CN104387553A - Biodegradable unsaturated polyurethane material and preparation method thereof - Google Patents
Biodegradable unsaturated polyurethane material and preparation method thereof 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
- C08G18/08—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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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a biodegradable unsaturated polyurethane material comprising a soft segment and a hard segment, wherein the soft segment comprises unsaturated polyester polyol polypropylene fumarate, and the hard segment comprises saturated aliphatic isocyanate and a small molecule glycol chain extender or a small molecule diamine chain extender. The material is prepared by taking polypropylene fumarate as large molecule dihydric alcohol, saturated aliphatic isocyanate as a raw material and small molecule glycol or small molecule diamine as a chain extender, and adopting a two-step chain extension method. The polyurethane elastomer namely the biodegradable unsaturated polyurethane material prepared by the preparation method disclosed by the invention has biodegradability, the material and a degradation product are harmless to human bodies, and the material has good biocompatibility. A polyurethane main chain structure comprises a lot of unsaturated electron-deficient double bonds to facilitate further modification of the material, and the material has a good application prospect.
Description
Technical field
The present invention relates to a kind of biodegradable unsaturated polyurethanes material and preparation method thereof, belong to biology medical material technical field.
Background technology
Biodegradable material, due to the characteristic of its degradable and safety non-toxic, has important application in fields such as agricultural, environmental protection, food and medical treatment.Especially in bio-medical field, the material that degradable in vivo and degraded product have no side effect, need not carry out second operation taking-up after in implanted body, therefore apply particularly extensive in useful for drug delivery, organizational project and regenerative medicine and gene therapy.Biodegradable material specifically can be divided into natural origin material and synthetic material.Natural degradable material mainly comprises T 500, chitosan, heparin and protein etc., generally has excellent biocompatibility, but long-term implantation has potential induce variation risk.Comparatively speaking, synthetic degradation material does not have the potentially dangerous of this respect, and biocompatibility also meets embody rule requirement, and the physical and chemical performance of material can obtain meticulous regulation and control simultaneously, thus has application prospect more widely in specific field.
Synthetic Biodegradable material mainly comprises polyester, polyethers, condensing model, urethane and polyamino acid etc.Wherein, be polyurethane material prepared by raw material by degradable polyester, there is excellent mechanical property, moulding process and biocompatibility, and controlled degradation rate and surface property, therefore there is in Bone Defect Repari, cardiovascular reparation etc. important application.Biodegradable polyurethane material is generally with tetramethylene diisocyanate or hexamethylene diisocyanate or 4, the representative examples of saturated aliphatic isocyanic ester such as 4 '-dicyclohexyl methane diisocyanate or 1B vulcabond are raw material, have the carcinogenic Biodegradation of PAHs product of mutagenesis in case produce.Adopt small molecules dibasic alcohol or diamine to be chainextender simultaneously, prepare high molecular urethane by two step chain extension methods.Synthesize a large amount of degradable polyurethane products and be used widely at present.Such as, be soft section by degradable polyesters such as poly-(6-caprolactone) (PCL), polycarbonate (PC), poly-β-hydroxybutyric acids (PHB), cooperation obtains a series of degradable polyurethane material.
At present, extensively, generally concentrate on saturated polyol polyester is raw material to the research of biological medical degradable polyurethane material, and the material prepared thus has good mechanical property and biological safety, but lacks enough biological activitys.Simultaneously can for the functional group of reaction due to main polymer chain lacking, therefore material modification needs to be realized by methods such as plasma body, aminolysis, photo-graftings, makes the functionalization of material become difficult complex steps, thus the further application of limiting material.Therefore, prepare a kind of biocompatibility with excellence, there is the Biodegradable polyurethane material of easy modification and functional method simultaneously, have great importance.
Summary of the invention
The object of the invention is the problem being difficult to effective modification in order to solve existing medical degradable polyurethane material, provide a kind of can the biodegradable unsaturated polyurethanes material and preparation method thereof of easy functionalization.
The object of the invention is to be achieved through the following technical solutions.
Biodegradable unsaturated polyurethanes material of the present invention, comprise soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester, and described hard section is representative examples of saturated aliphatic isocyanic ester and small molecules diol chain-extension agent or small molecules diamine chain stretching agent.
The number-average molecular weight of above-mentioned poly-fumaric acid propylene glycol ester is 500-3000.
Above-mentioned aliphatic isocyanates can be tetramethylene diisocyanate or hexamethylene diisocyanate (HDI) or HMDI (HMDI) or 1B vulcabond (LDI); Described small molecules diol chain-extension agent can be BDO (BDO); Small molecules diamine chain stretching agent can be 1B methyl esters (Lys-OMe).
The preparation method of biodegradable unsaturated polyurethanes material of the present invention, comprises the following steps:
1) poly-fumaric acid propylene glycol ester and dry toluene are mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, adopt the mole number of hydroxyl in ISO 2554-1974 method determination solution;
2) by step 1) the poly-fumaric acid propylene glycol ester solution of gained joins in dry there-necked flask, removal of solvent under reduced pressure toluene and residual water-content, then add solvent anhydrous dioxane again to dissolve, add representative examples of saturated aliphatic isocyanic ester again, and catalyst dibutyltin dilaurylate, under nitrogen protection in 60 ~ 80 DEG C of reaction 2 ~ 5h, obtain isocyanate-terminated prepolymer; Wherein in representative examples of saturated aliphatic isocyanic ester, the mole number of isocyanate group is 1.1 ~ 1.6:1 with the ratio of the mole number of hydroxyl in poly-fumaric acid propylene glycol ester, and dibutyl tin laurate consumption is the 0.2mol% of hydroxyl moles in solution;
3) in step 2) add small molecules glycol or small molecules diamines in the isocyanate-terminated prepolymer prepared, in 60 DEG C of chain extending reaction at least 6h, obtain polyurethane solution, the mole number of small molecules glycol or small molecules diamines is the difference of hydroxyl moles in isocyanate group mole number and poly-fumaric acid propylene glycol ester in representative examples of saturated aliphatic isocyanic ester;
4) 60 DEG C are kept, in step 3) add ethanol end-blocking in the polyurethane solution prepared;
5) by through step 4) polyurethane solution that processes pours in ethanol and precipitates, centrifugal, collection, the urethane solid of collection is dissolved in dioxane again, and again pour in ethanol and precipitate, repeatedly for several times, finally the urethane solid dioxane of gained is dissolved, lyophilize, obtain biodegradable unsaturated polyurethanes material.
Compared with existing medical polyurethane, the present invention has the following advantages:
1) poly-fumaric acid propylene glycol ester has excellent biodegradability and biocompatibility, its degraded product is mainly fumaric acid and propylene glycol, all external by tricarboxylic cycle eliminating in human body, have no side effect, therefore with poly-fumaric acid propylene glycol ester for urethane prepared by raw material has biodegradable performance.
2) with representative examples of saturated aliphatic isocyanic ester for raw material, make hard section degraded product without the toxic side effect such as carcinogenic.
3) with small molecules glycol or diamines for chainextender, make hard section degraded product without the toxic side effect such as carcinogenic.
4) polyurethane molecular backbone structure retains a large amount of unsaturated electron deficiency carbon-to-carbon double bond, can provide efficient reaction site under mild conditions, makes the modification of material and functionalization more simple effectively.
Accompanying drawing explanation
Fig. 1 is the synthetic line figure of biodegradable unsaturated polyurethanes material of the present invention.
Embodiment
Further illustrate the present invention below in conjunction with example, but these examples are not used for limiting the present invention.The synthetic line of biodegradable unsaturated polyurethanes material of the present invention is as Fig. 1.
Embodiment 1
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.6+Lys-OMe), comprise soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester PPF, and described hard section is aliphatic isocyanates HDI and small molecules diamine chain stretching agent Lys-OMe.
There is following structure.
By number-average molecular weight be 1000 PPF be mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, according to ISO 2554-1974 method, determine that obtaining hydroxyl moles in solution is 14.68mmol.
Getting above-mentioned PPF toluene solution adds in dry there-necked flask, 110 DEG C of decompression 1h, removing solvent toluene and residual water-content.Add solvent anhydrous dioxane 30mL again to dissolve, add 1.9752g hexamethylene diisocyanate (HDI), 0.03mmol catalyst dibutyltin dilaurylate, under nitrogen protection in 70 DEG C of reaction 3h.Be cooled to 60 DEG C, add 1.0267g lysine methyl ester dihydrochloride, after stirring 15min, add 1.3369g triethylamine, chain extending reaction 6h at 60 DEG C.Add 3g ethanol synthesis 1h and carry out end-blocking.After completion of the reaction urethane dioxane solution is poured in ethanol and precipitate, 3 times repeatedly.Finally be dissolved in dioxane solution, lyophilize 24h, obtains urethane.
Obtained urethane is dissolved in dioxane, pours in polytetrafluoro mould, air atmosphere normal temperature volatilization 72h, after remove residual solvents in 35 DEG C of vacuum-drying 48h, obtain polyurethane film.In order to investigate the mechanical property of urethane prepared by the present invention, test tensile strength and the elongation at break of urethane, batten is of a size of: length x width x thickness=50mm × 5mm × 0.5mm.Rate of extension is 100mm/min.Mechanics Performance Testing gained urethane breaking tenacity is 4.9MPa, and elongation at break is 960%.
In order to investigate the degradation property of urethane prepared by the present invention, carried out external degradation experiment, degraded medium is 5mol/L sodium hydroxide solution.The polyurethane film of 10mm × 10mm is put into 20mL seed bottle, adds 15mL sodium hydroxide solution, shake in 37 DEG C of waters bath with thermostatic control.Be hydrolyzed and take out sample after 15 days, with distilled water wash 3 times, in the dry 24h of 40 DEG C of vacuum drying ovens.Degraded adopts mass loss per-cent to represent: mass loss (%)=(W
0-W
1)/W
0× 100%.Wherein W
0and W
1quality before being respectively polyurethane samples degraded and after degraded.After degrading 15 days in degradation experiment display potassium hydroxide solution, mass loss is 76.48%.
Embodiment 2
Biodegradable unsaturated polyurethanes material (PPFU/HMDI 1.6+Lys-OMe), comprise soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester PPF, and described hard section is aliphatic isocyanates HMDI and small molecules diamine chain stretching agent Lys-OMe.
Its preparation comprises the following steps:
By number-average molecular weight be 1000 PPF be mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, according to ISO 2554-1974 method, determine that obtaining hydroxyl moles in solution is 14.68mmol.
Getting above-mentioned PPF toluene solution adds in dry there-necked flask, 110 DEG C of underpressure distillation 1h, removing solvent toluene and residual water-content.Add solvent anhydrous dioxane 30mL again to dissolve, add 3.0810g HMDI (HMDI), 0.03mmol catalyst dibutyltin dilaurylate, under nitrogen protection in 70 DEG C of reaction 3h.Be cooled to 60 DEG C, add 1.0267g lysine methyl ester dihydrochloride, after stirring 15min, add 1.3369g triethylamine, chain extending reaction 6h at 60 DEG C.Add 3g ethanol synthesis 1h and carry out end-blocking.After completion of the reaction urethane dioxane solution is poured in ethanol and precipitate, 3 times repeatedly.Finally be dissolved in dioxane solution, lyophilize 24h, obtains urethane.
Gained urethane breaking tenacity is 5.8MPa, and elongation at break is 640%; After degrading 15 days in sodium hydroxide solution, mass loss is 46.89%.
Embodiment 3
Biodegradable unsaturated polyurethanes material (PPFU/LDI 1.6+Lys-OMe), comprise soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester PPF, and described hard section is aliphatic isocyanates LDI and small molecules diamine chain stretching agent Lys-OMe.
There is following structure.
Its preparation comprises the following steps:
By number-average molecular weight be 1000 PPF be mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, according to ISO 2554-1974 method, determine that obtaining hydroxyl moles in solution is 14.68mmol.
Getting above-mentioned PPF toluene solution adds in dry there-necked flask, 110 DEG C of underpressure distillation 1h, removing solvent toluene and residual water-content.Add solvent anhydrous dioxane 30mL again to dissolve, add 2.6568g 1B vulcabond (LDI), 0.03mmol catalyst dibutyltin dilaurylate, under nitrogen protection in 70 DEG C of reaction 3h.Be cooled to 60 DEG C, add 1.0267g lysine methyl ester dihydrochloride, after stirring 15min, add 1.3369g triethylamine, chain extending reaction 6h at 60 DEG C.Add 3g ethanol synthesis 1h and carry out end-blocking.After completion of the reaction urethane dioxane solution is poured in ethanol and precipitate, 3 times repeatedly.Finally be dissolved in dioxane solution, lyophilize 24h, obtains urethane.
Gained urethane breaking tenacity is 1.3MPa, and elongation at break is 950%; After degrading 15 days in sodium hydroxide solution, mass loss is 100%.
Embodiment 4
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.6+BDO), comprise soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester PPF, and described hard section is aliphatic isocyanates HDI and small molecules diol chain-extension agent BDO.
There is following structure.
Its preparation comprises the following steps:
By number-average molecular weight be 1000 PPF be mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, according to ISO 2554-1974 method, determine that obtaining hydroxyl moles in solution is 14.68mmol.
Getting above-mentioned PPF toluene solution adds in dry there-necked flask, 110 DEG C of underpressure distillation 1h, removing solvent toluene and residual water-content.Add solvent anhydrous dioxane 30mL again to dissolve, add 1.9752g HDI, 0.03mmol catalyst dibutyltin dilaurylate, under nitrogen protection in 70 DEG C of reaction 3h.Be cooled to 60 DEG C, add 0.3969g BDO (BDO), chain extending reaction 6h at 60 DEG C.Add 3g ethanol synthesis 1h and carry out end-blocking.After completion of the reaction urethane dioxane solution is poured in ethanol and precipitate, 3 times repeatedly.Finally be dissolved in dioxane solution, lyophilize 24h, obtains urethane.
Gained urethane breaking tenacity is 4.3MPa, and elongation at break is 480%; After degrading 15 days in sodium hydroxide solution, mass loss is 78.64%.
Embodiment 5
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.3+BDO), comprise soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester PPF, and described hard section is aliphatic isocyanates HDI and small molecules diol chain-extension agent BDO.
There is following structure.
Its preparation comprises the following steps:
By number-average molecular weight be 1000 PPF be mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, according to ISO 2554-1974 method, determine that obtaining hydroxyl moles in solution is 14.68mmol.
Getting above-mentioned PPF toluene solution adds in dry there-necked flask, 110 DEG C of underpressure distillation 1h, removing solvent toluene and residual water-content.Add solvent anhydrous dioxane 30mL again to dissolve, add 1.6049g HDI, 0.03mmol catalyst dibutyltin dilaurylate, under nitrogen protection in 70 DEG C of reaction 3h.Be cooled to 60 DEG C, add 0.1985g BDO (BDO), chain extending reaction 6h at 60 DEG C.Add 3g ethanol synthesis 1h and carry out end-blocking.After completion of the reaction urethane dioxane solution is poured in ethanol and precipitate, 3 times repeatedly.Finally be dissolved in dioxane solution, lyophilize 24h, obtains urethane.
Gained urethane breaking tenacity is 2.6MPa, and elongation at break is 780%; After degrading 15 days in sodium hydroxide solution, mass loss is 100%.
Embodiment 6
Biodegradable unsaturated polyurethanes material (PPFU/HDI 1.3+BDO), comprise soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester PPF, and described hard section is aliphatic isocyanates HDI and small molecules diol chain-extension agent BDO.
There is following structure.
Its preparation comprises the following steps:
By number-average molecular weight be 2000 PPF be mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, according to ISO 2554-1974 method, determine that obtaining hydroxyl moles in solution is 7.35mmol.
Getting above-mentioned PPF toluene solution adds in dry there-necked flask, 110 DEG C of underpressure distillation 1h, removing solvent toluene and residual water-content.Add solvent anhydrous dioxane 30mL again to dissolve, add 0.8025g HDI, 0.015mmol catalyst dibutyltin dilaurylate, under nitrogen protection in 70 DEG C of reaction 3h.Be cooled to 60 DEG C, add 0.09931,4-butyleneglycol (BDO), chain extending reaction 6h at 60 DEG C.Add 3g ethanol synthesis 1h and carry out end-blocking.After completion of the reaction urethane dioxane solution is poured in ethanol and precipitate, 3 times repeatedly.Finally be dissolved in dioxane solution, lyophilize 24h, obtains urethane.
Gained urethane breaking tenacity is 2.1MPa, and elongation at break is 850%; After degrading 15 days in sodium hydroxide solution, mass loss is 100%.
Claims (4)
1. a biodegradable unsaturated polyurethanes material, it is characterized in that: this material comprises soft section and hard section, described soft section is that unsaturated polyester ester polyol gathers fumaric acid propylene glycol ester, and described hard section is representative examples of saturated aliphatic isocyanic ester and small molecules diol chain-extension agent or small molecules diamine chain stretching agent.
2. biodegradable unsaturated polyurethanes material according to claim 1, is characterized in that: the number-average molecular weight of described poly-fumaric acid propylene glycol ester is 500-3000.
3. biodegradable unsaturated polyurethanes material according to claim 2, it is characterized in that: described aliphatic isocyanates is tetramethylene diisocyanate or hexamethylene diisocyanate or HMDI or 1B vulcabond; Described small molecules diol chain-extension agent is BDO; Small molecules diamine chain stretching agent is 1B methyl esters.
4. prepare the method for biodegradable unsaturated polyurethanes material according to claim 1, comprise the following steps:
1) poly-fumaric acid propylene glycol ester and dry toluene are mixed with the poly-fumaric acid propylene glycol ester solution of massfraction 30%, adopt the mole number of hydroxyl in ISO 2554-1974 method determination solution;
2) the poly-fumaric acid propylene glycol ester solution of step 1) gained is joined in dry there-necked flask, removal of solvent under reduced pressure toluene and residual water-content, then add solvent anhydrous dioxane again to dissolve, add representative examples of saturated aliphatic isocyanic ester again, and catalyst dibutyltin dilaurylate, react 2 ~ 5h in 60 ~ 80 ° of C under nitrogen protection, obtain isocyanate-terminated prepolymer; Wherein in representative examples of saturated aliphatic isocyanic ester, the mole number of isocyanate group is 1.1 ~ 1.6:1 with the ratio of the mole number of hydroxyl in poly-fumaric acid propylene glycol ester, and dibutyl tin laurate consumption is 0.2 mol% of hydroxyl moles in solution;
3) in step 2) add small molecules glycol or small molecules diamines in the isocyanate-terminated prepolymer prepared, in 60 ° of C chain extending reaction at least 6h, obtain polyurethane solution, the mole number of small molecules glycol or small molecules diamines is the difference of hydroxyl moles in isocyanate group mole number and poly-fumaric acid propylene glycol ester in representative examples of saturated aliphatic isocyanic ester;
4) keep 60 ° of C, in polyurethane solution prepared by step 3), add ethanol end-blocking;
5) polyurethane solution through step 4) process is poured in ethanol precipitate, centrifugal, collection, the urethane solid of collection is dissolved in dioxane again, and again pour in ethanol and precipitate, repeatedly for several times, finally the urethane solid dioxane of gained is dissolved, lyophilize, obtain biodegradable unsaturated polyurethanes material.
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| CN106046309A (en) * | 2015-11-20 | 2016-10-26 | 徐永祥 | Completely-biodegradable cross-linked polyurethane and preparation method thereof, and porous sponge prepared from completely-biodegradable cross-linked polyurethane |
| CN106397721A (en) * | 2016-10-10 | 2017-02-15 | 同济大学 | Preparation method of biodegradable polyurethane containing unsaturated bond |
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| CN106046309A (en) * | 2015-11-20 | 2016-10-26 | 徐永祥 | Completely-biodegradable cross-linked polyurethane and preparation method thereof, and porous sponge prepared from completely-biodegradable cross-linked polyurethane |
| CN106397721A (en) * | 2016-10-10 | 2017-02-15 | 同济大学 | Preparation method of biodegradable polyurethane containing unsaturated bond |
| CN106397721B (en) * | 2016-10-10 | 2019-01-11 | 同济大学 | A kind of preparation method of the Biodegradable polyurethane containing unsaturated bond |
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