CN110003425A - A kind of preparation method of Biodegradable polyurethane composite material - Google Patents
A kind of preparation method of Biodegradable polyurethane composite material Download PDFInfo
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6446—Proteins and derivatives thereof
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The present invention relates to a kind of preparation methods of Biodegradable polyurethane composite material, belong to polyurethane material technical field.The present invention is with polyethylene glycol, hexamethylene diisocyanate is raw material, prepare Biodegradable polyurethane composite material, polyurethane can keep stability in water, but it can but degrade in vivo, intracorporal macrophage, leucocyte etc. releases oxonium ion, the oxyradicals such as hydroxyl, capture the hydrogen atom in polyurethane chain, so that chain fracture occurs for polyurethane, under the acidic materials in tissue fluid and esterase act on simultaneously, it is degraded to acid and alcohol, the disadvantage that homopolymerization physical performance can be overcome single as polyurethane prepared by raw material using polyethylene glycol, by the quality for adjusting different monomers, molecular weight etc., the different polyurethane material of availability, improve the hydrophilicity of polyurethane material, improve its biocompatibility, degradation rate is not only improved, and controllability can be changed, it is intracorporal in people to improve it Degradation capability.
Description
Technical field
The present invention relates to a kind of preparation methods of Biodegradable polyurethane composite material, belong to polyurethane material technology neck
Domain.
Background technique
Biodegradable polymer material be refer in a manner of safe and reliable, economic and PHYSIOLOGICALLY COMPATIBLE in structure or
Functionally instead of body part tissue or organ dysfunction, and a kind of high molecular material that catabolite has no toxic side effect to body,
Main includes natural, three sources of Microbe synthesis and chemical synthesis, wherein chemical synthesis Polymer Materials ' Structure controllability it is strong,
It has excellent performance, there is extensive research and application value.Polyurethane is to contain duplicate carbamate groups in molecular backbone
A kind of high molecular polymer, there is excellent mechanical strength and resistance to bend(ing), and Molecular Design freedom degree is big, as doctor
It is valued by people very early with material.And polyurethane material cannot naturally be degraded, the synthesis of Biodegradable polyurethane,
Mainly using biodegradable component or group by being blended or the method for copolymerization is as soft segment, or in the form of chain extender as
Hard section is introduced into polyurethane molecular structure, by adjusting the structure and ratio of soft and hard segments, so as to adjust the property of polyurethane
Energy.
It is compared with other bio-medical materials, the structure very phase of the micro phase separation structure and biological cell membrane of polyurethane
Seemingly, therefore while assigning the excellent physical mechanical property of material and easy processing forms, moreover it is possible to improve the blood compatibility that material is trembled
Property and biocompatibility.A large amount of zooperies and toxicity test all confirm medical polyurethane material it is nontoxic in clinical application,
No aberration inducing effect, to part without allergic reaction, while having good antibiotic property, solvent resistance, water resistance, and has very
One of high toughness, wear-resistant, performance is controllable, therefore be acknowledged as most valuable bio-medical synthetic material.
Degradable biological based polyurethanes material can both retain the biology of biological based component in its prepolymer to a certain extent
Degradability, and its biocompatibility can be improved, and its performance has very big adjustability, has a wide range of applications field.Especially
It has huge development potentiality in field of biomedicine, degradable polyurethane material, can be widely applied to organizational project, medicine
Object controls the multiple fields such as delivery systme, medical embedded material.
The synthesis of biology base degradable polyurethane material at present can mainly be given birth to by the method introducing for being blended or being copolymerized
Object degrades ingredient or group as soft segment, such as polylactic acid, polycaprolactone, polyglycolic acid and its copolymer, with poly- diisocyanate
Ester is as hard section, to form the blocked structure of soft and hard segments.By adjusting the ratio of soft and hard segments, its degradation speed can control
The main characters such as rate, elasticity modulus, crystallinity, tensile strength, elongation at break, and the ratio can be by artificially controlling and adjusting
Section.
Isocyanate groups in synthesis of polyurethane raw material have very high activity, can react from different hydroxyls,
Natural polymer mostly has degradability, and the natural polymer for containing polyhydroxy is polynary as polyurethane
One of alkoxide component prepares polyurethane material, can both reduce the dosage of polyalcohol, reduces cost, and it is good to assign polyurethane product
Good degradation property.
Degradable polyurethane is prepared using artificial synthesized polymer, is primarily referred to as synthesizing using molecular design theory
There is the polyurethane of the multifunction of good physical behavior and excellent degradation property simultaneously.The degradable polyurethane medically applied
Material belongs to such mostly, mainly includes polyether polyurethane, polyester polyurethane, polycarbonate polyurethane etc..Often at present
It is used as wound dressing, artificial skin, artificial heart valve, operation suture thread, drug controllable sustained-release system, nerve trachea, group
Knit engineering material etc..
The use scope of bio-based materials spreads each field very much, especially generally uses in biomedicine field.Have
Have the preparation of biodegradable macromolecular material carry drug body have it is certain convenient because this material after completing medical functions not
It need to perform the operation and be taken out, it is small molecule that it, which can be hydrolyzed or digest within a certain period of time, is then absorbed by body metabolism
Or excretion, the attention with people to this problem, biodegradable packaging material achieve rapid development, the mankind have found nature
Consciousness enhancing after the reproducibility of resource and to environmental protection, the application of bio-based materials can be more and more extensive.
Summary of the invention
The technical problems to be solved by the invention: it aiming at the problem that conventional urethane material is unable to natural biological degradation, mentions
A kind of preparation method of Biodegradable polyurethane composite material is supplied.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) polyurethane chain extender is added in dimethyl sulfoxide, 20~30min is stirred with 300~360r/min revolving speed under room temperature,
Obtain expanding chain pharmaceutical solution；
(2) mint fibers base polyester copolymer is placed in container, is passed through nitrogen protection, expanding chain pharmaceutical solution is slowly added dropwise to thin
In lotus fiber base polyester copolymer, 20~30min is stirred with 400~500r/min revolving speed under 70~80 DEG C of water-bath, is kept the temperature,
Obtain reaction system；
(3) nucleoprotamine, casein are added in reaction system, with 300~400r/min under 80~90 DEG C of water bath condition
Revolving speed stirs 3~4h, is cooled to room temperature, obtains reactant；
(4) deionized water is added in reactant, room temperature stands 20~40min, filters, and solid is placed in baking oven at 30~40 DEG C
Under conditions of dry 30~40min, obtain Biodegradable polyurethane composite material.
The mint fibers base polyester copolymer, dimethyl sulfoxide, nucleoprotamine, casein, is gone polyurethane chain extender
The parts by weight of ionized water are 30~40 parts of mint fibers base polyester copolymers, 10~20 parts of polyurethane chain extenders, 20~40 part two
Methyl sulfoxide, 6~8 parts of nucleoprotamine, 12~16 parts of casein, 60~80 parts of deionized waters.
Nitrogen described in step (2) be passed through rate be 30~40mL/min, expanding chain pharmaceutical solution drop rate be 10~
20mL/min。
The specific preparation step of polyurethane chain extender described in step (1) are as follows:
(1) hexamethylene diisocyanate is passed through nitrogen protection, 1,4-butanediol is slowly added to pretreated hexa-methylene
Diisocyanate is stirred to react 4~6h under the conditions of 60~80 DEG C of oil bath with 300~400r/min revolving speed, is cooled to room temperature,
Obtain reaction product；
(2) reaction product is filtered, filter cake is washed 3~5 times with n-hexane, then is placed in 2~4h of revolving in Rotary Evaporators, is obtained poly-
Urethane chain extender.
The parts by weight of the hexamethylene diisocyanate, 1,4-butanediol are 50~60 parts of hexa-methylene diisocyanates
Ester, 10~20 parts of 1,4-butanediol.
The rate that is passed through of nitrogen described in step (1) is 30~40mL/min, the drop rate of 1,4-butanediol is 20~
40mL/min。
The specific preparation step of mint fibers base polyester copolymer described in step (2) are as follows:
(1) will dehydration peppermint gluing fiber, dehydration polyethylene glycol be placed in vacuum reaction bottle, 80~100 DEG C, 4000~
1~2h is kept under conditions of 5000Pa, room temperature cooling obtains mixed system；
(2) 6-caprolactone, adipic acid, butyl titanate are added in mixed system, argon gas protection are passed through, in 120~140 DEG C of item
2~4h is stirred to react with 150~200r/min revolving speed under part, room temperature cooling obtains mint fibers base polyester copolymer.
The parts by weight of the dehydration peppermint gluing fiber, dehydration polyethylene glycol, 6-caprolactone, adipic acid, butyl titanate
For 10~15 parts of dehydration peppermint gluing fibers, 10~15 parts of dehydration polyethylene glycol, 20~30 parts of 6-caprolactones, 20~25 parts oneself two
Acid, 1~3 part of butyl titanate.
Dehydration peppermint gluing fiber described in step (1) and the specific preparation step for being dehydrated polyethylene glycol are as follows:
Polyethylene glycol, peppermint gluing fiber are placed in a vacuum drying oven, it is true under conditions of 60~80 DEG C, 2000~3000Pa
Empty 10~12h of drying and dehydrating must be dehydrated polyethylene glycol and dehydration peppermint gluing fiber.
The rate that is passed through of argon gas described in step (2) is 20~30mL/min.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention prepares Biodegradable polyurethane composite wood using polyethylene glycol, hexamethylene diisocyanate as raw material
Material, polyurethane can keep stability in water, but can but degrade in vivo, and polyurethane can cause in vivo inflammation anti-
It answers, intracorporal macrophage, leucocyte etc. release the oxyradicals such as oxonium ion, hydroxyl, capture the hydrogen in polyurethane chain
Atom, so that chain fracture occurs for polyurethane, while under acidic materials in tissue fluid and esterase effect, being degraded to acid and alcohol,
Using the disadvantage that polyethylene glycol can overcome homopolymerization physical performance single as polyurethane prepared by raw material, by the matter for adjusting different monomers
Amount, molecular weight etc., the different polyurethane material of availability, improve the hydrophilicity of polyurethane material, improve its life
Object compatibility, degradation rate are not only improved, and controllability can be changed, and the soft segment and hard segment structure of polyurethane are
Thermodynamics Immiscible Polymer Blends will form micro phase separation structure, and this structure is similar to biomembrane, and the surface of micro phase separation structure is certainly
It is different by the surface free energy that can be distributed in biology, make that it is intracorporal in people to improve it which reduce the adsorption capacity to blood platelet
Degradation capability；
(2) present invention prepares Biodegradable polyurethane composite material by addition peppermint gluing fiber, and mint fibers are a kind of
Plants antimicrobial fiber, mint fibers are very high to the bacteriostasis rate of gold-coloured staphylococci, Escherichia coli, and mint fibers also have good
Ice-cold sense of touch, ice-cold sense of touch refer to a kind of coolness that skin moment heat loss is excessive and generates, and moment walking guide heat is more,
People just feels more ice-cold, and peppermint gluing fiber is the natural fiber extracted from peppermint, has eye-catching, refrigerant, anti-inflammatory function
Effect, has good biocompatibility and degradability, and the compound polyurethane material of addition peppermint gluing fiber preparation has good
Good anti-microbial property and excellent biocompatibility；
(3) present invention prepares Biodegradable polyurethane composite material, casein is by addition casein and nucleoprotamine
Phosphor protein in object milk has good hygroscopicity, and casein is that milk meets a kind of protein polymers generated after acid,
Polypeptide in casein can form three-dimensional network space structure in conjunction with the macromolecular in polyurethane, can be to polyurethane material
Play good reinforcing effect, casein can be degradable by microorganism, have good biocompatibility, nucleoprotamine be from
A kind of sulfate of the alkaline protein extracted in fish fresh mature sperm is a kind of natural additive, has good life
Object compatibility, nucleoprotamine shows very strong bacteriostasis in neutral and alkaline medium, and has higher thermal stability, adds
Add casein and nucleoprotamine that can effectively improve the biocompatibility and anti-microbial property of Biodegradable polyurethane composite material.
Specific embodiment
Polyethylene glycol, peppermint gluing fiber are placed in a vacuum drying oven, in 60~80 DEG C, the condition of 2000~3000Pa
10~12h of lower vacuum dehydration, must be dehydrated polyethylene glycol and dehydration peppermint gluing fiber weighs respectively according to parts by weight
10~15 parts of dehydration peppermint gluing fibers, 10~15 parts of dehydration polyethylene glycol, 20~30 parts of 6-caprolactones, 20~25 parts oneself two
Dehydration peppermint gluing fiber, dehydration polyethylene glycol are placed in vacuum reaction bottle, 80~100 by acid, 1~3 part of butyl titanate
DEG C, 1~2h is kept under conditions of 4000~5000Pa, room temperature cooling obtains mixed system, by 6-caprolactone, adipic acid, metatitanic acid fourth
Ester be added mixed system in, with the air velocity of 20~30mL/min be passed through argon gas protection, under conditions of 120~140 DEG C with
150~200r/min revolving speed is stirred to react 2~4h, and room temperature cooling obtains mint fibers base polyester copolymer, then in parts by weight
Meter, 50~60 parts of hexamethylene diisocyanates, 10~20 parts of 1,4-butanediol respectively, by hexamethylene diisocyanate, with
The air velocity of 30~40mL/min is passed through nitrogen protection, and 1,4-butanediol is slowly added with the drop rate of 20~40mL/min
Enter pretreated hexamethylene diisocyanate, it is anti-with the stirring of 300~400r/min revolving speed under the conditions of 60~80 DEG C of oil bath
4~6h is answered, is cooled to room temperature, reaction product is obtained, reaction product is filtered, filter cake is washed 3~5 times with n-hexane, then is placed in rotation
Turn to rotate 2~4h in evaporimeter, obtain polyurethane chain extender, then according to parts by weight, weighs 30~40 parts of mint fibers bases respectively
Polyester copolymer, 10~20 parts of polyurethane chain extenders, 20~40 parts of dimethyl sulfoxides, 6~8 parts of nucleoprotamine, 12~16 parts it is dry
Polyurethane chain extender is added in dimethyl sulfoxide for casein, 60~80 parts of deionized waters, is turned under room temperature with 300~360r/min
Speed 20~30min of stirring, obtains expanding chain pharmaceutical solution, mint fibers base polyester copolymer is placed in container, with 30~40mL/min
Air velocity be passed through nitrogen protection, expanding chain pharmaceutical solution is slowly added dropwise with the flow velocity of 10~20mL/min to mint fibers base and is gathered
In ester copolymer, 20~30min is stirred with 400~500r/min revolving speed under 70~80 DEG C of water-bath, heat preservation obtains reactant
System nucleoprotamine, casein is added in reaction system, with 300~400r/min revolving speed under 80~90 DEG C of water bath condition
3~4h is stirred, is cooled to room temperature, obtains reactant, deionized water is added in reactant, room temperature stands 20~40min, it filters,
Solid is placed in baking oven dry 30~40min under conditions of 30~40 DEG C, obtains Biodegradable polyurethane composite material.
Embodiment 1
Polyethylene glycol, peppermint gluing fiber are placed in a vacuum drying oven, vacuum dehydration under conditions of 60 DEG C, 2000Pa
10h must be dehydrated polyethylene glycol and dehydration peppermint gluing fiber, according to parts by weight, it is fine weigh 10 parts of dehydration peppermint gluings respectively
Dimension, 10 parts of dehydration polyethylene glycol, 20 parts of 6-caprolactones, 20 parts of adipic acids, 1 part of butyl titanate by dehydration peppermint gluing fiber, take off
Water polyethylene glycol is placed in vacuum reaction bottle, and 1h is kept under conditions of 80 DEG C, 4000Pa, and room temperature cooling obtains mixed system, will
6-caprolactone, adipic acid, butyl titanate are added in mixed system, argon gas protection are passed through with the air velocity of 20mL/min, 120
2h is stirred to react with 150r/min revolving speed under conditions of DEG C, room temperature cooling obtains mint fibers base polyester copolymer, then by weight
Number meter, difference 50 parts of hexamethylene diisocyanates, 10 parts of 1,4-butanediol, by hexamethylene diisocyanate, with 30mL/
The air velocity of min is passed through nitrogen protection, and 1,4-butanediol is slowly added to pretreated six with the drop rate of 20mL/min
Methylene diisocyanate is stirred to react 4h under the conditions of 60 DEG C of oil bath with 300r/min revolving speed, is cooled to room temperature, must react
Product filters reaction product, and filter cake is washed 3 times with n-hexane, then is placed in Rotary Evaporators and is rotated 2h, obtains polyurethane chain extension
Agent, then according to parts by weight, 30 parts of mint fibers base polyester copolymers, 10 parts of polyurethane chain extenders, 20 parts of diformazans are weighed respectively
Base sulfoxide, 6 parts of nucleoprotamine, 12 parts of casein, 60 parts of deionized waters polyurethane chain extender are added in dimethyl sulfoxide, often
20min is stirred with 300r/min revolving speed under temperature, expanding chain pharmaceutical solution is obtained, mint fibers base polyester copolymer is placed in container, with
The air velocity of 30mL/min is passed through nitrogen protection, and expanding chain pharmaceutical solution is slowly added dropwise with the flow velocity of 10mL/min to mint fibers
In base polyester copolymer, 20min is stirred with 400r/min revolving speed under 70 DEG C of water-bath, heat preservation obtains reaction system, by milt egg
White, casein is added in reaction system, stirs 3h under 80 DEG C of water bath condition with 300r/min revolving speed, is cooled to room temperature, obtains
Deionized water is added in reactant reactant, and room temperature stands 20min, filters, and solid is placed in baking oven under conditions of 30 DEG C
Dry 30min, obtains Biodegradable polyurethane composite material.
Embodiment 2
Polyethylene glycol, peppermint gluing fiber are placed in a vacuum drying oven, vacuum dehydration under conditions of 70 DEG C, 2500Pa
11h must be dehydrated polyethylene glycol and dehydration peppermint gluing fiber, according to parts by weight, it is fine weigh 12 parts of dehydration peppermint gluings respectively
Dimension, 12 parts of dehydration polyethylene glycol, 25 parts of 6-caprolactones, 22 parts of adipic acids, 2 parts of butyl titanates by dehydration peppermint gluing fiber, take off
Water polyethylene glycol is placed in vacuum reaction bottle, and 1h is kept under conditions of 90 DEG C, 4500Pa, and room temperature cooling obtains mixed system, will
6-caprolactone, adipic acid, butyl titanate are added in mixed system, argon gas protection are passed through with the air velocity of 25mL/min, 130
3h is stirred to react with 175r/min revolving speed under conditions of DEG C, room temperature cooling obtains mint fibers base polyester copolymer, then by weight
Number meter, difference 55 parts of hexamethylene diisocyanates, 15 parts of 1,4-butanediol, by hexamethylene diisocyanate, with 35mL/
The air velocity of min is passed through nitrogen protection, and 1,4-butanediol is slowly added to pretreated six with the drop rate of 30mL/min
Methylene diisocyanate is stirred to react 5h under the conditions of 70 DEG C of oil bath with 350r/min revolving speed, is cooled to room temperature, must react
Product filters reaction product, and filter cake is washed 4 times with n-hexane, then is placed in Rotary Evaporators and is rotated 3h, obtains polyurethane chain extension
Agent, then according to parts by weight, 35 parts of mint fibers base polyester copolymers, 15 parts of polyurethane chain extenders, 30 parts of diformazans are weighed respectively
Base sulfoxide, 7 parts of nucleoprotamine, 14 parts of casein, 70 parts of deionized waters polyurethane chain extender are added in dimethyl sulfoxide, often
25min is stirred with 330r/min revolving speed under temperature, expanding chain pharmaceutical solution is obtained, mint fibers base polyester copolymer is placed in container, with
The air velocity of 35mL/min is passed through nitrogen protection, and expanding chain pharmaceutical solution is slowly added dropwise with the flow velocity of 15mL/min to mint fibers
In base polyester copolymer, 25min is stirred with 450r/min revolving speed under 75 DEG C of water-bath, heat preservation obtains reaction system, by milt egg
White, casein is added in reaction system, stirs 3h under 85 DEG C of water bath condition with 350r/min revolving speed, is cooled to room temperature, obtains
Deionized water is added in reactant reactant, and room temperature stands 30min, filters, and solid is placed in baking oven under conditions of 35 DEG C
Dry 35min, obtains Biodegradable polyurethane composite material.
Embodiment 3
Polyethylene glycol, peppermint gluing fiber are placed in a vacuum drying oven, vacuum dehydration under conditions of 80 DEG C, 3000Pa
12h must be dehydrated polyethylene glycol and dehydration peppermint gluing fiber, according to parts by weight, it is fine weigh 15 parts of dehydration peppermint gluings respectively
Dimension, 15 parts of dehydration polyethylene glycol, 30 parts of 6-caprolactones, 25 parts of adipic acids, 3 parts of butyl titanates by dehydration peppermint gluing fiber, take off
Water polyethylene glycol is placed in vacuum reaction bottle, keeps 2h under conditions of 100 DEG C, 5000Pa, and room temperature cooling obtains mixed system,
6-caprolactone, adipic acid, butyl titanate are added in mixed system, argon gas protection is passed through with the air velocity of 30mL/min,
4h is stirred to react with 200r/min revolving speed under conditions of 140 DEG C, room temperature cooling obtains mint fibers base polyester copolymer, then by weight
Number meter is measured, respectively 60 parts of hexamethylene diisocyanates, 20 parts of 1,4-butanediol, by hexamethylene diisocyanate, with
The air velocity of 40mL/min is passed through nitrogen protection, and 1,4-butanediol is slowly added to pre-process with the drop rate of 40mL/min
Hexamethylene diisocyanate, 6h is stirred to react with 400r/min revolving speed under the conditions of 80 DEG C of oil bath, is cooled to room temperature, obtains
Reaction product filters reaction product, and filter cake is washed 5 times with n-hexane, then is placed in Rotary Evaporators and is rotated 4h, obtains polyurethane
Chain extender, then according to parts by weight, 40 parts of mint fibers base polyester copolymers, 20 parts of polyurethane chain extenders, 40 parts are weighed respectively
Dimethyl sulfoxide, 8 parts of nucleoprotamine, 16 parts of casein, 80 parts of deionized waters, are added dimethyl sulfoxide for polyurethane chain extender
In, 30min is stirred with 360r/min revolving speed under room temperature, expanding chain pharmaceutical solution is obtained, mint fibers base polyester copolymer is placed in container
In, nitrogen protection is passed through with the air velocity of 40mL/min, expanding chain pharmaceutical solution is slowly added dropwise with the flow velocity of 20mL/min to thin
In lotus fiber base polyester copolymer, 30min is stirred with 500r/min revolving speed under 80 DEG C of water-bath, heat preservation obtains reaction system, will
Nucleoprotamine, casein are added in reaction system, stir 4h under 90 DEG C of water bath condition with 400r/min revolving speed, are cooled to room
Temperature obtains reactant, and deionized water is added in reactant, and room temperature stands 40min, filters, and solid is placed in baking oven at 40 DEG C
Under the conditions of dry 40min, obtain Biodegradable polyurethane composite material.
Reference examples: the Biodegradable polyurethane composite material of Dongguan company production.
The Biodegradable polyurethane composite material that embodiment and reference examples are prepared is detected, specific detection is such as
Under:
Mechanical property: " ASTMD638-2003: plastics are drawn the standard that tensile mechanical properties are formulated referring to American society for testing and materials
Stretch performance measurement method " execute, the preparation of sample comply with standard in IV class sample requirement.Test uses TA-Xtplus type
Food texture measurement, test temperature are 20 DEG C, humidity 65%, test rate 5mm/min.Testing parallel sample number is 5.It is calculated
Tensile strength, fracture elongation.
Degradation property: postscript that different film samples (10mm × 10mm × 10mm) are weighed under vacuum drying is W0, so
After place it in l0mL, 37 DEG C of PBS(pH=7.4) in bottle in simulated body fluid, replace a degradation solution daily, setting
After taking out sample in time, flushed three times with aquae destillata, it is dry in 40 DEG C of vacuum oven until constant weight, weighing are denoted as
W1 calculates weight-loss ratio according to formula.
Specific test result such as table 1.
1 performance characterization contrast table of table
As shown in Table 1, Biodegradable polyurethane composite material prepared by the present invention has good mechanical property and degradability
Energy.
Claims (10)
1. a kind of preparation method of Biodegradable polyurethane composite material, which is characterized in that specific preparation step are as follows:
(1) polyurethane chain extender is added in dimethyl sulfoxide, 20~30min is stirred with 300~360r/min revolving speed under room temperature,
Obtain expanding chain pharmaceutical solution；
(2) mint fibers base polyester copolymer is placed in container, is passed through nitrogen protection, expanding chain pharmaceutical solution is slowly added dropwise to thin
In lotus fiber base polyester copolymer, 20~30min is stirred with 400~500r/min revolving speed under 70~80 DEG C of water-bath, is kept the temperature,
Obtain reaction system；
(3) nucleoprotamine, casein are added in reaction system, with 300~400r/min under 80~90 DEG C of water bath condition
Revolving speed stirs 3~4h, is cooled to room temperature, obtains reactant；
(4) deionized water is added in reactant, room temperature stands 20~40min, filters, and solid is placed in baking oven at 30~40 DEG C
Under conditions of dry 30~40min, obtain Biodegradable polyurethane composite material.
2. a kind of preparation method of Biodegradable polyurethane composite material according to claim 1, which is characterized in that institute
The mint fibers base polyester copolymer stated, polyurethane chain extender, dimethyl sulfoxide, nucleoprotamine, casein, deionized water weight
Amount part is 30~40 parts of mint fibers base polyester copolymers, 10~20 parts of polyurethane chain extenders, 20~40 parts of dimethyl sulfoxides, 6
~8 parts of nucleoprotamine, 12~16 parts of casein, 60~80 parts of deionized waters.
3. a kind of preparation method of Biodegradable polyurethane composite material according to claim 1, which is characterized in that step
Suddenly the rate that is passed through of nitrogen described in (2) is 30~40mL/min, and expanding chain pharmaceutical solution drop rate is 10~20mL/min.
4. a kind of preparation method of Biodegradable polyurethane composite material according to claim 1, which is characterized in that step
Suddenly the specific preparation step of polyurethane chain extender described in (1) are as follows:
(1) hexamethylene diisocyanate is passed through nitrogen protection, 1,4-butanediol is slowly added to pretreated hexa-methylene
Diisocyanate is stirred to react 4~6h under the conditions of 60~80 DEG C of oil bath with 300~400r/min revolving speed, is cooled to room temperature,
Obtain reaction product；
(2) reaction product is filtered, filter cake is washed 3~5 times with n-hexane, then is placed in 2~4h of revolving in Rotary Evaporators, is obtained poly-
Urethane chain extender.
5. a kind of preparation method of Biodegradable polyurethane composite material according to claim 4, which is characterized in that institute
The parts by weight of the hexamethylene diisocyanate, 1,4-butanediol stated are 50~60 parts of hexamethylene diisocyanates, 10~20
Part 1,4-butanediol.
6. a kind of preparation method of Biodegradable polyurethane composite material according to claim 4, which is characterized in that step
Suddenly the rate that is passed through of nitrogen described in (1) is 30~40mL/min, and the drop rate of 1,4-butanediol is 20~40mL/min.
7. a kind of preparation method of Biodegradable polyurethane composite material according to claim 1, which is characterized in that step
Suddenly the specific preparation step of mint fibers base polyester copolymer described in (2) are as follows:
(1) will dehydration peppermint gluing fiber, dehydration polyethylene glycol be placed in vacuum reaction bottle, 80~100 DEG C, 4000~
1~2h is kept under conditions of 5000Pa, room temperature cooling obtains mixed system；
(2) 6-caprolactone, adipic acid, butyl titanate are added in mixed system, argon gas protection are passed through, in 120~140 DEG C of item
2~4h is stirred to react with 150~200r/min revolving speed under part, room temperature cooling obtains mint fibers base polyester copolymer.
8. a kind of preparation method of Biodegradable polyurethane composite material according to claim 7, which is characterized in that institute
State dehydration peppermint gluing fiber, dehydration polyethylene glycol, 6-caprolactone, adipic acid, butyl titanate parts by weight be 10~15 parts
It is dehydrated peppermint gluing fiber, 10~15 parts of dehydration polyethylene glycol, 20~30 parts of 6-caprolactones, 20~25 parts of adipic acids, 1~3 part
Butyl titanate.
9. a kind of preparation method of Biodegradable polyurethane composite material according to claim 7, which is characterized in that step
Suddenly the specific preparation step of dehydration peppermint gluing fiber described in (1) and dehydration polyethylene glycol are as follows:
Polyethylene glycol, peppermint gluing fiber are placed in a vacuum drying oven, it is true under conditions of 60~80 DEG C, 2000~3000Pa
Empty 10~12h of drying and dehydrating must be dehydrated polyethylene glycol and dehydration peppermint gluing fiber.
10. a kind of preparation method of Biodegradable polyurethane composite material according to claim 7, which is characterized in that
The rate that is passed through of argon gas described in step (2) is 20~30mL/min.
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| CN113603852A (en) * | 2021-07-26 | 2021-11-05 | 李洪有 | Bio-based degradable polyurethane and preparation method thereof |
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