CN102002142A - Biodegradable polyurethane and preparation method thereof - Google Patents
Biodegradable polyurethane and preparation method thereof Download PDFInfo
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- CN102002142A CN102002142A CN 201010288729 CN201010288729A CN102002142A CN 102002142 A CN102002142 A CN 102002142A CN 201010288729 CN201010288729 CN 201010288729 CN 201010288729 A CN201010288729 A CN 201010288729A CN 102002142 A CN102002142 A CN 102002142A
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- diisocyanate
- block copolymer
- polylactic acid
- acid block
- polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 22
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 73
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 50
- 239000004626 polylactic acid Substances 0.000 claims abstract description 46
- 229920001400 block copolymer Polymers 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 3
- 150000002009 diols Chemical class 0.000 claims abstract 11
- 229920001281 polyalkylene Polymers 0.000 claims abstract 11
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract 2
- 238000002347 injection Methods 0.000 claims abstract 2
- 239000007924 injection Substances 0.000 claims abstract 2
- 238000005086 pumping Methods 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 102
- -1 polyethylene carbonate Polymers 0.000 claims description 71
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 6
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 1
- VRPBIOFOAXOJIS-UHFFFAOYSA-N ethene Chemical group C=C.C=C.C=C.C=C VRPBIOFOAXOJIS-UHFFFAOYSA-N 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 45
- 238000001035 drying Methods 0.000 description 22
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 17
- 238000001914 filtration Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 7
- DFFDSQBEGQFJJU-UHFFFAOYSA-N butyl hydrogen carbonate Chemical compound CCCCOC(O)=O DFFDSQBEGQFJJU-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- UOSMUCBDKZXJBL-UHFFFAOYSA-N butane-1,1-diol;carbonic acid Chemical compound OC(O)=O.CCCC(O)O UOSMUCBDKZXJBL-UHFFFAOYSA-N 0.000 description 1
- WNPMPFBJTYCQEL-UHFFFAOYSA-N carbonic acid;ethyl carbamate Chemical compound OC(O)=O.CCOC(N)=O WNPMPFBJTYCQEL-UHFFFAOYSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical group OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000004102 tricarboxylic acid cycle Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种可生物降解聚氨酯及其制备方法。本发明的聚氨酯由聚碳酸亚烷酯-聚乳酸嵌段共聚物二醇、二异氰酸酯、扩链剂共聚而成，分子量为10000～1000000g/mol。该聚氨酯的制备方法是：将干燥的聚碳酸亚烷酯-聚乳酸嵌段共聚物二醇加入溶剂中溶解，加入二异氰酸酯；重复抽真空后充氮操作5～10次，最后一次通入氮气后保持压强为0.05～0.5MPa；在60～180℃温度下回流0.1～24h，然后加入扩链剂，再重复抽真空后充氮操作5～10次，最后一次通入氮气后保持压强为0.05～0.5MPa，继续反应0.1～24h，产物经沉淀处理后过滤干燥，得到目标产物。本发明方法反应平稳易控制，制备的聚氨酯具有良好的生物降解性能。The invention relates to a biodegradable polyurethane and a preparation method thereof. The polyurethane of the invention is formed by copolymerization of polyalkylene carbonate-polylactic acid block copolymer diol, diisocyanate and chain extender, and has a molecular weight of 10,000-1,000,000 g/mol. The preparation method of the polyurethane is as follows: adding the dry polyalkylene carbonate-polylactic acid block copolymer diol into the solvent to dissolve, adding diisocyanate; repeating the vacuum pumping and nitrogen filling operation for 5 to 10 times, and nitrogen gas for the last time Finally, keep the pressure at 0.05-0.5MPa; reflux at 60-180°C for 0.1-24 hours, then add chain extender, repeat the vacuuming and nitrogen filling operation for 5-10 times, and keep the pressure at 0.05 after the last nitrogen injection ～0.5MPa, continue to react for 0.1～24h, the product is filtered and dried after precipitation treatment, and the target product is obtained. The reaction of the method of the invention is stable and easy to control, and the prepared polyurethane 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 a class aliphatic polycarbonate has the favorable biological degradability energy.Wherein, the poly (propylene carbonate) polyvalent alcohol is telomerized under catalyst action by carbonic acid gas and propylene oxide and obtains, it is one of main raw material of production PAUR, the polyurethane elastomer stable chemical performance of making by it, has good machining property, wear-resisting, oil resistant, low temperature resistant, hydrolysis, and hydrolytic resistance is higher than conventional polyester, 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 synthesizing polymerized thylene carbonate urethane elastomer (CN 1865311A) by polymerized thylene carbonate ethyl ester glycol and vulcabond, be that the polycarbonate polyurethane elastomerics that the synthetic class of raw material has good biological property (thanks to emerging beneficial Liu Fang and for example with poly-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 elastomerics (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 (poly(lactic acid)) is a kind of aliphatic polyester, and it derives from Biological resources, can be degraded fully by microorganism again in environment, 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 poly(lactic acid) is nontoxic, has excellent biological compatibility, thereby in human body, can be biodegradable into lactic acid and enter tricarboxylic acid cycle, eventual degradation is that carbonic acid gas and water are discharged behind eubolism, therefore, poly(lactic acid) is widely used in aspects such as operating sutures, 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, therefore the elastomerics that 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 is
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 poly(lactic acid) is one or both the mixing in L type poly(lactic acid), the D type poly(lactic 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, ethylene glycol, glycol ether, 1,6-hexylene glycol, 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; 0.1～the 24h that refluxes under 60～180 ℃ of temperature adds chainextender then, and 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 obtains target urethane through precipitation process after-filtration drying.
Described solvent is a kind of in trichloromethane, toluene, acetone, tetrahydrofuran (THF) and the dimethyl formamide; 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 poly(lactic acid) section can both be by biological degradation, therefore urethane of the present invention also has the favorable biological degradability energy.Experiment showed, urethane of the present invention under composting conditions in three months its relative biological decomposition rate surpass 90%.The present invention prepares urethane by solution method, and reacting balance is easy to control, can regulate the soft or hard section content of final product by 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; 60 ℃ of backflow 0.1h heat up, add chainextender 1 then, the 4-butyleneglycol, 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 10Kg/mol, molecular weight distribution 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 1000Kg/mol, molecular weight distribution 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 (poly(lactic acid) in the segmented copolymer glycol partly is D type poly(lactic acid) for L type poly(lactic 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; 100 ℃ of backflow 3h heat up, add chainextender ethylene glycol then, 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 130Kg/mol, molecular weight distribution 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 tetrahydrofuran (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; 80 ℃ of backflow 10h heat up, add the chainextender glycol ether then, 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 280Kg/mol, molecular weight distribution 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 dimethyl formamide 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; 180 ℃ of backflow 24h heat up, add chainextender 1 then, the 6-hexylene glycol, 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 80Kg/mol, molecular weight distribution 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, poly(lactic acid) partly for L type poly(lactic acid), part for D type poly(lactic 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; 120 ℃ of backflow 2h heat up, add the chainextender TriMethylolPropane(TMP) then, 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 90Kg/mol, molecular weight distribution 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; 160 ℃ of backflow 8h heat up, add chainextender quinhydrones-two (beta-hydroxyethyl) ether then, 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 110Kg/mol, molecular weight distribution 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 the polymerized thylene carbonate ethyl ester for polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol of 34000g/mol, part is a poly (propylene carbonate), part is the polymerized thylene carbonate butyl ester, poly(lactic acid) partly is a L type poly(lactic acid), part is for D type poly(lactic 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; 90 ℃ of backflow 16h heat up, add chainextender 1 then, the 4-butyleneglycol, 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 through precipitation process after-filtration drying, and finally obtaining molecular weight is that 400Kg/mol, molecular weight distribution 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, poly(lactic acid) partly for L type poly(lactic acid), part for D type poly(lactic acid)) put into the 250ml reaction flask that the 100ml dimethyl formamide 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, fill nitrogen operation 9 times after repeating again to vacuumize, keeping pressure behind the last feeding nitrogen is 0.45MPa, continue reaction 9h, product is through precipitation process after-filtration drying, and finally obtaining molecular weight is that 680Kg/mol, molecular weight distribution 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, poly(lactic acid) partly for L type poly(lactic acid), part for D type poly(lactic 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 ethylene glycol then, the mole number of its adding is mole number poor of TMXDI and polymerized thylene carbonate alkane ester-polylactic-acid block copolymer glycol, fill nitrogen operation 8 times after repeating again to vacuumize, keeping pressure behind the last feeding nitrogen is 0.1MPa, continue reaction 23h, product is through precipitation process after-filtration drying, and finally obtaining molecular weight is that 59Kg/mol, molecular weight distribution are 1.72 urethane.
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