CN102002142B - Biodegradable polyurethane and preparation method thereof - Google Patents
Biodegradable polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a biodegradable polyurethane and a preparation method thereof. The polyurethane is copolymerized by alkylene polycarbonate-diol polylactic segmented copolymer, diisocyanate and a chain extender and with molecular weight 10000-1000000g/mol. The preparation method of polyurethane comprises the following steps of: dissolving dry alkylene polycarbonate-diol polylactic segmented copolymer into a solution and adding diisocyanate; performing nitrogenization after vacuumizing 5-10 times and maintaining pressure at 0.05-0.5MPa after the last nitrogenization; reflowing for 0.1-24h at 60-180 DEG C, and then adding the chain extender, performing nitrogenization after vacuumizing 5-10 times and maintaining pressure at 0.05-0.5MPa after the last nitrogenization, continuing the reaction for 0.1-24h and filtering and drying the product after precipitation treatment to obtain the target product. The method has the advantages of stable reaction, easy control, and the polyurethane prepared has good biodegradability.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of urethane, also relate to the preparation method of this urethane based on polymerized thylene carbonate alkane ester-polylactide.
Background technology
Polymerized thylene carbonate alkane ester is that one type of aliphatic polycarbonate has the favorable biological degradability ability.Wherein, The poly (propylene carbonate) polyvalent alcohol is telomerized under catalyst action by carbonic acid gas and propylene oxide and obtains, and is one of main raw material of producing PAUR, the polyurethane elastomer stable chemical performance of being processed by it; Has good machining property; Wear-resisting, oil resistant, low temperature resistant, hydrolysis, and hydrolytic resistance is higher than conventional polyester, and physical and mechanical properties is higher than polyether glycol urethane; Being widely used in sealing-ring, travelling belt, unworn liner, automobile shockproof buffer block and low speed tire etc., is one of current ideal rubber and plastic engineering materials.
In the used polymerized thylene carbonate esterdiol of preparation aliphatic polycarbonate type polyurethane, studying often both at home and abroad has polymerized thylene carbonate glycol ester glycol, polymerized thylene carbonate butanediol ester glycol, poly (propylene carbonate) glycol etc.Such as by polymerized thylene carbonate ethyl ester glycol and the synthetic polymerized thylene carbonate urethane elastomer (CN 1865311A) of vulcabond, be that the synthetic one type of polycarbonate polyurethane elastomerics with good biological property of raw material (thanks to emerging beneficial ， Liu Fang and for example to gather own diamyl glycol carbonate glycol; Clock elecscreen etc. the biomedical engineering magazine, 1999,16:121-122); Perhaps synthesize some solvent-proof aliphatic polycarbonate type polyurethane elastomericss (Harris R F, Joseph M D, Avisdson C D et al.J Appl Polym Sci; 1990; 41:487-507), perhaps with poly (propylene carbonate) two pure and mild tolylene diisocyanates be raw material synthesized the poly (propylene carbonate) polyurethane elastomer (Peng Han etc. the synthetic and performance of poly (propylene carbonate) polyurethane elastomer, chemistry world; 1995,8:426-428).
Polylactide (POLYACTIC ACID) is a kind of aliphatic polyester, and it derives from Biological resources, in environment, can be degraded fully by mikrobe again, can alleviate consuming excessively of petroleum resources, can solve the environmental problem that conventional plastic is brought again.On chemical structure, the polylactic acid chain segment in the polylactide under certain condition can crystallization, therefore has higher rigidity.Because POLYACTIC ACID is nontoxic; Has excellent biological compatibility; Thereby in human body, can be biodegradable into lactic acid and get into tricarboxylic acid cycle, eventual degradation is that carbonic acid gas and water are discharged behind homergy, therefore; POLYACTIC ACID is widely used in aspects such as operating suture, bone fixed repairing material, material implanted, drug release material, has become in the biological degradation field of medical materials one of the most valued material at present.
In sum; With the material copolymerization under certain condition of polymerized thylene carbonate alkane esterdiol and two kinds of different performances of polylactide and carry out chain extension; Polymerized thylene carbonate alkane ester-polylactide polyurethane material with development of new; It can be learnt from other's strong points to offset one's weaknesses on performance, thereby bring into play advantage separately to greatest extent.
Summary of the invention
The purpose of this invention is to provide a kind of novel biodegradable polyurethane that contains two hard sections; Comprise these two kinds hard sections of crystallizable polylactic acid chain segment and vulcabond segment in this polyurethane structural, the elastomerics that therefore makes will have higher elastic-restoring force.The present invention also provides the preparation method of this urethane.
Urethane of the present invention is formed by polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, vulcabond, chainextender copolymerization, and molecular weight is 10000～1000000g/mol, and structural formula does
Wherein, group A is that polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, group B are that vulcabond, group C are chainextender.
The weight-average molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000～100000g/mol; Polymerized thylene carbonate alkane ester wherein is one or more in polymerized thylene carbonate ethyl ester, poly (propylene carbonate), the polymerized thylene carbonate butyl ester, and POLYACTIC ACID is one or both the mixing in L type POLYACTIC ACID, the D type POLYACTIC ACID.Polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol causes the rac-Lactide ring opening copolymer by polymerized thylene carbonate alkane esterdiol and obtains under the effect of catalyzer, this method is maturation method (referenced patent ZL200910155893.6).
Described vulcabond is the cyanate that contains two cyanic acid groups in the molecule; Be hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), 4; 4 '-methylene-bis (phenylcarbimide) (MDI), liquefied mdi, isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), naphthalene-1, a kind of in 5-vulcabond (NDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methane diisocyanate (HMDI), the tetramethylxylylene diisocyanate (TMXDI).
Described chainextender is 3,3 '-two chloro-4,4 '-ditan diamines, 1,4-butyleneglycol, terepthaloyl moietie, glycol ether, 1,6-pinakon, TriMethylolPropane(TMP), quinhydrones-two (beta-hydroxyethyl) ether a kind of.
This urethane adopts the segmented copolymer glycol that contains polymerized thylene carbonate alkane ester section and polylactic acid chain segment to make through vulcabond and chainextender reaction, and concrete grammar is:
Dissolve in polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol adding solvent with thorough drying, add vulcabond then, the mol ratio of the vulcabond of adding and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2～100: 1; Fill nitrogen operation after repeating to vacuumize 5～10 times, feed for the last time that to keep pressure behind the nitrogen be 0.05～0.5MPa; At 60～180 ℃ of temperature refluxed 0.1～24h, add chainextender then, the mole number of the chainextender of adding is mole number poor of vulcabond and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; Fill nitrogen operation after repeating to vacuumize 5～10 times again, feed for the last time that to keep pressure behind the nitrogen be 0.05～0.5MPa, continue reaction 0.1～24h, product is dry through the precipitation process after-filtration, obtains target urethane.
Described solvent is a kind of in trichloromethane, toluene, acetone, THF and the N; Every gram polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol adds 1～100ml solvent.
Can add the catalyzer accelerated reaction after adding chainextender; Described catalyzer is a kind of in dibutyl tin laurate, stannous octoate, tin protochloride, diethylenetriamine, trolamine, the triethylamine; The quality of the catalyzer that adds is 0.001～10% of polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol quality.
Because the ester bond in polymerized thylene carbonate alkane ester section and the POLYACTIC ACID section can both be by biological degradation, therefore urethane of the present invention also has the favorable biological degradability ability.Experiment showed, urethane of the present invention under composting conditions in three months its relative biolysis rate surpass 90%.The present invention prepares urethane through solution method, and reacting balance is easy to control, can regulate the soft or hard section content of final product through the add-on that changes each reactant, thus the different polyurethane material of obtained performance.
Embodiment
Embodiment 1
With the weight-average molecular weight of 0.001mol thorough drying is that polymerized thylene carbonate ethyl ester-L type polylactic-acid block copolymer glycol of 2000g/mol is put into the 50ml reaction flask that the 2ml trichloromethane is housed; Wait to dissolve the hexamethylene diisocyanate (HDI) that the back adds 0.002mol; Fill nitrogen operation after repeating to vacuumize 5 times, feed for the last time that to keep pressure behind the nitrogen be 0.05MPa; The 60 ℃ of backflow 0.1h that heat up add chainextender 1, the 4-butyleneglycol then; The mole number of its adding is mole number poor of HDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; Fill nitrogen operation after repeating again to vacuumize 5 times, feed for the last time that to keep pressure behind the nitrogen be 0.05MPa, continue reaction 0.1h; Product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 10Kg/mol, MWD are 1.81 urethane.
Embodiment 2
With the weight-average molecular weight of 0.002mol thorough drying is that poly (propylene carbonate)-D type polylactic-acid block copolymer glycol of 100000g/mol is put into the 1000ml reaction flask that 500ml acetone is housed; Wait to dissolve the tolylene diisocyanate (TDI) that the back adds 0.004mol; Fill nitrogen operation after repeating to vacuumize 8 times, feed for the last time that to keep pressure behind the nitrogen be 0.1MPa; 70 ℃ of backflow 1h heat up; Add chainextender 3 then, 3 '-two chloro-4,4 '-ditan diamines; The mole number of its adding is mole number poor of TDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; The dibutyl tin laurate that adds 0.002g again fills nitrogen operation 6 times after repeating to vacuumize, feed for the last time that to keep pressure behind the nitrogen be 0.1MPa; Continue reaction 1h, product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 1000Kg/mol, MWD are 1.97 urethane.
Embodiment 3
With the weight-average molecular weight of 0.0002mol thorough drying is that polymerized thylene carbonate butyl ester-polylactic-acid block copolymer glycol (POLYACTIC ACID in the segmented copolymer glycol partly is D type POLYACTIC ACID for L type POLYACTIC ACID, part) of 10000g/mol is put into the 500ml reaction flask that 200ml toluene is housed; Wait to dissolve the back and add 4 of 0.02mol; 4 '-methylene-bis (phenylcarbimide) (MDI); Fill nitrogen operation after repeating to vacuumize 9 times, feed for the last time that to keep pressure behind the nitrogen be 0.5MPa; The 100 ℃ of backflow 3h that heat up add chainextender terepthaloyl moietie then, and the mole number of its adding is mole number poor of MDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; The stannous octoate that adds 0.2g again; Fill nitrogen operation after repeating to vacuumize 8 times, feed for the last time that to keep pressure behind the nitrogen be 0.5MPa, continue reaction 5h; Product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 130Kg/mol, MWD are 1.75 urethane.
Embodiment 4
With the weight-average molecular weight of 0.0001mol thorough drying is that polymerized thylene carbonate alkane ester-L type polylactic-acid block copolymer glycol (the polymerized thylene carbonate alkane ester moiety in the segmented copolymer glycol is that polymerized thylene carbonate ethyl ester, part are poly (propylene carbonate)) of 30000g/mol is put into the 100ml reaction flask that the 30ml THF is housed; Wait to dissolve the liquefied mdi that the back adds 0.005mol; Fill nitrogen operation after repeating to vacuumize 7 times, feed for the last time that to keep pressure behind the nitrogen be 0.1MPa; The 80 ℃ of backflow 10h that heat up add the chainextender glycol ether then, and the mole number of its adding is mole number poor of liquefied mdi and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; The tin protochloride that adds 0.03g again; Fill nitrogen operation after repeating to vacuumize 6 times, feed for the last time that to keep pressure behind the nitrogen be 0.1MPa, continue reaction 12h; Product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 280Kg/mol, MWD are 1.93 urethane.
Embodiment 5
With the weight-average molecular weight of 0.0006mol thorough drying is that polymerized thylene carbonate alkane ester-D type polylactic-acid block copolymer glycol (the polymerized thylene carbonate alkane ester moiety in the segmented copolymer glycol is that polymerized thylene carbonate ethyl ester, part are the polymerized thylene carbonate butyl ester) of 50000g/mol is put into the 250ml reaction flask that the 100ml N is housed; Wait to dissolve the isophorone diisocyanate (IPDI) that the back adds 0.036mol; Fill nitrogen operation after repeating to vacuumize 7 times, feed for the last time that to keep pressure behind the nitrogen be 0.2MPa; The 180 ℃ of backflow 24h that heat up add chainextender 1, the 6-pinakon then; The mole number of its adding is mole number poor of IPDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, adds the diethylenetriamine of 0.03g again, fills nitrogen operation 6 times after repeating to vacuumize; Keeping pressure behind the last feeding nitrogen is 0.2MPa; Continue reaction 24h, product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 80Kg/mol, MWD are 1.71 urethane.
Embodiment 6
With the weight-average molecular weight of 0.001mol thorough drying is that (the polymerized thylene carbonate alkane ester moiety in the segmented copolymer glycol is that poly (propylene carbonate), part are the polymerized thylene carbonate butyl ester for polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol of 8000g/mol; POLYACTIC ACID partly for L type POLYACTIC ACID, part for D type POLYACTIC ACID) put into the 100ml reaction flask that the 50ml trichloromethane is housed; Wait to dissolve the xylylene diisocyanate (XDI) that the back adds 0.01mol; Fill nitrogen operation after repeating to vacuumize 8 times, feed for the last time that to keep pressure behind the nitrogen be 0.25MPa; The 120 ℃ of backflow 2h that heat up add the chainextender TriMethylolPropane(TMP) then, and the mole number of its adding is mole number poor of XDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; The trolamine that adds 0.01g again; Fill nitrogen operation after repeating to vacuumize 5 times, feed for the last time that to keep pressure behind the nitrogen be 0.25MPa, continue reaction 7h; Product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 90Kg/mol, MWD are 1.59 urethane.
Embodiment 7
With the weight-average molecular weight of 0.001mol thorough drying is that polymerized thylene carbonate alkane ester-D type polylactic-acid block copolymer glycol (the polymerized thylene carbonate alkane ester moiety in the segmented copolymer glycol is that polymerized thylene carbonate ethyl ester, part are the polymerized thylene carbonate butyl ester for poly (propylene carbonate), part) of 12000g/mol is put into the 1000ml reaction flask that 600ml toluene is housed; Wait to dissolve the naphthalene-1 that the back adds 0.02mol; 5-vulcabond (NDI); Fill nitrogen operation after repeating to vacuumize 10 times, feed for the last time that to keep pressure behind the nitrogen be 0.3MPa; The 160 ℃ of backflow 8h that heat up add chainextender quinhydrones-two (beta-hydroxyethyl) ether then, and the mole number of its adding is mole number poor of NDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; The triethylamine that adds 0.006g again; Fill nitrogen operation after repeating to vacuumize 10 times, feed for the last time that to keep pressure behind the nitrogen be 0.3MPa, continue reaction 6h; Product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 110Kg/mol, MWD are 1.62 urethane.
Embodiment 8
With the weight-average molecular weight of 0.001mol thorough drying is that (the polymerized thylene carbonate alkane ester moiety in the segmented copolymer glycol is that polymerized thylene carbonate ethyl ester, part are the polymerized thylene carbonate butyl ester for poly (propylene carbonate), part for polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol of 34000g/mol; POLYACTIC ACID partly for L type POLYACTIC ACID, part for D type POLYACTIC ACID) put into the 500ml reaction flask that 200ml acetone is housed; Wait to dissolve the Methylcyclohexyl diisocyanate (HTDI) that the back adds 0.005mol; Fill nitrogen operation after repeating to vacuumize 9 times, feed for the last time that to keep pressure behind the nitrogen be 0.4MPa; The 90 ℃ of backflow 16h that heat up add chainextender 1, the 4-butyleneglycol then; The mole number of its adding is mole number poor of HTDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; Fill nitrogen operation after repeating again to vacuumize 5 times, feed for the last time that to keep pressure behind the nitrogen be 0.4MPa, continue reaction 10h; Product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 400Kg/mol, MWD are 1.67 urethane.
Embodiment 9
With the weight-average molecular weight of 0.001mol thorough drying is that (the polymerized thylene carbonate alkane ester moiety in the segmented copolymer glycol is that polymerized thylene carbonate ethyl ester, part are poly (propylene carbonate) for polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol of 57000g/mol; POLYACTIC ACID partly for L type POLYACTIC ACID, part for D type POLYACTIC ACID) put into the 250ml reaction flask that the 100ml N is housed; Wait to dissolve the dicyclohexyl methane diisocyanate (HMDI) that the back adds 0.002mol; Fill nitrogen operation after repeating to vacuumize 5 times, feed for the last time that to keep pressure behind the nitrogen be 0.45MPa; 150 ℃ of backflow 14h heat up; Add the chainextender TriMethylolPropane(TMP) then, the mole number of its adding is mole number poor of HMDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, fills nitrogen operation 9 times after repeating to vacuumize again; Keeping pressure behind the last feeding nitrogen is 0.45MPa; Continue reaction 9h, product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 680Kg/mol, MWD are 1.78 urethane.
Embodiment 10
With the weight-average molecular weight of 0.001mol thorough drying is that (the polymerized thylene carbonate alkane ester moiety in the segmented copolymer glycol is that poly (propylene carbonate), part are the polymerized thylene carbonate butyl ester for polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol of 5000g/mol; POLYACTIC ACID partly for L type POLYACTIC ACID, part for D type POLYACTIC ACID) put into the 100ml reaction flask that 50ml acetone is housed; Wait to dissolve the tetramethylxylylene diisocyanate (TMXDI) that the back adds 0.003mol; Fill nitrogen operation after repeating to vacuumize 5 times, feed for the last time that to keep pressure behind the nitrogen be 0.1MPa; 75 ℃ of backflow 22h heat up; Add chainextender terepthaloyl moietie then, the mole number of its adding is mole number poor of TMXDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, fills nitrogen operation 8 times after repeating to vacuumize again; Keeping pressure behind the last feeding nitrogen is 0.1MPa; Continue reaction 23h, product is dry through the precipitation process after-filtration, and finally obtaining molecular weight is that 59Kg/mol, MWD are 1.72 urethane.
Claims (6)
1. a method for preparing biodegradable polyurethane is characterized in that this method adopts the segmented copolymer glycol that contains polymerized thylene carbonate alkane ester section and polylactic acid chain segment to make through vulcabond and chainextender reaction, and concrete grammar is:
Dissolve in polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol adding solvent with thorough drying, add vulcabond then, the mol ratio of the vulcabond of adding and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2～100: 1; Fill nitrogen operation after repeating to vacuumize 5～10 times, feed for the last time that to keep pressure behind the nitrogen be 0.05～0.5MPa; At 60～180 ℃ of temperature refluxed 0.1～24h, add chainextender then, the mole number of the chainextender of adding is mole number poor of vulcabond and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol; Fill nitrogen operation after repeating to vacuumize 5～10 times again, feed for the last time that to keep pressure behind the nitrogen be 0.05～0.5MPa, continue reaction 0.1～24h, product is dry through the precipitation process after-filtration, obtains target urethane.
2. a kind of method for preparing biodegradable polyurethane as claimed in claim 1 is characterized in that:
The weight-average molecular weight of described polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol is 2000～100000g/mol; Polymerized thylene carbonate alkane ester wherein is one or more in polymerized thylene carbonate ethyl ester, poly (propylene carbonate), the polymerized thylene carbonate butyl ester, and POLYACTIC ACID is one or both in L type POLYACTIC ACID, the D type POLYACTIC ACID.
3. a kind of method for preparing biodegradable polyurethane as claimed in claim 1 is characterized in that:
Described vulcabond is the cyanate that contains two cyanic acid groups in the molecule; Be hexamethylene diisocyanate, tolylene diisocyanate, 4; 4 '-methylene-bis (phenylcarbimide), liquefied mdi, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, a kind of in 5-vulcabond, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, the tetramethylxylylene diisocyanate.
4. a kind of method for preparing biodegradable polyurethane as claimed in claim 1 is characterized in that:
Described chainextender is 3,3 '-two chloro-4,4 '-ditan diamines, 1,4-butyleneglycol, terepthaloyl moietie, glycol ether, 1,6-pinakon, TriMethylolPropane(TMP), quinhydrones-two (beta-hydroxyethyl) ether a kind of.
5. a kind of according to claim 1 method for preparing biodegradable polyurethane is characterized in that: described solvent is a kind of in trichloromethane, toluene, acetone, THF and the N; Every gram polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol adds 1～100ml solvent.
6. a kind of according to claim 1 method for preparing biodegradable polyurethane adds the catalyzer accelerated reaction behind the adding chainextender; Described catalyzer is a kind of in dibutyl tin laurate, stannous octoate, tin protochloride, diethylenetriamine, trolamine, the triethylamine; The quality of the catalyzer that adds is 0.001～10% of polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol quality.
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| CN102838717A (en) * | 2011-10-25 | 2012-12-26 | 海南大学 | Preparation of thermoplastic polyurethane elastomer with polypropylene carbonate as soft segment |
| CN103113551B (en) * | 2013-01-22 | 2014-12-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method of rosin-based shape-memory polyurethane |
| CN103665307B (en) * | 2013-12-06 | 2015-10-07 | 上海华峰材料科技研究院（有限合伙） | A kind of polyether polyols with reduced unsaturation capable of being fast degraded and its preparation method and application |
| CN105175676B (en) * | 2015-10-14 | 2018-01-02 | 中国科学院宁波材料技术与工程研究所 | Medical infusion apparatus PLA based polyurethanes elastomeric material and preparation method thereof |
| CN105294970A (en) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | Bio-based thermoplastic polyurethane elastomer material and preparation method thereof |
| CN105419676A (en) * | 2015-12-28 | 2016-03-23 | 河北华腾万富达精细化工有限责任公司 | Adhesion promoter, and preparation method and application thereof |
| NL2016526B1 (en) * | 2016-03-31 | 2017-11-02 | Polyganics Ip B V | Improved biomedical polyurethanes |
| CN107652660A (en) * | 2017-09-21 | 2018-02-02 | 安徽宏飞钓具有限公司 | It is a kind of to apply to polymer composite degradable in imitated baits |
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| NL2019652B1 (en) * | 2017-09-29 | 2019-04-08 | Polyganics Ip B V | Tissue-adhesive sealant device |
| CN110283326A (en) * | 2018-12-12 | 2019-09-27 | 杭州师范大学 | A kind of degradable modification poly (propylene carbonate) and preparation method thereof |
| CN109851744B (en) * | 2018-12-21 | 2021-02-05 | 苏州为尔康生物科技有限公司 | Degradable polyurethane biomaterial and preparation method and application thereof |
| CN111440434A (en) * | 2020-05-18 | 2020-07-24 | 新昌县同生生物技术股份有限公司 | Flame-retardant composite material of polyurethane-polylactic acid block copolymer and preparation method thereof |
| EP4328255A1 (en) | 2021-04-21 | 2024-02-28 | Asahi Kasei Kabushiki Kaisha | Polycarbonate diol composition |
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| CN100558786C (en) * | 2007-08-02 | 2009-11-11 | 同济大学 | A kind of preparation method of polylactic acid group block copolymer |
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