it is that the polyurethane catheter that 4.8mm length is 360mm is placed in ethyl alcohol, is cleaned by ultrasonic 30 points
It takes out and dries after clock, be placed in 40 milliliters of formula (A2) 5 seconds in multifunctional polyurethane pre-polymer solution, take out in merging baking oven
60~62 DEG C dry 2 hours, and the modified polyurethane catheter in surface is made.Polyurethane catheter weight after weighing surface before modified
Amount difference is 0.8842 gram, rate of body weight gain 4.3337%, is impregnated 10 seconds in deionized water, takes out and weighs 4.6735 grams of weight gain again.
The water contact angle of polyurethane catheter surface is respectively 78.5 ° and 30.5 ° after before modified, and its is heavy after immersion for a long time in water
Amount does not change, and illustrates that polyurethane catheter surface coating does not fall off, surface lubrication persistence is stablized.
Embodiment 3
According to the method and operating procedure of embodiment 1, by the formula (c in embodiment 11) shown in structure N, N- dimethyl amine
It is formula (c that base polyethylene glycol -600, which changes,3) shown in structure the double Polyethylene glycol-2000s of N- benzamido group, 4- methoxy-benzyl chlorine changes
It is changed to dodecyl bromide, it is '-diphenylmethane diisocyanate that toluene di-isocyanate(TDI), which changes, and formula (A is made3) multifunctional polyurethane
Pre-polymer solution.Formula (A is measured using the method for embodiment 13) multifunctional polyurethane pre-polymer solution isocyanate group matter
Measuring percentage composition is 6.22%.
It is 3mm outer diameter by internal diameter is that the polyvinyl chloride conduit that 4.8mm length is 360mm and polyurethane catheter are respectively placed in second
In alcohol, ultrasonic cleaning is taken out after 30 minutes dries, and is placed in 40 milliliters of formula (A3) multifunctional polyurethane prepolymer and 1.8 milliliters
5 seconds in the mixed solution of glycerol, takes out in merging baking oven and dry 2 hours for 60~62 DEG C, the modified polychlorostyrene second in surface is made
Alkene conduit.Through weigh surface before modified after polyvinyl chloride conduit weight difference be 1.0177 grams, rate of body weight gain 3.0907%, go from
It is impregnated 10 seconds in sub- water, takes out and weigh 5.0957 grams of weight gain again.The water contact angle point on polyvinyl chloride conduit surface after before modified
It Wei not be 80.6 ° and 28.5 °.Polyurethane catheter weight difference after weighing surface before modified is 1.3183 grams, and rate of body weight gain is
6.4632%, it impregnates 10 seconds in deionized water, takes out and weigh 6.5865 grams of weight gain again.Polyurethane catheter surface after before modified
Water contact angle is respectively 78.5 ° and 28.3 °, and its weight does not change after immersion for a long time in water, illustrates polyurethane guide
Pipe surface coating does not fall off, surface lubrication persistence is stablized.
Claims (8)
1. a kind of application of multifunctional polyurethane prepolymer in medical catheter surface is modified, it is characterised in that: will be through over cleaning
The clean medical catheter is uniformly impregnated in the multifunctional polyurethane pre-polymer solution；Completely described more function have been dipped in taking-up
The medical catheter of energy polyurethane prepolymer solution is placed in temperature in the baking oven between 20~80 DEG C, is dried 2~72
Hour, the modified medical catheter of the multifunctional polyurethane pre-polymer surface is made.
2. application of a kind of multifunctional polyurethane prepolymer in medical catheter surface is modified according to claim 1, special
Sign is that the medical catheter refers to the medical catheter made of polyvinyl chloride, polyurethane, silicon rubber or natural rubber.
3. application of a kind of multifunctional polyurethane prepolymer in medical catheter surface is modified according to claim 1, special
Sign is that the multifunctional polyurethane pre-polymer solution includes component as described below: 10~100 parts of multifunctional polyurethane prepolymer,
0~30 part of chain extender, 0~10 part of trimethylamine, 0~3.0 part of organotin catalysts, 50~500 parts of solvent；
Wherein the multifunctional polyurethane prepolymer has structure shown in general formula (A):
R in its formula of (A)1、R2And R3It is respectively selected from C1~C18One of alkyl；M is selected from one of 1,2 or 3；
WithSelected from C1~C18Alkylene orOne of, wherein n is selected from the nature between 1~20000
Number；X-Selected from Cl-Or Br-。
The chain extender is selected from ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, 1,
One of 4- cyclohexanediol, triethanolamine, N methyldiethanol amine；
The trimethylamine be selected from triethylamine, tri-n-butylamine, N, N- dimethyl benzylamine, N,N-dimethylformamide, triethylene diamine,
Dialkylpiperazines, alkyl imidazole, 11 carbon -7- alkene of 1,8- diazabicyclo [5.4.0], triethylene diamine carboxylate, dialkyl group
One of piperazine carboxylic acid salt or alkyl imidazole carboxylate；
The organotin catalysts are selected from dibutyltin dilaurate, stannous octoate, stannous oxalate, two maleic acid of dialkyl group
Tin, two (dodecyl sulphur) one of dibutyl tins or dibutyltin diacetate；
The solvent be selected from tetrahydrofuran, 1,4- dioxane, chlorine benzene,toluene,xylene, chloroform, 1,2- dichloroethanes, oneself
Alkane, hexamethylene, decahydronaphthalene, ethyl acetate, N-Methyl pyrrolidone, acetone, butanone, cyclohexanone, n,N-Dimethylaniline, adjacent benzene
Dicarboxylic acid dimethyl ester, diethyl phthalate, dibutyl phthalate, N,N-dimethylformamide, N, N- dimethyl second
One or more of amide or dimethyl sulfoxide.
4. application of a kind of multifunctional polyurethane prepolymer in medical catheter surface is modified according to claim 1, special
Sign is that the preparation method of the multifunctional polyurethane prepolymer is as described below: at room temperature, by alkylating reagent, the poly- second of hydroxylamine base
Two pure and mild polyisocyanates are dissolved in organic solvent respectively, and after stirring and dissolving, alkylating reagent solution, alkanolamine solution are made respectively
And polyisocyanate solution；Alkylating reagent solution is added in the alkanolamine solution, 10~120 DEG C of reaction temperature is controlled, stirs
After mixing reaction 0.5~15 hour, the polyisocyanate solution is added, reaction temperature is adjusted to 20~80 DEG C, continues to stir
The solution of the multifunctional polyurethane prepolymer of structure shown in general formula (A) is made in reaction 0.5~15 hour.
5. application of a kind of multifunctional polyurethane prepolymer in medical catheter surface is modified according to claim 4, special
Sign is that the alkylating reagent is selected from benzyl chloride, 4- methoxy-benzyl chlorine, 4- ethoxy benzyl chlorine, 4- dodecyloxy benzyl
Chlorine, benzyl bromide, dodecyl bromide, 1- bromobutane, 1- bromooctane, 5- chloromethyl salicylaldehyde, 4,4 '-dichloromethyl diphenyl ether, 3-
Chloromethane yl diphenyl ether, 2- chloroethyl ethyl ether, 2- bromoethyl ethylether, to benzyl dichloride, 4,4 '-biphenyl-benzyl dichlorides or 1,4- dibromo
One of butane.
6. application of a kind of multifunctional polyurethane prepolymer in medical catheter surface is modified according to claim 4, special
Sign is that the hydroxylamine base polyethylene glycol has structure shown in general formula (B):
R in its formula of (B)1And R2Hydrogen or alkyl are not chosen or are respectively selected from C1~C18One of alkyl；M is selected from 1,2
Or one of 3；Selected from C1~C18Alkylene orOne of, wherein n is selected from 1~20000
Between natural number.
7. application of a kind of multifunctional polyurethane prepolymer in medical catheter surface is modified according to claim 4, special
Sign is that the polyisocyanates has structure shown in general formula (C):
P in its formula of (C) is selected from 1~5 positive integer,Selected from C1~C18Alkylene orIn
One kind, wherein n be selected from 1~20000 between natural number；
The mole dosage of the polyisocyanates and the alkylating reagent is the hydroxylamine base polyethylene glycol mole dosage respectively
1.1~3.5 times and 1.0~6.0 times.
8. application of a kind of multifunctional polyurethane prepolymer in medical catheter surface is modified according to claim 4, special
Sign is that the organic solvent is selected from tetrahydrofuran, 1,4- dioxane, chlorine benzene,toluene,xylene, chloroform, bis- chloroethene of 1,2-
Alkane, hexane, hexamethylene, decahydronaphthalene, ethyl acetate, N-Methyl pyrrolidone, acetone, butanone, cyclohexanone, N, N- dimethyl benzene
Amine, repefral, diethyl phthalate, dibutyl phthalate, N,N-dimethylformamide, N, N- bis-
One or more of methylacetamide or dimethyl sulfoxide；The quality dosage of the solvent is general formula (B) polyisocyanates
0.5~500 times of quality dosage.
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| CN112279970A (en) * | 2020-10-21 | 2021-01-29 | 江苏海洋大学 | Application of hydroxyl-terminated polymer in preparation of multifunctional interpenetrating network polymer |
| CN112281494A (en) * | 2020-10-21 | 2021-01-29 | 江苏海洋大学 | Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing |
| CN112778894A (en) * | 2021-01-06 | 2021-05-11 | 北京化工大学 | Novel antibacterial and mildew-proof polyurethane paint film based on triethanolamine and preparation method thereof |
| CN113061230A (en) * | 2021-03-25 | 2021-07-02 | 江苏海洋大学 | Self-closed polyurethane prepolymer |
| CN116283674A (en) * | 2023-03-06 | 2023-06-23 | 江苏海洋大学 | Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279970A (en) * | 2020-10-21 | 2021-01-29 | 江苏海洋大学 | Application of hydroxyl-terminated polymer in preparation of multifunctional interpenetrating network polymer |
| CN112281494A (en) * | 2020-10-21 | 2021-01-29 | 江苏海洋大学 | Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing |
| CN112281494B (en) * | 2020-10-21 | 2022-03-11 | 江苏海洋大学 | Application of blocked polyurethane prepolymer in preparation of cellulose-based functional dressing |
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| CN112778894A (en) * | 2021-01-06 | 2021-05-11 | 北京化工大学 | Novel antibacterial and mildew-proof polyurethane paint film based on triethanolamine and preparation method thereof |
| CN113061230A (en) * | 2021-03-25 | 2021-07-02 | 江苏海洋大学 | Self-closed polyurethane prepolymer |
| CN113061230B (en) * | 2021-03-25 | 2022-05-06 | 江苏海洋大学 | Self-closed polyurethane prepolymer |
| CN116283674A (en) * | 2023-03-06 | 2023-06-23 | 江苏海洋大学 | Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof |
| CN116283674B (en) * | 2023-03-06 | 2023-11-24 | 江苏海洋大学 | Isocyanate crosslinking agent containing disulfo betaine and preparation method thereof |
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