CN111909356A - Medical polyurethane material and preparation method thereof - Google Patents
Medical polyurethane material and preparation method thereof Download PDFInfo
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- CN111909356A CN111909356A CN202010856315.1A CN202010856315A CN111909356A CN 111909356 A CN111909356 A CN 111909356A CN 202010856315 A CN202010856315 A CN 202010856315A CN 111909356 A CN111909356 A CN 111909356A
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Abstract
The invention discloses a medical polyurethane material and a preparation method thereof, wherein the polyurethane material is prepared by taking diisocyanate and polymer polyol as reactants and adding a modifier, an accelerant and the like for reaction; diphenylmethane diisocyanate and 1, 6-hexamethylene diisocyanate are selected from the diisocyanate; polycarbonate polyol, polyethylene glycol and polytetramethylene ether glycol are selected from polymer polyol; the modifier is a mixture of 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4' -amino-4-nitrodiphenylamine-2-sulfonic acid; the accelerant is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynyl phenetole; the finally prepared polyurethane material has high tensile strength and elongation at break, and also has high antibacterial performance, and can be used as a medical material.
Description
Technical Field
The invention relates to the field of organic polymer synthesis, in particular to a medical polyurethane material and a preparation method thereof.
Background
Polyurethane is a general name of a polymer containing carbamate groups (-NHCOO-) on a molecular main chain, has the characteristics of good wear resistance, high tensile strength and elongation at break, easiness in molding and processing and the like, and is widely applied to the fields of textile, packaging, food processing, medical treatment and health care and the like. Currently, polyurethane products mainly include the following: foams, elastomers, fiber plastics, fibers, leather shoe resins, coatings, adhesives, sealants, and the like; among them, polyurethane elastomers have been widely used in the medical field, for example, as medical films, due to their characteristics of high strength, good toughness, no harm to human body, etc.; however, the application of the existing polyurethane material in the medical and medical field is not mature, because the existing common polyurethane material does not have antibacterial performance, and if the polyurethane material is used as a medical material, the requirement of human health cannot be met, so that the development of the polyurethane material is limited to a certain extent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a medical polyurethane material and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: a medical polyurethane material comprises the following substances in parts by weight:
30-50 parts of diphenylmethane isocyanate;
10-20 parts of 1, 6-hexamethylene diisocyanate;
5-15 parts of polycarbonate polyol;
5-15 parts of polyethylene glycol;
5-15 parts of polytetramethylene ether glycol;
5-10 parts of micromolecular polyol;
3-6 parts of chain extender
3-6 parts of a modifier;
2-4 parts of an accelerator;
1-2 parts of a catalyst.
As a further improvement of the invention, the number average molecular weight of the polycarbonate polyol is 500-4000; the number average molecular weight of the polyethylene glycol is 400-3000; the number average molecular weight of the polytetramethylene ether glycol is 500-5000.
As a further improvement of the invention, the small-molecule polyol is a mixture of 1, 6-hexanediol, diiodoneopentyl glycol and 3-aminopropylsilanetriol in a mass ratio of 1:2: 2.
As a further improvement of the invention, the modifier is a mixture of 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4' -amino-4-nitrodiphenylamine-2-sulfonic acid in a mass ratio of 3:2: 1.
Wherein the structural formula of the 1, 2-bis (3, 5-diphenyl isothiazole-4-yl) disulfane is shown in the specification
As a further improvement of the invention, the accelerator is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynylphenetole in a mass ratio of 2:1: 1.
As a further improvement of the invention, the chain extender is a mixture of 3-amino-2-4-chlorophenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, the mass ratio of which is 2:1: 4.
As a further improvement of the invention, the catalyst is an organic zinc catalyst.
As a further improvement of the invention, the preparation method of the medical polyurethane material is characterized in that: the method comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, firstly putting diphenylmethane isocyanate, 1, 6-hexamethylene diisocyanate, polycarbonate polyol, polyethylene glycol, polytetramethylene ether glycol, micromolecule polyol, an accelerant and a catalyst into a reaction container to be stirred and mixed, and reacting for 2-6h at the temperature of 100-160 ℃ after being uniformly mixed to form a prepolymer;
step two: and putting the prepolymer, the chain extender and the modifier into a reaction container, stirring and mixing, and reacting for 4-8 hours at the temperature of 140-200 ℃ after uniformly mixing to obtain the medical polyurethane material.
The invention has the beneficial effects that: the isocyanate-terminated polyurethane adhesive is prepared by taking diisocyanate and polymer polyol as reactants and adding micromolecular polyol, a chain extender, a modifier, an accelerator and the like for reaction; diphenylmethane diisocyanate and 1, 6-hexamethylene diisocyanate are selected from the diisocyanate; two benzene rings exist in the diphenylmethane diisocyanate, and two NCO groups are respectively and symmetrically connected to the 4 th positions of the two benzene rings, the highly symmetrical structure not only endows the thermoplastic polyurethane with rigidity, but also can enable a hard section to crystallize, and the phenomenon of micro-phase separation can be generated between the hard section and the soft section due to the high order of the hard section, so that the polyurethane is endowed with excellent physical and mechanical properties, and the 1, 6-hexamethylene diisocyanate does not contain the benzene rings, thereby being beneficial to improving the toughness of the polyurethane resin; under the combined action of diphenylmethane diisocyanate and 1, 6-hexamethylene diisocyanate, the polyurethane material with relatively high tensile strength and elongation at break can be obtained; polycarbonate polyol, polyethylene glycol and polytetramethylene ether glycol are selected from polymer polyol, wherein the polycarbonate polyol contains a carbonate bond in a chain segment, so that the tensile strength of a polyurethane material is improved, and the hydrolysis resistance of the polyurethane material is improved; by selecting the diisocyanate and the polymer polyol, the finally prepared polyurethane material has relatively high tensile strength, elongation at break and certain antibacterial property.
In order to further improve the tensile strength and antibacterial performance of the polyurethane material, the invention adds a modifier which is a mixture of 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4 '-amino-4-nitrodiphenylamine-2-sulfonic acid, wherein 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane contains structures such as thiazolyl, disulfide bond and phenyl, diallyl chlorophosphite contains structures such as carbon-carbon double bond and phosphorous acid group, 4' -amino-4-nitrodiphenylamine-2-sulfonic acid contains structures such as amino and sulfonic acid group, and due to the existence of the structures, the substances have synergistic effect, and by adding the three substances, the antibacterial property of the polyurethane material can be greatly improved, so that the polyurethane material has good antibacterial property, can be used as a medical material, and simultaneously further improves the tensile strength of the polyurethane material, thereby meeting the requirement of actual production.
The polyurethane material is also added with an accelerant which is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynylphenetole, and the addition of the accelerant is favorable for improving the compatibility between the accelerant and diisocyanate and polymer polyol, so that various reactants can fully play a role, and the polyurethane material with ideal performance can be obtained finally, and the antibacterial performance of the polyurethane material is further improved due to the existence of structures such as epoxy groups in the accelerant.
In addition, three low molecular weight substances, namely 3-amino-2-4-chlorphenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, are selected on the chain extender; the materials contain active functional groups such as amino, hydroxyl and the like, wherein both the amino and the hydroxyl can react with diisocyanate to generate hard segments rich in-NHCON-, -NHCOO-, and can form hydrogen bond aggregation areas; researches show that the short chain extender is matched with the long chain extender, the polyurethane elastomer synthesized by the short chain extender has better mechanical property, and the short chain extender shortens the distance between hard segments, so that the hydrogen bond action between the hard segments is more obvious, the aggregation of hard segment molecules is facilitated, the microphase separation of the polyurethane elastomer molecules is promoted, and the polyurethane elastomer has better mechanical property; in addition, as the chain extender also contains groups such as sulfonic group, chlorine group and the like, the antibacterial property of the polyurethane material can be further improved due to the existence of the groups; under the combined action of the three substances, the tensile strength and the antibacterial property of the polyurethane material can be further improved, and the application range of the polyurethane material is widened.
The finally prepared polyurethane material has high tensile strength and elongation at break, and also has high antibacterial performance, and can be used as a medical material.
Detailed Description
Example 1
A medical polyurethane material comprises the following substances in parts by weight:
40 parts of diphenylmethane isocyanate;
15 parts of 1, 6-hexamethylene diisocyanate;
10 parts of polycarbonate polyol;
10 parts of polyethylene glycol;
10 parts of polytetramethylene ether glycol;
8 parts of small molecular polyol;
chain extender 5 parts
4 parts of a modifier;
3 parts of an accelerant;
1 part of catalyst.
The polycarbonate polyol has a number average molecular weight of 2000; the number average molecular weight of the polyethylene glycol is 2000;
the number average molecular weight of the polytetramethylene ether glycol is 3000.
The small molecular polyol is a mixture of 1, 6-hexanediol, diiodoneopentyl glycol and 3-aminopropylsilanetriol, and the mass ratio of the small molecular polyol to the 3-aminopropylsilanetriol is 1:2: 2.
The modifier is a mixture of 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4' -amino-4-nitrodiphenylamine-2-sulfonic acid, and the mass ratio of the modifier to the modifier is 3:2: 1.
The accelerator is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynyl phenetole, and the mass ratio of the accelerator to the ethynyl phenetole is 2:1: 1.
The chain extender is a mixture of 3-amino-2-4-chlorphenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, and the mass ratio of the chain extender to the hydroquinone di (beta-hydroxyethyl) ether is 2:1: 4.
The catalyst is an organic zinc catalyst.
A preparation method of a medical polyurethane material comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, firstly putting diphenylmethane isocyanate, 1, 6-hexamethylene diisocyanate, polycarbonate polyol, polyethylene glycol, polytetramethylene ether glycol, micromolecule polyol, an accelerant and a catalyst into a reaction container, stirring and mixing, uniformly mixing, and reacting for 4 hours at the temperature of 120 ℃ to form a prepolymer;
step two: and putting the prepolymer, the chain extender and the modifier into a reaction container, stirring and mixing, uniformly mixing, and reacting for 6 hours at the temperature of 160 ℃ to obtain the medical polyurethane material.
Example 2
A medical polyurethane material comprises the following substances in parts by weight:
50 parts of diphenylmethane isocyanate;
10 parts of 1, 6-hexamethylene diisocyanate;
15 parts of polycarbonate polyol;
10 parts of polyethylene glycol;
5 parts of polytetramethylene ether glycol;
9 parts of small molecular polyol;
chain extender 3 parts
5 parts of a modifier;
3 parts of an accelerant;
and 2 parts of a catalyst.
The number average molecular weight of the polycarbonate polyol is 1000; the number average molecular weight of the polyethylene glycol is 1000; the number average molecular weight of the polytetramethylene ether glycol is 2000.
The small molecular polyol is a mixture of 1, 6-hexanediol, diiodoneopentyl glycol and 3-aminopropylsilanetriol, and the mass ratio of the small molecular polyol to the 3-aminopropylsilanetriol is 1:2: 2.
The modifier is a mixture of 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4' -amino-4-nitrodiphenylamine-2-sulfonic acid, and the mass ratio of the modifier to the modifier is 3:2: 1.
The accelerator is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynyl phenetole, and the mass ratio of the accelerator to the ethynyl phenetole is 2:1: 1.
The chain extender is a mixture of 3-amino-2-4-chlorphenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, and the mass ratio of the chain extender to the hydroquinone di (beta-hydroxyethyl) ether is 2:1: 4.
The catalyst is an organic zinc catalyst.
A preparation method of a medical polyurethane material comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, firstly putting diphenylmethane isocyanate, 1, 6-hexamethylene diisocyanate, polycarbonate polyol, polyethylene glycol, polytetramethylene ether glycol, micromolecule polyol, an accelerant and a catalyst into a reaction container, stirring and mixing, uniformly mixing, and reacting for 4 hours at the temperature of 140 ℃ to form a prepolymer;
step two: and putting the prepolymer, the chain extender and the modifier into a reaction container, stirring and mixing, and reacting at 180 ℃ for 6 hours after uniformly mixing to obtain the medical polyurethane material.
Example 3
A medical polyurethane material comprises the following substances in parts by weight:
35 parts of diphenylmethane isocyanate;
20 parts of 1, 6-hexamethylene diisocyanate;
5 parts of polycarbonate polyol;
10 parts of polyethylene glycol;
15 parts of polytetramethylene ether glycol;
5 parts of small molecular polyol;
chain extender 6 parts
5 parts of a modifier;
3 parts of an accelerant;
1 part of catalyst.
The number average molecular weight of the polycarbonate polyol is 3000; the number average molecular weight of the polyethylene glycol is 1500; the number average molecular weight of the polytetramethylene ether glycol is 2000.
The small molecular polyol is a mixture of 1, 6-hexanediol, diiodoneopentyl glycol and 3-aminopropylsilanetriol, and the mass ratio of the small molecular polyol to the 3-aminopropylsilanetriol is 1:2: 2.
The modifier is a mixture of 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4' -amino-4-nitrodiphenylamine-2-sulfonic acid, and the mass ratio of the modifier to the modifier is 3:2: 1.
The accelerator is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynyl phenetole, and the mass ratio of the accelerator to the ethynyl phenetole is 2:1: 1.
The chain extender is a mixture of 3-amino-2-4-chlorphenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, and the mass ratio of the chain extender to the hydroquinone di (beta-hydroxyethyl) ether is 2:1: 4.
The catalyst is an organic zinc catalyst.
A preparation method of a medical polyurethane material comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, firstly putting diphenylmethane isocyanate, 1, 6-hexamethylene diisocyanate, polycarbonate polyol, polyethylene glycol, polytetramethylene ether glycol, micromolecule polyol, an accelerant and a catalyst into a reaction container, stirring and mixing, uniformly mixing, and reacting for 4 hours at the temperature of 120 ℃ to form a prepolymer;
step two: and putting the prepolymer, the chain extender and the modifier into a reaction container, stirring and mixing, uniformly mixing, and reacting for 5 hours at the temperature of 160 ℃ to obtain the medical polyurethane material.
Comparative example 1
A medical polyurethane material comprises the following substances in parts by weight:
40 parts of diphenylmethane isocyanate;
15 parts of 1, 6-hexamethylene diisocyanate;
10 parts of polycarbonate polyol;
10 parts of polyethylene glycol;
5-15 parts of polytetramethylene ether glycol;
8 parts of small molecular polyol;
chain extender 5 parts
1 part of catalyst.
The polycarbonate polyol has a number average molecular weight of 2000; the number average molecular weight of the polyethylene glycol is 2000; the number average molecular weight of the polytetramethylene ether glycol is 3000.
The small molecular polyol is a mixture of 1, 6-hexanediol, diiodoneopentyl glycol and 3-aminopropylsilanetriol, and the mass ratio of the small molecular polyol to the 3-aminopropylsilanetriol is 1:2: 2.
The chain extender is a mixture of 3-amino-2-4-chlorphenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, and the mass ratio of the chain extender to the hydroquinone di (beta-hydroxyethyl) ether is 2:1: 4.
The catalyst is an organic zinc catalyst.
A preparation method of a medical polyurethane material comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, firstly putting diphenylmethane isocyanate, 1, 6-hexamethylene diisocyanate, polycarbonate polyol, polyethylene glycol, polytetramethylene ether glycol, micromolecule polyol and a catalyst into a reaction container together, stirring and mixing, uniformly mixing, and reacting for 4 hours at the temperature of 120 ℃ to form a prepolymer;
step two: and (3) putting the prepolymer and the chain extender into a reaction container, stirring and mixing, uniformly mixing, and reacting for 6 hours at the temperature of 160 ℃ to obtain the medical polyurethane material.
Performance testing
The test method comprises the following steps: the mechanical properties (tensile strength and elongation at break) were tested on the samples prepared in examples 1-3 and comparative example 1 according to the requirements of the national standard GB/T1040.2-2006;
the samples prepared in examples 1-3 and comparative example 1 were tested for antibacterial performance (bactericidal efficiency against staphylococcus aureus, escherichia coli) according to the standard requirements of "QB/T2591 antibacterial plastic-antibacterial performance test method and antibacterial effect";
mechanical properties
Test specimen | Tensile strength/MPa | Elongation at break/% |
Example 1 | 68 | 610 |
Example 2 | 76 | 650 |
Example 3 | 72 | 570 |
Comparative example 1 | 42 | 360 |
As can be seen from the above table, the medical polyurethane materials prepared in the embodiments 1 to 3 of the present invention have high tensile strength and elongation at break, can meet the requirements of practical production, and can be used as medical materials.
Antibacterial property
Test specimen | Sterilization efficiency (%) against Staphylococcus aureus | Sterilization efficiency for Escherichia coli (%) |
Example 1 | 90% | 91% |
Example 2 | 82% | 83% |
Example 3 | 87% | 85% |
Comparative example 1 | 52% | 54% |
As can be seen from the above table, the medical polyurethane materials prepared in the embodiments 1-3 of the present invention have the sterilization efficiency of over 80% for Staphylococcus aureus and Escherichia coli, have strong antibacterial performance, and can meet the requirements of medical materials.
The medical polyurethane material is prepared by taking diisocyanate and polymer polyol as reactants and adding micromolecular polyol, a chain extender, a modifier, an accelerator and the like into the reactants for reaction; diphenylmethane diisocyanate and 1, 6-hexamethylene diisocyanate are selected from the diisocyanate; two benzene rings exist in the diphenylmethane diisocyanate, and two NCO groups are respectively and symmetrically connected to the 4 th positions of the two benzene rings, the highly symmetrical structure not only endows the thermoplastic polyurethane with rigidity, but also can enable a hard section to crystallize, and the phenomenon of micro-phase separation can be generated between the hard section and the soft section due to the high order of the hard section, so that the polyurethane is endowed with excellent physical and mechanical properties, and the 1, 6-hexamethylene diisocyanate does not contain the benzene rings, thereby being beneficial to improving the toughness of the polyurethane resin; under the combined action of diphenylmethane diisocyanate and 1, 6-hexamethylene diisocyanate, the polyurethane material with relatively high tensile strength and elongation at break can be obtained; polycarbonate polyol, polyethylene glycol and polytetramethylene ether glycol are selected from polymer polyol, wherein the polycarbonate polyol contains a carbonate bond in a chain segment, so that the tensile strength of a polyurethane material is improved, and the hydrolysis resistance of the polyurethane material is improved; by selecting the diisocyanate and the polymer polyol, the finally prepared polyurethane material has relatively high tensile strength, elongation at break and certain antibacterial property.
As one of the key points of the invention, in order to further improve the tensile strength and antibacterial performance of the polyurethane material, the invention adds a modifier, wherein the modifier is 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4 '-amino-4-nitrodiphenylamine-2-sulfonic acid, the 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane contains structures such as thiazolyl, disulfide bond and phenyl, the diallyl chlorophosphite contains structures such as carbon-carbon double bond and phosphorous acid group, the 4' -amino-4-nitrodiphenylamine-2-sulfonic acid contains structures such as amino and sulfonic acid group, and due to the existence of the structures, the surprising discovery shows that the substances generate synergistic action, by adding the three substances, the antibacterial property of the polyurethane material can be greatly improved, so that the polyurethane material has good antibacterial property, can be used as a medical material, and simultaneously further improves the tensile strength of the polyurethane material, thereby meeting the requirements of actual production.
As another key point of the invention, the polyurethane material is also added with an accelerant which is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynylphenetole, and the addition of the accelerant is helpful to improve the compatibility between the accelerant and diisocyanate and polymer polyol, so that various reactants can fully play a role, and the polyurethane material with ideal performance can be obtained finally, and on the other hand, the antibacterial performance of the polyurethane material is further improved due to the existence of structures such as epoxy groups and the like in the accelerant.
In addition, three low molecular weight substances, namely 3-amino-2-4-chlorphenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, are selected on the chain extender; the materials contain active functional groups such as amino, hydroxyl and the like, wherein both the amino and the hydroxyl can react with diisocyanate to generate hard segments rich in-NHCON-, -NHCOO-, and can form hydrogen bond aggregation areas; researches show that the short chain extender is matched with the long chain extender, the polyurethane elastomer synthesized by the short chain extender has better mechanical property, and the short chain extender shortens the distance between hard segments, so that the hydrogen bond action between the hard segments is more obvious, the aggregation of hard segment molecules is facilitated, the microphase separation of polyurethane elastomer molecules is promoted, and the polyurethane elastomer has better mechanical property; in addition, as the chain extender also contains groups such as sulfonic group, chlorine group and the like, the antibacterial property of the polyurethane material can be further improved due to the existence of the groups; under the combined action of the three substances, the tensile strength and the antibacterial property of the polyurethane material can be further improved, and the application range of the polyurethane material is widened.
The finally prepared polyurethane material has high tensile strength and elongation at break, and also has high antibacterial performance, and can be used as a medical material.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. A medical polyurethane material is characterized in that: the composition comprises the following substances in parts by weight:
30-50 parts of diphenylmethane diisocyanate;
10-20 parts of 1, 6-hexamethylene diisocyanate;
5-15 parts of polycarbonate polyol;
5-15 parts of polyethylene glycol;
5-15 parts of polytetramethylene ether glycol;
5-10 parts of micromolecular polyol;
3-6 parts of chain extender
3-6 parts of a modifier;
2-4 parts of an accelerator;
1-2 parts of a catalyst.
2. The medical polyurethane material according to claim 1, wherein: the number average molecular weight of the polycarbonate polyol is 500-4000; the number average molecular weight of the polyethylene glycol is 400-3000; the number average molecular weight of the polytetramethylene ether glycol is 500-5000.
3. The medical polyurethane material according to claim 1, wherein: the small molecular polyol is a mixture of 1, 6-hexanediol, diiodoneopentyl glycol and 3-aminopropylsilanetriol, and the mass ratio of the small molecular polyol to the 3-aminopropylsilanetriol is 1:2: 2.
4. The medical polyurethane material according to claim 1, wherein: the modifier is a mixture of 1, 2-bis (3, 5-diphenylisothiazol-4-yl) disulfane, diallyl chlorophosphite and 4' -amino-4-nitrodiphenylamine-2-sulfonic acid, and the mass ratio of the modifier to the modifier is 3:2: 1.
5. The medical polyurethane material according to claim 1, wherein: the accelerator is a mixture of 4-methoxyphenyl dimethylvinylsilane, 1, 2-epoxy-5-hexene and 4-ethynyl phenetole, and the mass ratio of the accelerator to the ethynyl phenetole is 2:1: 1.
6. The medical polyurethane material according to claim 1, wherein: the chain extender is a mixture of 3-amino-2-4-chlorphenyl-2-hydroxypropane sodium sulfonate, thiophene-2, 3-dicarboxylic acid and hydroquinone di (beta-hydroxyethyl) ether, and the mass ratio of the chain extender to the hydroquinone di (beta-hydroxyethyl) ether is 2:1: 4.
7. The medical polyurethane material according to claim 1, wherein: the catalyst is an organic zinc catalyst.
8. The method for preparing a polyurethane material for medical use according to any one of claims 1 to 7, wherein: the method comprises the following steps:
the method comprises the following steps: preparing raw materials according to the set weight parts, firstly putting diphenylmethane isocyanate, 1, 6-hexamethylene diisocyanate, polycarbonate polyol, polyethylene glycol, polytetramethylene ether glycol, micromolecule polyol, an accelerant and a catalyst into a reaction container to be stirred and mixed, and reacting for 2-6h at the temperature of 100-160 ℃ after being uniformly mixed to form a prepolymer;
step two: and putting the prepolymer, the chain extender and the modifier into a reaction container, stirring and mixing, and reacting for 4-8 hours at the temperature of 140-200 ℃ after uniformly mixing to obtain the medical polyurethane material.
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CN115403916A (en) * | 2022-05-16 | 2022-11-29 | 上海年与轻科技(集团)有限公司 | Piezoelectric power generation device shell material for chip in shoe and preparation method thereof |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2844610A1 (en) * | 1978-10-13 | 1980-04-30 | Hoechst Ag | METHOD FOR PRODUCING 4-NITRO-4'-AMINO-DIPHENYLAMINE-2-SULFONIC ACID AND 2-NITRO-4'-AMINO-DIPHENYLAMINE-4-SULPHONIC ACID |
CN101987885A (en) * | 2009-08-05 | 2011-03-23 | 合肥普尔德医疗用品有限公司 | Antibacterial, waterproof and moisture permeable type composite functional material and preparation method and application thereof |
CN102454107A (en) * | 2010-10-26 | 2012-05-16 | 北京崇高纳米科技有限公司 | Polyurethane synthetic leather capable of inhibiting bacteria and resisting mildew and preparation method thereof |
CN102911510A (en) * | 2012-10-25 | 2013-02-06 | 上海贝通色彩科技有限公司 | Ink-jet dye compound and preparation method thereof |
CN106519158A (en) * | 2016-10-26 | 2017-03-22 | 江南大学 | Preparation method of hyperbranched poly (urethane-amine) with hydroxide radical serving as end group and internal branched units provided with vinyl |
CN107201183A (en) * | 2017-07-18 | 2017-09-26 | 温州南力实业有限公司 | The preparation and the application in shoemaking of polyurethane binder that a kind of footwear ultraviolet light solidifies |
CN108440738A (en) * | 2018-03-27 | 2018-08-24 | 叶陈瑶 | A kind of high-elastic Antibacterial polyurethane and its preparation method and application |
CN108503783A (en) * | 2018-04-11 | 2018-09-07 | 苏州大学 | Thermoplastic polyurethane elastomer and preparation method thereof |
CN109134812A (en) * | 2018-07-13 | 2019-01-04 | 汕头大学 | A kind of composite antibacterial polyurethane blocks polymer and its preparation and application |
CN111117518A (en) * | 2019-12-13 | 2020-05-08 | 北京东方雨虹防水技术股份有限公司 | Mildew-proof bactericide, long-acting mildew-proof modified silicone mildew-proof sealant in service period and preparation method thereof |
CN111233783A (en) * | 2020-03-13 | 2020-06-05 | 温州大学 | Synthesis method of bithiazole-4-yl disulfide derivative |
CN111253904A (en) * | 2020-03-25 | 2020-06-09 | 詹志豪 | High-adhesion UV adhesive and preparation method thereof |
-
2020
- 2020-08-24 CN CN202010856315.1A patent/CN111909356A/en active Pending
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2844610A1 (en) * | 1978-10-13 | 1980-04-30 | Hoechst Ag | METHOD FOR PRODUCING 4-NITRO-4'-AMINO-DIPHENYLAMINE-2-SULFONIC ACID AND 2-NITRO-4'-AMINO-DIPHENYLAMINE-4-SULPHONIC ACID |
CN101987885A (en) * | 2009-08-05 | 2011-03-23 | 合肥普尔德医疗用品有限公司 | Antibacterial, waterproof and moisture permeable type composite functional material and preparation method and application thereof |
CN102454107A (en) * | 2010-10-26 | 2012-05-16 | 北京崇高纳米科技有限公司 | Polyurethane synthetic leather capable of inhibiting bacteria and resisting mildew and preparation method thereof |
CN102911510A (en) * | 2012-10-25 | 2013-02-06 | 上海贝通色彩科技有限公司 | Ink-jet dye compound and preparation method thereof |
CN106519158A (en) * | 2016-10-26 | 2017-03-22 | 江南大学 | Preparation method of hyperbranched poly (urethane-amine) with hydroxide radical serving as end group and internal branched units provided with vinyl |
CN107201183A (en) * | 2017-07-18 | 2017-09-26 | 温州南力实业有限公司 | The preparation and the application in shoemaking of polyurethane binder that a kind of footwear ultraviolet light solidifies |
CN108440738A (en) * | 2018-03-27 | 2018-08-24 | 叶陈瑶 | A kind of high-elastic Antibacterial polyurethane and its preparation method and application |
CN108503783A (en) * | 2018-04-11 | 2018-09-07 | 苏州大学 | Thermoplastic polyurethane elastomer and preparation method thereof |
CN109134812A (en) * | 2018-07-13 | 2019-01-04 | 汕头大学 | A kind of composite antibacterial polyurethane blocks polymer and its preparation and application |
CN111117518A (en) * | 2019-12-13 | 2020-05-08 | 北京东方雨虹防水技术股份有限公司 | Mildew-proof bactericide, long-acting mildew-proof modified silicone mildew-proof sealant in service period and preparation method thereof |
CN111233783A (en) * | 2020-03-13 | 2020-06-05 | 温州大学 | Synthesis method of bithiazole-4-yl disulfide derivative |
CN111253904A (en) * | 2020-03-25 | 2020-06-09 | 詹志豪 | High-adhesion UV adhesive and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
LING LI等: "DBU-Promoted Demethoxylative Thioannulation of Alkynyl Oxime Ethers with Sulfur for the Synthesis of Bisisothiazole-4-yl Disulfides", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
魏晓慧等: "抗菌水性聚氨酯研究进展", 《聚氨酯工业》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115403916A (en) * | 2022-05-16 | 2022-11-29 | 上海年与轻科技(集团)有限公司 | Piezoelectric power generation device shell material for chip in shoe and preparation method thereof |
CN115403916B (en) * | 2022-05-16 | 2024-03-01 | 上海年与轻科技(集团)有限公司 | Piezoelectric power generation device shell material for shoe inner chip and preparation method thereof |
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