CN107286313A - A kind of degradable polyurethane foam and its application - Google Patents

A kind of degradable polyurethane foam and its application Download PDF

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Publication number
CN107286313A
CN107286313A CN201710556919.2A CN201710556919A CN107286313A CN 107286313 A CN107286313 A CN 107286313A CN 201710556919 A CN201710556919 A CN 201710556919A CN 107286313 A CN107286313 A CN 107286313A
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China
Prior art keywords
polyurethane foam
polyurethane
polyol
foam according
degradable
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Pending
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CN201710556919.2A
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Chinese (zh)
Inventor
荆晶晶
冉永峰
张锐利
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SHAANXI RUISHENG BIOLOGICAL SCIENCE AND TECHNOLOGY Co Ltd
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SHAANXI RUISHENG BIOLOGICAL SCIENCE AND TECHNOLOGY Co Ltd
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Priority to CN201710556919.2A priority Critical patent/CN107286313A/en
Publication of CN107286313A publication Critical patent/CN107286313A/en
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    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
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    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/64—Use of materials characterised by their function or physical properties specially adapted to be resorbable inside the body
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    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
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    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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Abstract

The present invention relates to technical field of biological materials, more particularly to a kind of degradable polyurethane foam and its application.The degradable polyurethane foam preparation technology is simple, and the cycle is shorter, can avoid introducing impurity, and the product water imbibition obtained is preferably, and porosity is higher, capable of being fast degraded, is suitable for clinical practice.The polyurethane foam is dissolved in organic solvent by polyurethane, and obtained by being freeze-dried, wherein, the polyurethane is used as soft segment by oligomer polyol, polyisocyanates is prepared as hard section with chain extender by the one-step method of body, and the oligomer polyol is hydrophilic polyol and the mixture of degradable polyol.The embodiment of the present invention is used to prepare hemostatic material, wound dressing or ear nose padding.

Description

A kind of degradable polyurethane foam and its application
Technical field
The present invention relates to technical field of biological materials, more particularly to a kind of degradable polyurethane foam and its application.
Background technology
As the pressure in the life of people, work constantly increases, often occur ear chamber, nasal cavity even in terms of body cavity Focus, such as nasal polyp, nose tumour, nosebleed, tympanitis, the purpose of healing can be reached by clinical operation, but also can Bleeding and mucous membrane is caused to be adhered to a certain extent.
At present, clinically main to clog ear nose chamber to reach the purpose of hemostasis using filler, initial hemostatic material is Gauze and cotton, the absorbability of these hemostatic materials are limited, and structure is more fragile, easily occur fibre shedding, and staying Second operation is needed to be removed after being placed in vivo.
In order to avoid above-mentioned adverse reaction, a kind of hemostatic material is clinically needed, this hemostatic material had both had certain Mechanical strength, can play the purpose of filling, have good hydrophily and suitable degradability again.In consideration of it, this area Technical staff carried out it is substantial amounts of research and development experiment, wherein, the patent of an Application No. 201110382475.8 discloses one Novel chitosan hemostatic sponge and preparation method thereof is planted, it is mainly using water soluble chitosan, glycerine and poloxamer through at a high speed Stirring injection molding, quick-frozen, the demoulding and freeze-drying acquisition, styptic sponge high resilience under drying, with higher water suction Power and high-expansion, but the product meets water after use can lose elasticity, cause the compressing of ear nose chamber uncomfortable；Another application Number disclose a kind of biomedical foams for 101816801A patent there is provided a kind of polyurethane foam, this polyurethane foam The soft segment of foam is obtained using hydrophily glycol and the copolymerization of degradable polymer glycol, and soft segment is blocked after purification again using performed polymer Reacted with the polyisocyanates with hard section function, this polyurethane foam has certain liquid absorption capacity, wetting state Lower high resilience, and it is capable of being fast degraded, it is adapted to clinical practice, still, this preparation method is synthesized using multistep processes, and soft segment Preparation technology is complicated, and the cycle is longer, is readily incorporated impurity, is unfavorable for industrial applications.
The content of the invention
To reach above-mentioned purpose, the embodiment of the present invention provides a kind of degradable polyurethane foam and its application, and this can drop The polyurethane foam preparation technology of solution is simple, and the cycle is shorter, can avoid introducing impurity, and the product water imbibition obtained compared with Good, capable of being fast degraded, porosity is higher, is suitable for clinical practice.
On the one hand, the embodiment of the present invention provides a kind of degradable polyurethane foam,
The polyurethane foam is dissolved in organic solvent by polyurethane, and is obtained by being freeze-dried, wherein, the poly- ammonia Ester is by oligomer polyol as soft segment, and polyisocyanates is prepared as hard section with chain extender by the one-step method of body, The oligomer polyol is hydrophilic polyol and the mixture of degradable polyol.
Optionally, the one-step method of the body is specifically included：
1) it is added dropwise after oligomer polyol is dehydrated in the polyisocyanates, 2-8h is reacted at 60-100 DEG C；
2) to it is described 1) obtained by product in add chain extender, continue to react 6-20h, obtain the polyurethane.
Optionally ,-the NCO in the polyisocyanates and-OH in oligomer polyol mol ratio is 1:1- 1:3。
Optionally, it is described 2) described in-OH in chain extender with it is described 1) obtained by product in-NCO mol ratio be 1:1。
Optionally, the mol ratio of the hydrophilic polyol and the degradable polyol is 2:8-8:2.
Optionally, the hydrophilic polyol is in polyethylene glycol, PVP, polyvinyl alcohol and polypeptide One or more.
Optionally, the degradable polyol be selected from polycaprolactone glycol, it is polylactic acid diol, PPDO, poly- One or more in caprolactone trimethylene carbonate, polycaprolactone lactide and poly (glycolide-co-lactide).
Optionally, the polyisocyanates be selected from methyl diphenylene diisocyanate, Isosorbide-5-Nitrae-fourth diisocyanate, 1,6- oneself Any one in diisocyanate and toluene di-isocyanate(TDI).
Optionally, the chain extender is selected from small molecule dihydric alcohol and the compound with hard section functional group carries out hydroxyl envelope The one or more in chain extender behind end.
Optionally, the molecular weight of the polyurethane is 80000-120000.
Optionally, the tensile strength of the polyurethane is >=10MPa.
Optionally, the elongation at break of the polyurethane is 500%~1000%.
Optionally, the water absorption rate of the polyurethane foam is 15~30 times of own wt.
Optionally, the porosity of the polyurethane foam is 85%-95%.
On the other hand, the embodiment of the present invention provides a kind of polyurethane foam as described above and applied as hemostatic material, wound Material is used as the application of ear nose padding.
The embodiment of the present invention provides a kind of degradable polyurethane foam and its application, due to the degradable polyurethane by Hydrophilic polyol and degradable polyol are polymerize as soft segment with polyisocyanates and chain extender by the one-step method of body Form, by introducing hydrophily soft segment and degradability soft segment, hydrophilicity that can be to polyurethane and degraded in polyurethane Performance is adjusted, and is combined soft segment and hard section using one-step method, can obtain the polymerization from softness to hard different performance Thing, so as to obtain the polyurethane with good mechanical performance and degradation property, also, the polyurethane foam hole obtained Gap rate is higher, with good water imbibition, and also high resilience in a moistened state, is suitable for clinical practice, and uses a step Method compared with using multistep processes in the prior art, and preparation technology is simple, and the cycle is shorter, can avoid introducing excessive impurity, favorably In industrial applications.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with Other accompanying drawings are obtained according to these accompanying drawings.
Mass loss rate changes with time pass when Fig. 1 is polyurethane foam A-F provided in an embodiment of the present invention degraded System's figure.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made Embodiment, belongs to the scope of protection of the invention.
On the one hand, the embodiment of the present invention provides a kind of degradable polyurethane foam,
The polyurethane foam is dissolved in organic solvent by polyurethane, and is obtained by being freeze-dried, wherein, the poly- ammonia Ester is by oligomer polyol as soft segment, and polyisocyanates is prepared as hard section with chain extender by the one-step method of body, The oligomer polyol is hydrophilic polyol and the mixture of degradable polyol.
Wherein, the one-step method of body refers to oligomer polyol, polyisocyanates and chain extender and other auxiliary agents one Secondary mixing, reacts the method for shaping.
The embodiment of the present invention provides a kind of degradable polyurethane foam, because the degradable polyurethane is more by hydrophily First alcohol and degradable polyol are polymerized as soft segment with polyisocyanates and chain extender by the one-step method of body, are led to Cross and hydrophily soft segment and degradability soft segment are introduced in polyurethane, the hydrophilicity and degradation property of polyurethane can be carried out Regulation, and combined soft segment and hard section using one-step method, the polymer from softness to hard different performance can be obtained, so as to It is enough to obtain the polyurethane with good mechanical performance and degradation property, also, the polyurethane foam porosity obtained is higher, With good absorbability, and also high resilience in a moistened state, it is suitable for clinical practice, and use one-step method and existing skill Compared in art using multistep processes, preparation technology is simple, and the cycle is shorter, can avoid introducing impurity, be conducive to industrial applications.
In order to improve the absorbability of the polyurethane foam so that the polyurethane foam disclosure satisfy that clinically to hemostatic material The performance requirement of material, it is preferred that the hydrophilic polyol be selected from polyethylene glycol, PVP, polyvinyl alcohol and One or more in polypeptide.
Further, because the hydrophily of polyethylene glycol is fabulous, and industrialization production, in copolymer structure formula Middle polyethylene glycol segment can assign the good flexibility of copolymer and water-wet behavior, therefore, the hydrophilic polyol are preferred For polyethylene glycol.
For high polymer material, the size of molecular weight will directly affect its performance, and molecular size range is moderate, can be effective Increase Chain Flexibility, it is to avoid strand winding crystallization, in order to which the performance to polyurethane control effectively, it is preferred that described The molecular weight of polyethylene glycol is 600-4000.
Because the degradation property of degradable polyol has direct influence to the degradation property of the polyurethane foam, because This, in order to improve the degradation property of the polyurethane foam, it is preferred that the degradable polyol be selected from polycaprolactone glycol, Polylactic acid diol, PPDO, PTMC (PTMC), polycaprolactone lactide and random PGA One or more in lactide.Wherein, molecular weight is usually used in preparing poly- ammonia for 1000-2000 polycaprolactone glycol (PCL) Ester elastomer, polylactic acid diol (PLA) has good biodegradability, and biocompatibility can be complete by microorganism after use Degradable, ultimately generates carbon dioxide and water, free from environmental pollution, and PPDO (PDS) is colourless half hitch polycrystalline macromolecule, With high-crystallinity and hydrophily, degradation in vivo is glyoxalic acid, or is further degraded to glycine, and body is discharged by urine Outside, modulus of elasticity is relatively low.PTMC (PTMC) has very submissive engineering properties and unique degradability, The engineering properties and biological degradability of polymer can be changed.The degradation property of poly (glycolide-co-lactide) and polycaprolactone carbonic ester compared with To be excellent, and with good biocompatibility, it is widely used as biodegradation material.These polymer have good life Thing compatibility, good moulding processability, degradation property, and catabolite is nontoxic, pollution-free.
These degradable polymer polyalcohols can be obtained by commercial sources, can also make acquisition by oneself.
It should be noted that compared with homopolymer, copolymer (such as poly (glycolide-co-lactide) and polycaprolactone carbonic ester) With more excellent degradability and hydrophily, the hydrophilicity and degradation property of polyurethane are more conducively adjusted.And it is unformed poly- Compound refers to for high molecular crystalline state, does not crystallize completely, molecule segment arrangement random coil, with obvious Glass transition temperature, the degradation property of polymer can be adjusted.Semi-crystalline polymer is that may partly form crystalline phase and part The polymer of amorphous phase, can regulate and control to slow down the degradation property of amorphous polymer.It is preferred, therefore, that described degradable polynary One or more of the alcohol in amorphous non-crystalline copolymer and hemicrystalline random copolymer.
Exemplary, the degradable polyol can be selected from unbodied polycaprolactone lactide and hemicrystalline random One or both of poly (glycolide-co-lactide).
In one embodiment of the invention, the unbodied polycaprolactone lactide can be rubbed by the third friendship fat and caprolactone You are than being 1:1 copolymerization is obtained.In embodiments of the present invention, by controlling the mol ratio of the lactide and caprolactone so that should The characteristics of polycaprolactone lactide has high PLA intensity, very fast degradation rate and good PCL pliabilities concurrently, can be to unbodied The mechanical strength and degradation property of polycaprolactone lactide are adjusted, to meet degradation property and machine clinically to polyurethane The requirement of tool intensity.
In another embodiment of the present invention, the hemicrystalline random poly (glycolide-co-lactide) can be handed over by lactide and second Ester is using mol ratio as 7:3 copolymerization are obtained.In embodiments of the present invention, by controlling the mol ratio of lactide and glycolide, equally The mechanical strength and degradation property of hemicrystalline random poly (glycolide-co-lactide) can be adjusted, to meet clinically to poly- The degradation property of urethane and the requirement of mechanical strength.
Further, the polycaprolactone trimethylene carbonate can be by caprolactone and trimethylene carbonate with 4:6 Mol ratio copolymerization obtain., equally can be to polycaprolactone three by controlling the mol ratio of caprolactone and trimethylene carbonate The mechanical strength and degradation property of carbonate are adjusted, to meet degradation property and machinery clinically to polyurethane The requirement of intensity.
Wherein, the polyisocyanates can be selected from methyl diphenylene diisocyanate, Isosorbide-5-Nitrae-fourth diisocyanate, 1,6- One or more in hexamethylene diisocyanate and toluene di-isocyanate(TDI).Wherein, methyl diphenylene diisocyanate abbreviation MDI, Synthesis for polyurethane；Isosorbide-5-Nitrae-fourth diisocyanate (BDI) can be applied to biomedical sector, and be the main of polyurethane Raw material, 1, hexamethylene-diisocyanate is HDI, the toluene di-isocyanate(TDI) abbreviation TDI for the straight chain type for being easy to degraded, is mainly used in system Standby polyurethane resin.
The polyisocyanates is preferably easily to the straight chain type 1 of degraded, hexamethylene-diisocyanate.
Wherein, the species to the chain extender is not also limited.
It is preferred that, the chain extender can be that small molecule dihydric alcohol and the compound with hard section functional group pass through hydroxyl The one or more in chain extender after end-blocking.Wherein, small molecule dihydric alcohol is conventional chain extender, with hard section functional group Compound acted on by the way that chain extension can either be played after hydroxy-end capped, hard section can also be introduced in polyurethane molecular, so as to Enough mechanical performances to polyurethane are further adjusted.
, wherein it is desired to which explanation, is polymerize by oligomer polyol, polyisocyanates and chain extender mixed once It is different according to the order of addition of raw material and the ratio of raw material due to the randomness of polymerisation during reaction, the poly- ammonia formed The structure of ester is also differed, exemplary, oligomer polyol, polyisocyanates and chain extender is being added simultaneously, oligomer Polyalcohol (uses OH-R1- OH is represented), polyisocyanates (being represented with OCN-R-NCO) and chain extender (use HO-R2- OH is represented), institute Shown in the primary structure of the polyurethane of acquisition such as following formula (I), shown in specific equation such as following formula (II).
In a preferred embodiment of the present invention, the one-step method of the body is specifically included：
1) it is added dropwise after oligomer polyol is dehydrated in the polyisocyanates, 4-6h is reacted at 60-100 DEG C；
2) to it is described 1) obtained by product in add chain extender, continue to react 6-10h, obtain the polyurethane.
, wherein it is desired to explanation, it is described 1) and the difference for 2) being merely representative of feed time, not by the 1) institute Product separating-purifying come out, but it is described 1) obtained by product in be directly added into the chain extender, belong to single step reaction.
In embodiments of the present invention, by first by hydrophilic polyol and degradable polyol respectively with the polyisocyanic acid Polyisocyanate polyaddition forms the polymer segment of soft or hard combination, then by obtaining polyurethane with the chain extending reaction of chain extender, result in by Polymer segment and be total to by degradable polyol and polyisocyanates that hydrophilic polyol and polyisocyanates copolymerization are obtained The block copolymer of the poly- polymer segment composition obtained, can avoid hydrophilic polyol and degradable polyol polymerization cycle It is longer, then prepolymer purified out with hard section polyisocyanic acid polyisocyanate polyaddition so that be readily incorporated impurity in processing procedure, and by The polyurethane that one-step method is obtained also there is soft segment and hard section to combine the polymer for obtaining different performance, can be to the drop of polyurethane Solution performance and hydrophilicity are adjusted, to meet clinical demand.
In the another preferred embodiment of the present invention, in-the NCO and the polymer polyatomic alcohol in the polyisocyanates - OH mol ratio be 1:1-1:3, to ensure the end-blocking of oligomer polyol completion isocyano in single step reaction.
Further, it is described 2) described in-OH in chain extender with it is described 1) obtained by product in-NCO mol ratio For 1:1.Specifically, content that can be to-the NCO in the product obtained by 1) in 1) course of reaction is monitored in real time, with right - OH in the chain extender and it is described 1) obtained by product in-NCO mol ratio be controlled, at the same time it can also according to institute Detection 1) obtained by product in-NCO content determine the reaction time 1), to be carried out to the reaction process 1) Effectively control.
Wherein, according to the hydrophilic polyol added by a kind of or several mixtures and add it is degradable polynary Alcohol is a kind of or several mixtures, and the conversion ratio of monomer difference, the company of different blocks in the polyurethane obtained Connect mode and number can be different.
Exemplary, when the hydrophilic polyol is polyethylene glycol (PEG), the degradable polyol OH-R1-OH To represent, the polyisocyanates is 1, hexamethylene-diisocyanate, and the polyisocyanates and the polymer polyatomic alcohol with- NCO:- OH mol ratio is 1:1-1:3 when being mixed, and the primary structure of the polyurethane is by first polymer segment and the The diblock copolymer of dimerization polymer segments composition, wherein, the first polymer segment is by polyethylene glycol and 1, and oneself is two different by 6- Cyanate copolymerization is obtained, and the second polymer segment is by unbodied polycaprolactone lactide or hemicrystalline random poly- second Lactide lactide and 1, hexamethylene-diisocyanate copolymerization is obtained, shown in specific reaction equation such as following formula (III).
In one embodiment of the invention, the molecular weight of the polyurethane is 80000-120000, and molecular weight is too high to be influenceed Degradation rate, molecular weight is too low to influence the mechanical property use requirement using process.
In a preferred embodiment of the present invention, the tensile strength of the polyurethane is >=10MPa.Tensile strength refers to sample The maximum stress born before breaking.The tensile strength of the polyurethane within the range, disclosure satisfy that clinically to biological hemostatic material The demand of material and packing material.
In the another preferred embodiment of the present invention, the elongation at break of the polyurethane is 500%-1000%.Fracture is stretched Long rate refers to shift value of the sample when breaking and former long ratio.The elongation at break of the polyurethane within the range, equally It disclosure satisfy that the demand clinically to biological hemostatic material and packing material.
It is preferred that, one kind in dioxane, dimethyl sulfoxide (DMSO), dichloromethane and chloroform of the organic solvent or It is several.Found by many experiments, these organic solvents are preferable to the dissolubility of the polyurethane, are conducive to polyurethane to form poly- ammonia Ester foam.
, wherein it is desired to explanation, when being dissolved by above-mentioned organic solvent to the polyurethane, the poly- ammonia being made into The weight percentage of ester solution is 2.0%-10%.
In one embodiment of the invention, the water absorption rate of the polyurethane foam is 15-30 times of own wt.Pass through experiment It was found that, the polyurethane foam is soaked in phosphate buffer solution in 37 DEG C, it can absorb the liquid of itself 15-30 times of dry weight Body.
In one embodiment of the invention, the porosity of the polyurethane foam is 85%-95%.The hole of the polyurethane foam Gap rate is higher, and with good liquid absorption capacity, expansion rate is relatively low.
On the other hand, the embodiment of the present invention provides a kind of polyurethane foam as described above and applied as hemostatic material, wound Material is used as the application of ear nose padding.
The embodiment of the present invention provides a kind of application of polyurethane foam as described above.Due to the degradable polyurethane by Hydrophilic polyol and degradable polyol as soft segment, polymerize with polyisocyanates and chain extender by the one-step method of body and Into, can be to the hydrophilicity and degradability of polyurethane by introducing hydrophily soft segment and degradability soft segment in polyurethane It can be adjusted, and be combined soft segment and hard section using one-step method, the polymer from softness to hard different performance can be obtained, So as to obtain the polyurethane with good mechanical performance and degradation property, also, the polyurethane foam hole obtained Rate is higher, with good water imbibition, and also high resilience in a moistened state, is suitable for clinical practice, therefore, it can this Polyurethane foam is used as hemostasis as hemostatic material, wound dressing, can also be implanted in the body as ear nose padding, can be used for Hemostasis, and certain in the period of in good supporting role can be played to ear nose cavity, and with certain degradation cycle, and most Final decline solution is complete.And one-step method is used compared with using multistep processes in the prior art, preparation technology is simple, and the cycle is shorter, can Avoid introducing impurity, be conducive to industrial applications.
For the technique effect that the objective explanation present invention is brought, this is described in detail below by embodiment and experimental example Invention.Following examples are only illustrated by taking the actual interpolation concentration of each component in specific implementation process as an example, when actual use, The concentration of each component is not constituted on the realization of the object of the invention to be influenceed.
Embodiment 1
Describe for convenience, the polyurethane foam prepared by embodiment 1 is designated as A.
Specific preparation method is as follows：
1st, the preparation of polylactide-caprolactone (PCLA)
By lactide and 6-caprolactone with 1:1 mol ratio ring-opening polymerization, using butanediol (BDO) be initiator and Stannous octoate (0.001wt%) synthesizes for catalyst, and the weight ratio of initiator B DO and monomer is 0.001%, BDO and caprolactone After refined, water removal, add in three mouthfuls or single-necked flask, nitrogen charging gas shielded is put into heat-collecting magnetic stirring device or mechanical agitation, In 130 DEG C of oil bath reaction 24h, after cooling, dichloromethane dissolving, absolute ethyl alcohol is separated out.The vacuum that purified product is put into 40 DEG C is done Dry case dries 24h.
Then entered by infrared spectrum, nuclear-magnetism (H-NMR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) Row is characterized, and display has synthesized PCLA, and DSC heat analysis shows that sample only one of which glass transition temperature, between -40 to -30 DEG C, does not have Have crystalline melting peak appearance, illustrate that prepolymer is not crystallized, belong to unformed prepolymer PCLA, GPC detect molecular weight is 2276 or so.
2nd, the preparation of polyurethane
PCLA is taken, and polyethylene glycol PEG1000 is soft segment oligomer polyol, with hexamethylene diisocyanate and fourth Glycol (BDO) prepares degradable polyurethane.
Specifically, taking the PCLA prepared, and the PEG1000 of corresponding mole is added, condenser pipe is housed in a bottleneck And thermometer, another bottleneck fills mechanical agitation, in the oil bath for being placed in 110 DEG C, completely after melting, vacuumizes 1-3Pa, and water removal 2~ 5h.Be cooled to after 60 DEG C, inflated with nitrogen release vacuum, under mechanical stirring be added dropwise liquid hexamethylene diisocyanate ,-NCO with- OH mol ratio is 2:1, the certain solvent Isosorbide-5-Nitrae-dioxane of sticky rear addition is reacted, passes through every 20min and detects course of reaction Middle isocyanates-NCO content, it is 3h to determine the reaction time.
The BDO of dissolving is added dropwise afterwards, reacts and dioxane is continuously added in 10h, course of reaction, the equal of solution is kept Matter, stops reaction after viscosity is constant.Then polymer solution is precipitated in water or n-hexane, 40 DEG C of vacuum drying is placed in Case dries 24h, and the molecular weight of gpc analysis polymer is about 100,000.Characterized by infrared spectrum and nuclear-magnetism H spectrums, obtain it Nuclear magnetic data is：1H-NMR CDCl3δ(ppm):1.35(m,2H),1.40(m,2H),1.52(2,3H),1.68(m,2H),1.62 (m,2H),2.31(t,2H),3.27(m,2H),3.68(t,2H),4.08(t,2H),4.24(t,2H),5.17(m,1H),8.95 (t,1H)；2265cm on infrared spectrum-1Locate the disappearance of isocyanate group characteristic peak, and 3365cm-1Place-N-H stretching vibration Peak occurs, 1689cm-1Locate the appearance of the stretching vibration absworption peak of C=O keys in urethane, show to have prepared polycaprolactone lactide type Polyether polyols.PCLA (PEG1000)-HDI-BDO type polyurethanes as shown in following formula (IV), and root can be determined to obtain Determine that monomer conversion ratio is about 85% according to nuclear-magnetism H spectrums.
3rd, polyurethane foam A preparation
It is 2.5% that above-mentioned polyurethane, which is dissolved in Isosorbide-5-Nitrae-dioxane, and is diluted to weight percentage, and is added a small amount of Water.Poured into by 3 μm of filter in mold, after -40 DEG C freeze, 24h is freeze-dried under 10Pa pressure, and dry to perseverance Weight, obtains polyurethane foam A.
Embodiment 2
Describe for convenience, the polyurethane foam prepared by embodiment 2 is designated as B.
1st, polylactide-caprolactone (PCLA) is prepared as described in Example 1.
2nd, the preparation of hydroxy-end capped BDO-HDI-BDO (BHB) chain extender
Obtained by excessive butanediol BDO with hexamethylene diisocyanate (HDI) reaction.Take the BDO for drying and removing water 10 times of excess HDI are placed in there-necked flask, and the HDI of liquid is added dropwise in there-necked flask under mechanical stirring for nitrogen charging gas shielded, 65 DEG C of reaction 5h, reaction uses dry acetone washing and filtering after terminating, obtains white powder, dried in 50 DEG C of vacuum drying chambers 24h.Then the sign of DSC, IR and hydroxyl value is carried out.DSC, which is shown, is made purity more than 95%, the chain extender that 98 DEG C or so of fusing point BHB, hydroxyl value test result is 308mg/KOH, close to theoretical value.
3rd, polyurethane B preparation
PCLA is taken, and polyethylene glycol PEG600 is soft segment oligomer polyol, HDI, and hydroxy-end capped BDO- HDI-BDO (BHB) and BDO mixture prepares degradable polyurethane.
Specifically, take the PCLA prepared, and add the PEG600 of corresponding mole, a bottleneck equipped with condenser pipe and Thermometer, another bottleneck fills mechanical agitation, in the oil bath for being placed in 115 DEG C, completely after melting, vacuumizes 1-3Pa, removes water 2-5h. It is cooled to after 80 DEG C, inflated with nitrogen releases vacuum, liquid hexamethylene diisocyanate ,-NCO and-OH is added dropwise under mechanical stirring Mol ratio be 2:1, react it is sticky after add certain solvent DMSO, by every 20min detect isocyanates in course of reaction- NCO content, it is 6h to determine the reaction time.
Chain extender BHB and butanediol BDO is dissolved with DMSO afterwards, mol ratio between the two is 0.3:1 ,-OH in both Molal quantity sum and-NCO mol ratio are 1:1, after be slowly dropped in prepolymerization system, stirring reaction, in course of reaction constantly Add dimethyl sulfoxide (DMSO) DMSO, keep the homogeneous of solution, stop reaction after viscosity is constant (reaction time is 6h).Then will be poly- Polymer solution is precipitated in water or n-hexane, and the vacuum drying chamber for being placed in 40 DEG C dries 24h, the molecular weight of gpc analysis polymer About 120,000.Characterized by infrared spectrum and nucleus magnetic hydrogen spectrum, it may be determined that be prepared for PCLA (PEG600)-HDI-BHB/ BDO type polyurethanes, and determine that monomer conversion ratio is about 90% according to nuclear-magnetism H spectrums.
4th, polyurethane foam B preparation
The in the mixed solvent that above-mentioned polyurethane is dissolved in into 1,4- dioxane and dimethyl sulfoxide is diluted to weight percent and contained Measure as 10%, and add a small amount of water.Poured into by 3 μm of filter in mold, it is cold under 10Pa pressure after -40 DEG C freeze Dry 24h is freezed, and is dried to constant weight, polyurethane foam B is obtained.
Embodiment 3
Describe for convenience, the polyurethane foam prepared by embodiment 3 is designated as C.
Specific preparation method is as follows：
1st, the preparation of polylactide-co-glycolide prepolymer (PLGA)
By propiolactone and glycolide with 7:3 mol ratio ring-opening polymerization, using BDO be initiator and Stannous octoate is catalyst synthetic prepolymer.The caprolactone of certain mol proportion, butanediol (0.001%) is taken to be added to 100ml tri- In mouthful flask, nitrogen charging gas shielded is put into oil bath heating in heat-collecting magnetic stirring device, magnetic agitation, 140 DEG C of reaction 10h, afterwards Add a certain amount of glycolide monomer and continue to react stopping reaction after 5h, after cooling, dichloromethane dissolving, absolute ethyl alcohol is separated out. The vacuum drying chamber that purified product is put into 40 DEG C dries 24h.
Then characterization test is carried out by IR, nuclear-magnetism, DSC, GPC, IR spectrograms show the increasing of carbonic acid ester bond absorption peak strength By force, and in nucleus magnetic hydrogen spectrum figure, δ 4.81, LA diagnostic protons displacement, δ 5.28GA diagnostic protons displacement shows synthesis PLGA prepolymers, DSC shows that obtaining prepolymer has melting peak, and glass transition temperature Tg shows to synthesize between -35~-25 DEG C Semi-crystalline random prepolymer, GPC detect molecular weight be 2532 or so.
2nd, the preparation of polyurethane
PLGA is taken, and polyethylene glycol PEG1000 is soft segment oligomer polyol, BDO is that chain extender prepares degradable poly Urethane PU.
Specifically, taking the PLGA prepared, and the PEG1000 of corresponding mole is added, condenser pipe is housed in a bottleneck And thermometer, another bottleneck fills mechanical agitation, in the oil bath for being placed in 115 DEG C, completely after melting, vacuumizes 1-3Pa, and water removal 2~ 5h.Be cooled to after 60 DEG C, inflated with nitrogen release vacuum, under mechanical stirring be added dropwise liquid hexamethylene diisocyanate ,-NCO with- OH mol ratio is 1:1, the certain solvent DMSO of sticky rear addition is reacted, passes through every 20min and detects isocyanic acid in course of reaction Ester-NCO content, it is 2h to determine the reaction time.
The chain extender BDO of dissolving is added dropwise afterwards, reacts and dioxane or dimethyl Asia is continuously added in 8h, course of reaction Sulfone DMSO etc., keeps the homogeneous of solution, stops reaction after viscosity is constant.Polymer solution is then precipitated to water or n-hexane In, the vacuum drying chamber for being placed in 40 DEG C dries 24h, and the molecular weight of gpc analysis polymer is about 100,000.Pass through infrared spectrum and core Magnetic H spectrums are characterized, and obtaining its nuclear magnetic data is：1H-NMR：CDCl3δ(ppm)：1.40 (m, 2H), 1.52 (2,3H), 1.62 (m, 2H), 1.68 (m, 2H), 3.27 (m, 2H), 3.68 (t, 2H), 4.08 (t, 2H), 4.81 (s, 2H), 5.28 (m, 1H), 8.95 (t,1H)；2265cm on infrared spectrum-1Locate the disappearance of isocyanate group characteristic peak, and 3365cm-1Place-N-H stretching vibration Peak occurs, 1689cm-1Locate the appearance of the stretching vibration absworption peak of C=O keys in urethane, show to have prepared poly (glycolide-co-lactide) type Polyether polyols, PLGA (PEG)-HDI-BDO type polyurethanes as shown in following formula (V), and monomer is determined according to nuclear-magnetism H spectrums Conversion ratio is about 95%.
3rd, polyurethane foam C preparation
It is 2% that above-mentioned polymer, which is dissolved in dimethyl sulfoxide (DMSO), and is diluted to weight percentage, and adds a small amount of water.It is logical The filter for crossing 3 μm is poured into mold, after -40 DEG C of freezings, and 24h is freeze-dried under 10Pa pressure, and is dried to constant weight, is obtained Polyurethane foam C.
Embodiment 4
Describe for convenience, the polyurethane foam prepared by embodiment 4 is designated as D.
1st, polylactide-co-glycolide prepolymer (PLGA) is prepared as described in Example 3.
2nd, the preparation of hydroxy-end capped BDO-HDI-BDO (BHB) chain extender
Method according to embodiment 2 prepares hydroxy-end capped BDO-HDI-BDO (BHB) chain extender.
3rd, the preparation of polyurethane
PLGA is taken, and polyethylene glycol PEG600 is soft segment oligomer polyol, BDO-HDI-BDO and BDO mixing conducts Degradable polyurethane PU is prepared for chain extender.
Specifically, take the PLGA prepared, and add the PEG600 of corresponding mole, a bottleneck equipped with condenser pipe and Thermometer, another bottleneck fills mechanical agitation, in the oil bath for being placed in 115 DEG C, completely after melting, vacuumizes 1-3Pa, removes water 2~5h. It is cooled to after 100 DEG C, inflated with nitrogen releases vacuum, liquid tetramethylene diisocyanate ,-NCO and-OH is added dropwise under mechanical stirring Mol ratio be 3:1, react it is sticky after add certain solvent DMSO, by every 20min detect isocyanates in course of reaction- NCO content, it is 8h to determine the reaction time.
Chain extender BHB and butanediol BDO is dissolved with DMSO afterwards, mol ratio between the two is 0.6:1 ,-OH in both Molal quantity sum and-NCO mol ratio are 1:1, after be slowly dropped in prepolymerization system, stirring reaction, in course of reaction constantly Add dimethyl sulfoxide (DMSO) DMSO, keep the homogeneous of solution, stop reaction after viscosity is constant (reaction time is 20h).Then will Polymer solution is precipitated in water or n-hexane, and the vacuum drying chamber for being placed in 40 DEG C dries 24h, the molecule of gpc analysis polymer Amount about 80,000.Characterized by infrared spectrum and nuclear-magnetism H spectrums, it is determined that obtaining the poly- ammonia of PLGA (PEG)-HDI-BHB/BDO types Ester, and determine that monomer conversion ratio is about 90% according to nuclear-magnetism H spectrums.
3rd, polyurethane foam D preparation
It is 5% that above-mentioned polymer, which is dissolved in dimethyl sulfoxide (DMSO), and is diluted to weight percentage, and adds a small amount of water.It is logical The filter for crossing 3 μm is poured into mold, after -40 DEG C of freezings, and 24h is freeze-dried under 10Pa pressure, and is dried to constant weight, is obtained Polyurethane foam D.
Embodiment 5
Describe for convenience, the polyurethane foam prepared by embodiment 5 is designated as E.
1st, the preparation (PTMCL) of polycaprolactone trimethylene carbonate
Take 6-caprolactone using vacuum distillation under nitrogen protection is preceding needed, collect 60 DEG C, 35Pa cut.With 4:6 Mol ratio accurate weighing 6-caprolactone and trimethylene carbonate, are placed in polymerization pipe, decompression vacuum pumping 3 times, then directly add Enter stannous octoate (SnOct2) catalyst, again decompression vacuum pumping 3 times.After being closed under vacuum, polymerization pipe is completely immersed in silicone oil Middle heating, adds ethylene glycol and makees initiator, in 130 DEG C of polymerisation in bulk 24h.Product CHCl3Dissolving, in methyl alcohol precipitating and clear After washing, dry to constant weight, obtain constituting different P (TMC-co-CL) copolymers.
Through infrared and nuclear-magnetism characterize institute for expection polymer.DSC shows that polymer only has glass at -54.1 DEG C or so Change transition temperature, the polymer for showing synthesis is amorphous polymer.
2nd, the preparation of polyurethane
PTMCL is taken, and polyethylene glycol PEG600 is soft segment oligomer polyol, butanediol BDO is that chain extender preparation can Degradable polyurethane PU.
Specifically, taking the PTMCL prepared, and the PEG600 of corresponding mole is added, condenser pipe is housed in a bottleneck And thermometer, another bottleneck fills mechanical agitation, in the oil bath for being placed in 115 DEG C, completely after melting, vacuumizes 1-3Pa, and water removal 2~ 5h.It is cooled to after 100 DEG C, inflated with nitrogen releases vacuum, the mol ratio that liquid HDI ,-NCO and-OH are added dropwise under mechanical stirring is 2: 1, the sticky rear content for adding certain solvent DMSO, isocyanates-NCO in course of reaction being detected by every 20min is reacted, really The reaction time is determined for 4h.
The BDO of dissolving is added dropwise afterwards, reacts and dioxane is continuously added in 15h, course of reaction, the equal of solution is kept Matter, stops reaction after viscosity is constant.Then polymer solution is precipitated in water or n-hexane, 40 DEG C of vacuum drying is placed in Case dries 24h, and the molecular weight of gpc analysis polymer is about 110,000.Characterized by infrared spectrum and nuclear-magnetism H spectrums, obtain it Nuclear magnetic data is：1H-NMR：CDCl3δ (ppm) 1.34 (m, 2H), 1.40 (m, 2H), 1.62 (m, 2H), 1.68 (m, 2H), 1.72 (m, 2H), 2.07 (m, 2H), 2.28 (t, 2H), 4.08 (t, 2H), 4.17 (t, 2H), 8.95 (t, 1H)；On infrared spectrum 2265cm-1Locate the disappearance of isocyanate group characteristic peak, and 3365cm-1Place-N-H stretching vibration peak occurs, 1776cm-1Place The appearance of the flexible stretching vibration absworption peak of shaking of C=O keys in carbonic ester, shows to have prepared polycaprolactone carbonate polyurethane polyureas Compound.It can determine to obtain the structure as shown in following formula (VI), and determine that monomer conversion ratio is about according to nuclear-magnetism H spectrums 95%.
3rd, polyurethane foam E preparation
It is 4% that above-mentioned polymer, which is dissolved in dimethyl sulfoxide (DMSO), and is diluted to weight percentage, and adds a small amount of water.It is logical The filter for crossing 3 μm is poured into mold, after -40 DEG C of freezings, and 24h is freeze-dried under 10Pa pressure, and is dried to constant weight, is obtained Polyurethane foam E.
Embodiment 6
Describe for convenience, the polyurethane foam prepared by embodiment 6 is designated as F.
1st, polycaprolactone trimethylene carbonate PTMCL is prepared as described in Example 5.
2nd, hydroxy-end capped BDO-HDI-BDO (BHB) chain extender is prepared according to the method for embodiment 2.
3rd, the preparation of polyurethane
Polycaprolactone trimethylene carbonate is taken, and polyethylene glycol PEG600 is soft segment oligomer polyol, BDO- HDI-BDO (BHB) and BDO is that mixed chain extender prepares degradable polyurethane.
Specifically, taking the polycaprolactone trimethylene carbonate prepared, and the PEG600 of corresponding mole is added, One bottleneck is equipped with condenser pipe and thermometer, and another bottleneck fills mechanical agitation, in the oil bath for being placed in 115 DEG C, completely after melting, takes out true Empty 1-3Pa, removes water 2~5h.It is cooled to after 60 DEG C, inflated with nitrogen releases vacuum, liquid hexa-methylene two is added dropwise under mechanical stirring Isocyanates ,-NCO and-OH mol ratio is 3:1, the certain solvent DMSO of sticky rear addition is reacted, is detected by every 20min Isocyanates-NCO content in course of reaction, it is 6h to determine the reaction time.
Chain extender BHB and butanediol BDO is dissolved with DMSO afterwards, mol ratio between the two is 1:0.5 ,-OH in both Molal quantity sum and-NCO mol ratio are 1:1, after be slowly dropped in prepolymerization system, stirring reaction 20h, in course of reaction not It is disconnected to add dimethyl sulfoxide (DMSO) DMSO, the homogeneous of solution is kept, stops reaction after viscosity is constant.Then polymer solution is precipitated Into water or n-hexane, the vacuum drying chamber for being placed in 40 DEG C dries 24h, and the molecular weight of gpc analysis polymer is about 110,000.Pass through Infrared spectrum and nuclear-magnetism H spectrums, which carry out sign, can determine to obtain PTMCL (PEG600)-HDI-BHB/BDO type polyurethanes, and root Determine that monomer conversion ratio is about 88% according to nuclear-magnetism H spectrums.
4th, polyurethane foam F preparation
It is 10% that above-mentioned polymer, which is dissolved in dioxane, and is diluted to weight percentage, and adds a small amount of water.It is logical The filter for crossing 3 μm is poured into mold, after -40 DEG C of freezings, and 24h is freeze-dried under 10Pa pressure, and is dried to constant weight, is obtained Polyurethane foam F.
Experimental example
1st, the mechanical property to the embodiment 1-6 polyurethane obtained is characterized
Specifically, taking the polyurethane obtained in right amount respectively, it is dissolved in chloroform, solvent is removed in vacuum drying at 40 DEG C, Film is made by solvent evaporation method.
Made film is measured into modulus, tensile strength and elongation at break, the specific experiment data such as institute of table 1 respectively Show.
Table 1
Modulus of elasticity (MPa) Tensile strength (MPa) Elongation at break (%)
Embodiment 1 21 15 643
Embodiment 2 53 35 590
Embodiment 3 19 21 500
Embodiment 4 42 29 621
Embodiment 5 15 10 598
Embodiment 6 38 32 1000
As shown in Table 1, the mechanical property for the polyurethane that the embodiment of the present invention is obtained, tensile strength reaches that Clinical practice will Ask, and with higher compliance, with the compliance with organizing to contact.It is elastic preferable, it is possible to provide certain extruding support Performance, reaches actual operation requirements.Mixed using hard section B block HB with BDO as chain extender, due to the presence of block hard section, Intermolecular force strengthens, and the mechanical property of the polyurethane foam of preparation is more preferable.
2nd, the degradation property of the embodiment 1-6 polyurethane obtained is characterized
In 37 DEG C of phosphate buffer solution, the polyurethane foam can constantly degrade, and produce fragment.
Each 0.5g of polyurethane foam A-F prepared by Example 1-6, are put into the phosphate buffer solution prepared, instead Multiple extruding stands a few minutes afterwards for several times, weighs.Lid is covered, in the thermostat water bath for being placed into 37 DEG C, in 6h, 12h, 24h, 48h, 72h, 168h etc. by strainer filtering, take out the foam of non-fragmentation, after moisture evaporation is complete, survey its corresponding matter respectively Amount, mass loss rate is shown in Fig. 1.
By degradation process it is known that PCLA-PEG polyurethane foams provided in an embodiment of the present invention (A, B) are to have in 6h Obvious fragment drops, after degrading 7 days, and almost degradable is fragment, it is adaptable to short-period cavity hemostasis, and PLGA- PEG polyurethane foams (C, D) type is due to being oligomer polyol with hemicrystalline soft segment, and corresponding polyurethane is then degraded slightly slowly, Go for the wound hemostasis of longer degradation cycle.PTMCL-PEG polyurethane foams (E, F) are then degraded relatively slowly, are due to carbon Sour ester linkage hydrolyzing is relatively stablized, and goes for the wound hemostasis of longer degradation cycle, but if in vivo, its hydrolysis rate meeting It is faster than carbonic acid ester bond.
3rd, the absorbability of the polyurethane foam A-F to being obtained is characterized
Specifically, polyurethane foam A-F is cut into cubic shaped, itself dry weight is 200mg, and porosity is respectively 90%th, 92%, 92%, 85%, 95% and 93%, and the pH value at 37 DEG C is 7.4 phosphoric acid respectively by polyurethane foam A-F Soaked in salt buffer solution, extrude complete to foam water suction after immersion repeatedly, through measurement, polyurethane foam A-F is able to inhale The liquid of about 20 times, 25 times, 26 times, 15 times, 30 times and 27 times of itself dry weight is received, expansion rate, which is respectively less than, is equal to 3%, in wetting shape It is elastic larger under state.
From the foregoing, it will be observed that polyurethane foam provided in an embodiment of the present invention has good liquid absorption capacity, and expansion rate Small, in a moistened state elastic larger, rich in elastic force, disclosure satisfy that the performance requirement of ear nose padding.
In summary, by introducing hydrophily soft segment and degradability soft segment in polyurethane, and by close in soft segment The mol ratio of aqueous polyalcohol and degradable polyol is effectively adjusted, can be to the hydrophilicity and degradation property of polyurethane It is adjusted, and is combined soft segment and hard section using one-step method, the polymer of different mechanical properties can be obtained, so that institute The polyurethane of acquisition has good mechanical performance and degradation property, also, the polyurethane foam porosity obtained is higher, tool There are good water imbibition, and also high resilience in a moistened state, be suitable for clinical practice, therefore, it can the polyurethane foam Foam is as hemostatic material, and wound dressing is used as hemostasis, can also be implanted in the body as ear nose padding, available for stopping blooding, and Good supporting role can be played in certain in the period of to ear nose cavity, and with certain degradation cycle, and finally degrade Completely.And one-step method is used compared with using multistep processes in the prior art, preparation technology is simple, and the cycle is shorter, can avoid drawing Enter impurity, be conducive to industrial applications.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.

Claims (15)

1. a kind of degradable polyurethane foam, it is characterised in that
The polyurethane foam is dissolved in organic solvent by polyurethane, and is obtained by being freeze-dried, wherein, the polyurethane by Oligomer polyol is as soft segment, and polyisocyanates is prepared as hard section with chain extender by the one-step method of body, described Oligomer polyol is hydrophilic polyol and the mixture of degradable polyol.
2. polyurethane foam according to claim 1, it is characterised in that
The one-step method of the body is specifically included：
1) it is added dropwise after oligomer polyol is dehydrated in the polyisocyanates, 2-8h is reacted at 60-100 DEG C；
2) to it is described 1) obtained by product in add the chain extender, continue to react 6-20h, obtain the polyurethane.
3. polyurethane foam according to claim 2, it is characterised in that
The mol ratio of-NCO and-the OH in the oligomer polyol in the polyisocyanates is 1:1-1:3.
4. polyurethane foam according to claim 2, it is characterised in that
It is described 2) described in-OH in chain extender with it is described 1) obtained by product in-NCO mol ratio be 1:1.
5. polyurethane foam according to claim 1, it is characterised in that
The mol ratio of the hydrophilic polyol and the degradable polyol is 2:8-8:2.
6. polyurethane foam according to claim 1, it is characterised in that
The one kind or several of the hydrophilic polyol in polyethylene glycol, PVP, polyvinyl alcohol and polypeptide Kind.
7. polyurethane foam according to claim 1, it is characterised in that
The degradable polyol is selected from polycaprolactone glycol, polylactic acid diol, PPDO, the methylene of polycaprolactone three One or more in base carbonic ester, polycaprolactone lactide and poly (glycolide-co-lactide).
8. polyurethane foam according to claim 1, it is characterised in that
The polyisocyanates is selected from methyl diphenylene diisocyanate, Isosorbide-5-Nitrae-fourth diisocyanate, 1, hexamethylene-diisocyanate With the one or more in toluene di-isocyanate(TDI).
9. polyurethane foam according to claim 1, it is characterised in that
Chain extension after compound progress of the chain extender selected from small molecule dihydric alcohol and with hard section functional group is hydroxy-end capped One or more in agent.
10. polyurethane foam according to claim 1, it is characterised in that
The molecular weight of the polyurethane is 80000-120000.
11. polyurethane foam according to claim 1, it is characterised in that
Tensile strength >=10MPa of the polyurethane.
12. polyurethane foam according to claim 1, it is characterised in that
The elongation at break of the polyurethane is 500%~1000%.
13. polyurethane foam according to claim 1, it is characterised in that
The water absorption rate of the polyurethane foam is 15~30 times of own wt.
14. polyurethane foam according to claim 1, it is characterised in that
The porosity of the polyurethane foam is 85%-95%.
15. as described in claim any one of 1-14 polyurethane foam is as hemostatic material, wound dressing or is used as ear nose The application of padding.
CN201710556919.2A 2017-07-10 2017-07-10 A kind of degradable polyurethane foam and its application Pending CN107286313A (en)

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CN109338504A (en) * 2018-09-17 2019-02-15 浙江华峰氨纶股份有限公司 A kind of degradable spandex high performance polyurethane of biology and preparation method thereof
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CN113831496A (en) * 2021-09-28 2021-12-24 长春工业大学 Glycolic acid-based polyurethane foam and preparation method thereof
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CN114478996A (en) * 2022-02-14 2022-05-13 赢聚化学技术研发(南京)有限公司 Preparation method of degradable hydrophilic polyurethane cosmetic puff
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WO2020043834A1 (en) * 2018-08-30 2020-03-05 Stichting Katholieke Universiteit Polyurethane sheet
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CN109338504B (en) * 2018-09-17 2021-04-20 华峰化学股份有限公司 High-performance polyurethane for biodegradable spandex and preparation method thereof
US20200188179A1 (en) * 2018-12-13 2020-06-18 Advanced Medical Solutions Limited Ribbon wound dressing
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Application publication date: 20171024