CN101857668B - Biodegradable polymer and preparation method thereof - Google Patents
Biodegradable polymer and preparation method thereof Download PDFInfo
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- CN101857668B CN101857668B CN 201010215724 CN201010215724A CN101857668B CN 101857668 B CN101857668 B CN 101857668B CN 201010215724 CN201010215724 CN 201010215724 CN 201010215724 A CN201010215724 A CN 201010215724A CN 101857668 B CN101857668 B CN 101857668B
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- 229920002988 biodegradable polymer Polymers 0.000 title claims abstract description 27
- 239000004621 biodegradable polymer Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 59
- -1 alcohol ester Chemical class 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 150000005690 diesters Chemical class 0.000 claims description 63
- 150000001298 alcohols Chemical class 0.000 claims description 32
- 150000007520 diprotic acids Chemical class 0.000 claims description 32
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 29
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 29
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 26
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-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
- ZKPLXWZIWFAZNZ-UHFFFAOYSA-N carbon dioxide;2-methyloxirane;7-oxabicyclo[4.1.0]heptane Chemical compound O=C=O.CC1CO1.C1CCCC2OC21 ZKPLXWZIWFAZNZ-UHFFFAOYSA-N 0.000 claims description 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 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 3
- 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 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- KEJQTHYHDVZLMT-UHFFFAOYSA-N bis(2-methylpropyl)tin Chemical compound CC(C)C[Sn]CC(C)C KEJQTHYHDVZLMT-UHFFFAOYSA-N 0.000 claims description 3
- 125000005586 carbonic acid group Chemical group 0.000 claims description 3
- 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 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 11
- 238000006065 biodegradation reaction Methods 0.000 abstract description 59
- 238000006116 polymerization reaction Methods 0.000 abstract description 32
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000004970 Chain extender Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract 3
- 230000008018 melting Effects 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 101
- 239000000126 substance Substances 0.000 description 84
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 238000004458 analytical method Methods 0.000 description 56
- 238000000034 method Methods 0.000 description 36
- 238000010792 warming Methods 0.000 description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 238000001035 drying Methods 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- 238000004448 titration Methods 0.000 description 28
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 25
- 150000002148 esters Chemical class 0.000 description 22
- 235000011089 carbon dioxide Nutrition 0.000 description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000002361 compost Substances 0.000 description 14
- 230000008021 deposition Effects 0.000 description 14
- 238000000151 deposition Methods 0.000 description 14
- 230000004927 fusion Effects 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 238000000926 separation method Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 12
- 239000001384 succinic acid Substances 0.000 description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 11
- 125000001931 aliphatic group Chemical group 0.000 description 11
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 235000005074 zinc chloride Nutrition 0.000 description 10
- 239000011592 zinc chloride Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- SVTBMSDMJJWYQN-RXMQYKEDSA-N (4r)-2-methylpentane-2,4-diol Chemical compound C[C@@H](O)CC(C)(C)O SVTBMSDMJJWYQN-RXMQYKEDSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- QEYNXBRMPSQXIG-UHFFFAOYSA-N carbon dioxide;2-methyloxirane Chemical compound O=C=O.CC1CO1 QEYNXBRMPSQXIG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides a preparation method of a biodegradable polymer, which comprises the steps: mixing carbon dioxide-epoxide copolymer with hydroxyl at both ends of the molecular chain and poly-binary acid dihydric alcohol ester with hydroxyl at both ends of the molecular chain and heating to the melting state to obtain a melting mixture; the molecular weight of the carbon dioxide-epoxide copolymer is 500-15000; the molecular weight of the poly-binary acid dihydric alcohol ester is 300-10000; and under the protection of inert gases, diisocyanate is added into the melting mixture for polymerization to obtain the biodegradable polymer. The invention also provides the biodegradable polymer which is prepared by the preparation method in the technical scheme. Compared with the prior art, the diisocyanate as the chain extender causes that the obtained biodegradable polymer has higher molecular weight and good mechanical property; simultaneously, since the cross bonding does not happen, the polymer has better biodegradation performance.
Description
Technical field
The present invention relates to the high molecular polymer technical field, relate in particular to a kind of biodegradable polymers and preparation method thereof.
Background technology
Biodegradable material is meant can be by the material of microbiological degradation such as bacterium, mould, owing to it can not cause negative impact to become the focus of research to environment.1969, aboveground auspicious the putting down with carbonic acid gas and epoxide of Japanese scientist was raw material, under the effect of catalyzer, synthesized carbonic acid gas-epoxide co-polymer (Inoue, S.; Koinuma, H.; Tsuruta, T.Makromol Chem 1969,130,210.), this carbonic acid gas epoxide co-polymer can be degraded by microorganisms fully, and the preparation process is simple, cost is lower, has a good application prospect.But characteristics such as that carbonic acid gas-epoxide co-polymer has is non-crystallizable, second-order transition temperature is lower cause mechanical properties such as the strength of materials that this multipolymer forms, toughness relatively poor, thereby have limited its application in packing, food, medicine and other fields.
In order to enlarge the range of application of carbonic acid gas-epoxide polymer as the biological degradation type material; Prior art discloses the multiple method of improving carbonic acid gas-epoxide co-polymer performance, like the carbonic acid gas and the epoxide co-polymer of synthetic macromolecule amount, compound with regular structure; Or with carbonic acid gas, epoxide and the adjustable polymkeric substance of other monomer copolymerizations formation structure composition; Or with carbonic acid gas-epoxide co-polymer and other mixed with polymers etc., these methods have improved the second-order transition temperature of polymkeric substance to a certain extent, but the mechanical property of polymkeric substance not be improved significantly.
Publication number is that to disclose a kind of be the method for feedstock production aliphatic polycarbonate type polyurethane foam materials with aliphatic polycarbonate polybasic alcohol and vulcabond or polymeric isocyanate to the Chinese patent document of CN1400229; Vulcabond or polymeric isocyanate and by carbonic acid gas and epoxide synthetic aliphatic polycarbonate polybasic alcohol polymerization reaction take place under the effect of catalyzer, whipping agent, crosslinked or chainextender, suds-stabilizing agent and other auxiliary agents; The aliphatic polycarbonate type polyurethane foam materials intensity that obtains is high, wear resistance is good; Can be used for furniture, carpet, mattress etc.; But because aliphatic polycarbonate polybasic alcohol and vulcabond or polymeric isocyanate can take place crosslinked; Make the Drawing abillity and the biodegradability that obtain all relatively poor; Be of limited application, and can have a negative impact environment.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of biodegradable polymers and preparation method thereof, and biodegradable polymers provided by the invention can be had excellent mechanical property simultaneously by biolysis.
The invention provides a kind of preparation method of biodegradable polymers, comprising:
Carbonic acid gas-the epoxide co-polymer that the molecular chain two ends is hydroxyl mixes with the diprotic acid binary alcohol esters that gathers that the molecular chain two ends are hydroxyl, is heated to molten state, obtains molten mixture; The molecular weight of said carbonic acid gas epoxide co-polymer is 500 ~ 15000, and the said molecular weight that gathers the diprotic acid binary alcohol esters is 300 ~ 10000;
Under protection of inert gas, in said molten mixture, add vulcabond and carry out polyreaction, obtain biodegradable polymers.
Preferably, said carbonic acid gas-epoxide co-polymer and said mol ratio of gathering the diprotic acid binary alcohol esters are 1:0.05 ~ 19.
Preferably, said carbonic acid gas-epoxide co-polymer is carbonic acid gas-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, carbonic acid gas-PEP-101, carbonic acid gas-epoxy cyclohexane multipolymer, carbonic acid gas-oxyethane-epoxy cyclohexane multipolymer or carbon dioxide-epoxy propane-epoxy cyclohexane multipolymer.
Preferably, the said diprotic acid binary alcohol esters that gathers is for gathering propanedioic acid second diester, gather the propanedioic acid propylene diester, gather propanedioic acid fourth diester, gather propanedioic acid penta diester, gather the own diester of propanedioic acid, gather propanedioic acid diester in heptan, poly-succinic second diester, poly-succinic propylene diester, poly-succinic fourth diester, poly-succinic penta diester, the own diester of poly-succinic, poly-succinic diester in heptan, gathering pentanedioic acid second diester, gather the pentanedioic acid propylene diester, gather pentanedioic acid fourth diester, gather pentanedioic acid penta diester, gather the own diester of pentanedioic acid, gather pentanedioic acid diester in heptan, gather hexanodioic acid second diester, gather the hexanodioic acid propylene diester, gather hexanodioic acid fourth diester, gather hexanodioic acid penta diester, polyhexamethylene adipate, gather hexanodioic acid diester in heptan, gather pimelic acid second diester, gather the pimelic acid propylene diester, gather pimelic acid fourth diester, gather pimelic acid penta diester, gather the own diester of pimelic acid or gather pimelic acid diester in heptan.
Preferably; Said vulcabond is hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, Methylcyclohexyl diisocyanate or tetramethylxylylene diisocyanate.
Preferably, the quality of said vulcabond be said carbonic acid gas-epoxide co-polymer with gather diprotic acid binary alcohol esters quality and 0.5% ~ 10%.
Add catalyzer when preferably, in said molten mixture, adding vulcabond.
Preferably, said catalyzer is stannous octoate or two LAURIC ACID 99 MIN diisobutyl tin.
Preferably, the quality of said catalyzer be said carbon dioxide copolymer with gather diprotic acid binary alcohol esters quality and 0.1 ‰ ~ 10 ‰.
The present invention also provides a kind of biodegradable polymers, and this biodegradable polymers is according to the described preparing method's preparation of technique scheme.
Compared with prior art; At first to be hydroxyl, molecular weight with the molecular chain two ends be that 300 ~ 10000 the diprotic acid binary alcohol esters that gathers mixes and is heated to molten state with to be hydroxyl, molecular weight be carbonic acid gas-epoxide co-polymer of 500 ~ 15000 at the molecular chain two ends in the present invention; Add the vulcabond polymerization reaction take place then, generate biodegradable polymkeric substance.Since carbonic acid gas-epoxide co-polymer with gather the diprotic acid binary alcohol esters and all only contain the hydroxyl that is positioned at the molecular chain two ends; Therefore; Vulcabond only has the effect of chain extension in polyreaction; It is crosslinked that polymkeric substance is taken place, thereby can not reduce the processing characteristics and the biodegradability of the polymkeric substance that obtains.Simultaneously, because the chain extension effect of vulcabond, degradable type polymericular weight provided by the invention is higher, and mechanical property is better, and experiment shows that the tensile strength of degradability polymkeric substance provided by the invention can reach 53MPa, and elongation at break can reach 255%.In addition, preparing method's technical process provided by the invention is simple, and cost is lower, is easy to suitability for industrialized production.
Embodiment
The invention provides a kind of preparation method of biodegradable polymers, comprising:
Carbonic acid gas-the epoxide co-polymer that the molecular chain two ends is hydroxyl mixes with the diprotic acid binary alcohol esters that gathers that the molecular chain two ends are hydroxyl, is heated to molten state, obtains molten mixture; The molecular weight of said carbonic acid gas-epoxide co-polymer is 500 ~ 15000, and the said molecular weight that gathers the diprotic acid binary alcohol esters is 300 ~ 10000;
Under protection of inert gas, in said molten mixture, add vulcabond and carry out polyreaction, obtain biodegradable polymers.
The present invention is the carbonic acid gas-epoxide co-polymer of hydroxyl with the molecular chain two ends and the diprotic acid binary alcohol esters that gathers that the molecular chain two ends are hydroxyl is a raw material, is chainextender with the vulcabond, obtains biodegradable polymkeric substance through frit reaction.
According to the present invention, the carbonic acid gas-epoxide co-polymer that at first the molecular chain two ends is hydroxyl mixes with the diprotic acid binary alcohol esters that gathers that the molecular chain two ends are hydroxyl, is heated to molten state, obtains molten mixture.According to the present invention, said carbonic acid gas-epoxide co-polymer and said mol ratio of gathering the diprotic acid binary alcohol esters are preferably 1:0.05 ~ 19, and more preferably 1:0.2 ~ 10 most preferably are 1:0.5 ~ 3.
Among the present invention; Carbonic acid gas-epoxide co-polymer that said molecular chain two ends are hydroxyl comprises carbonate group repeating unit and ether repeating unit; Wherein, the content of said carbonate group repeating unit is preferably 20% ~ 99% of copolymer quality, and more preferably 40% ~ 70%.In order to make the polymer degradation performance that obtains better, the molecular weight that said molecular chain two ends are the carbonic acid gas-epoxide co-polymer of hydroxyl is 500 ~ 15000, is preferably 1000 ~ 10000, more preferably 3000 ~ 8000.
According to the present invention, said carbonic acid gas-epoxide co-polymer is preferably carbonic acid gas-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, carbonic acid gas-PEP-101, carbonic acid gas-epoxy cyclohexane multipolymer, carbonic acid gas-oxyethane-epoxy cyclohexane multipolymer or carbon dioxide-epoxy propane-epoxy cyclohexane multipolymer.
The present invention does not have particular restriction to the source that said molecular chain two ends are the carbonic acid gas-epoxide co-polymer of hydroxyl, can be for buying from market, and also can be for preparing according to following steps:
Epoxide, catalyzer and molecular weight regulator are mixed in reaction kettle;
In said reaction kettle, charge into dioxide gas, under 3.5MPa ~ 5MPa, 60 ℃ ~ 100 ℃ condition, react, obtain carbonic acid gas-epoxide co-polymer that the molecular chain two ends are hydroxyl.
Said catalyzer is preferably the rare-earth ternary catalyst of zinc alkyl(s), rare-earth salts and glycerine composition or the bimetallic catalyst of potassium cobalticyanide and other metals composition.
According to the present invention; Said molecular chain two ends are the multipolymer that the diprotic acid binary alcohol esters is aliphatic dibasic acid and aliphatic dihydroxy alcohol that gathers of hydroxyl; Wherein, aliphatic dibasic acid is preferably one or more in propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid and the pimelic acid; Aliphatic dihydroxy alcohol is preferably one or more in terepthaloyl moietie, Ucar 35, butyleneglycol, pentanediol, pinakon and the heptanediol.Therefore, saidly gather that the diprotic acid binary alcohol esters includes but not limited to gather propanedioic acid second diester, gathers the propanedioic acid propylene diester, gathers propanedioic acid fourth diester, gathers propanedioic acid penta diester, gathers the own diester of propanedioic acid, gathers propanedioic acid diester in heptan, poly-succinic second diester, poly-succinic propylene diester, poly-succinic fourth diester, poly-succinic penta diester, the own diester of poly-succinic, poly-succinic diester in heptan, gather pentanedioic acid second diester, gather the pentanedioic acid propylene diester, gather pentanedioic acid fourth diester, gather pentanedioic acid penta diester, gather the own diester of pentanedioic acid, gather pentanedioic acid diester in heptan, gather hexanodioic acid second diester, gather the hexanodioic acid propylene diester, gather hexanodioic acid fourth diester, gather hexanodioic acid penta diester, polyhexamethylene adipate, gather hexanodioic acid diester in heptan, gather pimelic acid second diester, gather the pimelic acid propylene diester, gather pimelic acid fourth diester, gather pimelic acid penta diester, gather the own diester of pimelic acid, gather pimelic acid diester in heptan, poly-succinic terepthaloyl moietie succinic acid-butanediol ester and poly-succinic Ucar 35 succinic acid-butanediol ester.
In order to make the polymer degradation performance that obtains better, the molecular weight that gathers the diprotic acid binary alcohol esters that said molecular chain two ends are hydroxyl is 300 ~ 10000, is preferably 1000 ~ 8000, more preferably 3000 ~ 6000.
The present invention does not have particular restriction to the source of gathering the diprotic acid binary alcohol esters that said molecular chain two ends are hydroxyl, can be for buying from market, and also can be for according to following method preparation:
After aliphatic dibasic acid, the pure and mild catalyst mix of binary aliphatic, obtain mixture;
Heat said mixture to molten state, carry out polycondensation after the decompression, what obtain that the molecular chain two ends are hydroxyl gathers the diprotic acid binary alcohol esters.
Carbonic acid gas-the epoxide co-polymer that the molecular chain two ends is hydroxyl mixes with the diprotic acid binary alcohol esters that gathers that the molecular chain two ends are hydroxyl; Be heated to molten state; After obtaining molten mixture; Under protection of inert gas, carry out polyreaction to wherein adding vulcabond, obtain biodegradable polymkeric substance.
Said vulcabond contains two NCOs, can react with carbonic acid gas-epoxide co-polymer and the hydroxyl that gathers on the diprotic acid binary alcohol esters molecular chain, thereby play the effect of chain extension, improves the mechanical property of the polymkeric substance that obtains.Because carbonic acid gas-epoxide co-polymer all is positioned at the molecular chain two ends with the hydroxyl that gathers on the diprotic acid binary alcohol esters, thereby can not take place crosslinkedly, can not reduce the degradation property of the polymkeric substance that obtains.
According to the present invention; Said vulcabond is preferably hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1; 5-vulcabond or tetramethylxylylene diisocyanate, more preferably hexamethylene diisocyanate or tolylene diisocyanate.
According to the present invention, the consumption of said vulcabond be preferably said carbonic acid gas-epoxide co-polymer with gather diprotic acid binary alcohol esters quality and 0.5% ~ 10%, more preferably 1% ~ 8%, most preferably be 2% ~ 6%.
In order to improve the speed of said polyreaction, the present invention preferably adds catalyzer in said molten mixture when adding vulcabond.Said catalyzer is preferably stannous octoate or two LAURIC ACID 99 MIN diisobutyl tin, more preferably stannous octoates.Said catalyst consumption be preferably said carbon dioxide copolymer with gather diprotic acid binary alcohol esters quality and 0.1 ‰ ~ 10 ‰, more preferably 0.2 ‰ ~ 6 ‰.
Under the effect of catalyzer, what carbonic acid gas-epoxide co-polymer, the molecular chain two ends that the molecular chain two ends are hydroxyl were hydroxyl gathers diprotic acid binary alcohol esters and vulcabond polymerization reaction take place, obtains biodegradable polymers.According to the present invention, the temperature of said polyreaction is preferably 120 ℃ ~ 200 ℃, more preferably 150 ℃ ~ 180 ℃; The time of said polyreaction is preferably 3min ~ 180min, more preferably 10min ~ 120min.
The present invention also provides a kind of biodegradable polymers, and said biodegradable polymers is according to the described preparing method's preparation of above technical scheme.According to the present invention, the number-average molecular weight of said biodegradable polymers is preferably 35000 ~ 500000, and more preferably 50000 ~ 250000, MWD is preferably 1.5 ~ 4, and more preferably 1.5 ~ 3.5.
After obtaining degradable polymer; Method according to GB1040 provides is carried out the test of mechanical properties such as tensile strength and elongation at break to said polymkeric substance; The result shows that the tensile strength of biodegradable polymers provided by the invention, elongation at break are all higher, and mechanical property is better.
To the performance test of said degradable polymer biodegrade, the result shows that the biolysis rate of biodegradable polymers provided by the invention is all more than 70% according to the method that provides among the U.S. ASTM6400, and biodegradability is better.
In order further to understand the present invention, biodegradable polymers provided by the invention and preparation method thereof is described in detail below in conjunction with embodiment.
Embodiment 1
In the dry polymerization reaction kettle of argon shield, adding 3200g propylene oxide, 10g is that rare-earth ternary catalyst and the 120mL that sec.-propyl zinc, Tricholroacetic Acid yttrium and the glycerine of 30:1.5:10 is formed passes through the W 166 of thorough drying by mol ratio; After stirring 1h; Adding carbonic acid gas makes reaction kettle pressure reach 4MPa; Be warming up to 70 ℃ of reaction 5h, reaction mixture after deposition, separation, drying, is obtained carbon dioxide-epoxy propane copolymer; Adopt gel permeation chromatography (GPC) analysis, the number-average molecular weight of this multipolymer is 1200; Through titrimetry, the hydroxyl value of this multipolymer is 91.2; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 40wt%;
With the 3600g mol ratio is that Succinic Acid and terepthaloyl moietie and the 5g tetra-n-butyl titanate of 1:2.2 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 175 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 150MPa, continue reaction 3h, poly-succinic second two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 4500; Through titrimetry, the hydroxyl value of this oligopolymer is 22.5;
Said carbon dioxide-epoxy propane copolymer of 2400g and said poly-succinic second two ester oligomers of 9000g are joined in the reactor drum; Be warming up to 120 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 775.2g hexamethylene diisocyanate and 2.28g stannous octoate then, 120 ℃ are continued reaction 10min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 38000, and MWD is 1.9;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 35MPa, and elongation at break is 96%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 83%.
Embodiment 2
In the dry polymerization reaction kettle of argon shield, adding 3200g epoxy cyclohexane, 8g is that rare-earth ternary catalyst and the 80mL that sec.-propyl zinc, Tricholroacetic Acid yttrium and the glycerine of 30:1.5:10 is formed passes through the W 166 of thorough drying by mol ratio; After stirring 1h; Adding carbonic acid gas makes reaction kettle pressure reach 4MPa; Be warming up to 70 ℃ of reaction 5h, reaction mixture after deposition, separation, drying, is obtained carbonic acid gas-epoxy cyclohexane multipolymer; Through gpc analysis, the number-average molecular weight of this multipolymer is 2500; Through titrimetry, the hydroxyl value of this multipolymer is 43.8; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 30wt%;
With the 3600g mol ratio is that Succinic Acid and Ucar 35 and the 3g titanium isopropylate of 1:1.8 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 175 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 150MPa, continue reaction 3h, the poly-succinic propylene diester oligopolymer that obtains; Through gpc analysis, the number-average molecular weight of this oligopolymer is 4500; Through titrimetry, the hydroxyl value of this oligopolymer is 24.5;
The said carbonic acid gas of 5000g-epoxy cyclohexane multipolymer and the said poly-succinic propylene diester of 9000g oligopolymer are joined in the reactor drum; Be warming up to 120 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 588g hexamethylene diisocyanate and 2.8g stannous octoate then, 120 ℃ are continued reaction 10min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 56000, and MWD is 1.8;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 42MPa, and elongation at break is 86%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 78%.
Embodiment 3
In the dry polymerization reaction kettle of argon shield, add propylene oxide and the bimetallic catalyst of epoxy cyclohexane, 12g zinc chloride and potassium cobalticyanide composition and the W 166 of 80mL process thorough drying that the 3200g mol ratio is 1:1; After stirring 1h; Adding carbonic acid gas makes reaction kettle pressure reach 4MPa; Be warming up to 90 ℃ of reaction 2h, reaction mixture after deposition, separation, drying, is obtained carbon dioxide-epoxy propane-epoxy cyclohexane multipolymer; Through gpc analysis, the number-average molecular weight of this multipolymer is 5000; Through titrimetry, the hydroxyl value of this multipolymer is 21.9; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 35wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:1.5 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 150MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 5100; Through titrimetry, the hydroxyl value of this oligopolymer is 21.6;
The said carbon dioxide-epoxy propane of 5000g-epoxy cyclohexane multipolymer and said poly-succinic fourth two ester oligomers of 5100g are joined in the reactor drum; Be warming up to 120 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 585.8g hexamethylene diisocyanate and 5.05g stannous octoate then, 120 ℃ are continued reaction 10min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 61000, and MWD is 1.9;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 46MPa, and elongation at break is 87%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 75%.
Embodiment 4
In the dry polymerization reaction kettle of argon shield, add propylene oxide and the bimetallic catalyst of epoxy hexane, 13g zinc chloride and potassium cobalticyanide composition and the W 166 of 60mL process thorough drying that the 3200g mol ratio is 1:1; After stirring 1h; Adding carbonic acid gas makes reaction kettle pressure reach 4MPa; Be warming up to 90 ℃ of reaction 2h, reaction mixture after deposition, separation, drying, is obtained carbon dioxide-epoxy propane-epoxy cyclohexane multipolymer; Through gpc analysis, the number-average molecular weight of this multipolymer is 3500; Through titrimetry, the hydroxyl value of this multipolymer is 31.6; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 32wt%;
With the 3600g mol ratio is that hexanodioic acid and terepthaloyl moietie and the 8g stannous octoate of 1:1.8 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, what obtain gathers hexanodioic acid second two ester oligomers; Through gpc analysis, the number-average molecular weight of this oligopolymer is 5500; Through titrimetry, the hydroxyl value of this oligopolymer is 20.0;
Said carbon dioxide-epoxy propane-ethylene oxide copolymer of 3500g and said hexanodioic acid second two ester oligomers that gather of 5500g are joined in the reactor drum; Be warming up to 120 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 504g hexamethylene diisocyanate and 10.8g stannous octoate then, be warming up to 160 ℃ and continue reaction 30min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 70000, and MWD is 2.1;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 48MPa, and elongation at break is 125%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 75%.
Embodiment 5
In the dry polymerization reaction kettle of argon shield, adding 3200g propylene oxide, 6g is that rare-earth ternary catalyst and the 50mL that sec.-propyl zinc, Tricholroacetic Acid yttrium and the glycerine of 30:1.5:10 is formed passes through the W 166 of thorough drying by mol ratio; After stirring 1h; Adding carbonic acid gas makes reaction kettle pressure reach 4MPa; Be warming up to 90 ℃ of reaction 6h, reaction mixture after deposition, separation, drying, is obtained carbon dioxide-epoxy propane copolymer; Adopt gel permeation chromatography (GPC) analysis, the number-average molecular weight of this multipolymer is 8000; Through titrimetry, the hydroxyl value of this multipolymer is 13.5; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 25wt%;
With the 3600g mol ratio is that hexanodioic acid and butyleneglycol and the 8g stannous octoate of 1:1.8 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 175 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, what obtain gathers hexanodioic acid fourth two ester oligomers; Through gpc analysis, the number-average molecular weight of this oligopolymer is 8000; Through titrimetry, the hydroxyl value of this oligopolymer is 13.8;
Said carbon dioxide-epoxy propane copolymer of 8000g and said hexanodioic acid fourth two ester oligomers that gather of 8000g are joined in the reactor drum; Be warming up to 140 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 352g hexamethylene diisocyanate and 3.2g stannous octoate then, be warming up to 160 ℃ and continue reaction 20min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 58000, and MWD is 1.7;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 43MPa, and elongation at break is 143%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 72%.
Embodiment 6
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g propylene oxide, 10g zinc chloride and potassium cobalticyanide composition and the W 166 of 60mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbon dioxide-epoxy propane copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 3500; Through titrimetry, the hydroxyl value of this multipolymer is 31.6; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 30wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:1.6 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 4500; Through titrimetry, the hydroxyl value of this oligopolymer is 24.2;
Said carbon dioxide-epoxy propane copolymer of 7000g and said poly-succinic fourth two ester oligomers of 4500g are joined in the reactor drum; Be warming up to 140 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add the 460g hexamethylene diisocyanate then, be warming up to 160 ℃ and continue reaction 60min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 108000, and MWD is 1.9;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 52MPa, and elongation at break is 145%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 71%.
Embodiment 7
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g propylene oxide, 10g zinc chloride and potassium cobalticyanide composition and the W 166 of 60mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbon dioxide-epoxy propane copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 3500; Through titrimetry, the hydroxyl value of this multipolymer is 31.6; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 30wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:1.6 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 4500; Through titrimetry, the hydroxyl value of this oligopolymer is 24.2;
Said carbon dioxide-epoxy propane copolymer of 7000g and said poly-succinic fourth two ester oligomers of 4500g are joined in the reactor drum; Be warming up to 140 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add the 460g hexamethylene diisocyanate then, be warming up to 160 ℃ and continue reaction 120min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 185000, and MWD is 2.2;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 51MPa, and elongation at break is 180%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 77%.
Embodiment 8
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g propylene oxide, 12g zinc chloride and potassium cobalticyanide composition and the W 166 of 80mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbon dioxide-epoxy propane copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 5000; Through titrimetry, the hydroxyl value of this multipolymer is 21.8; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 35wt%;
With the 3600g mol ratio is that Succinic Acid and glycol and the 8g stannous octoate of 1:1.4 joins in the 5L polymerization reaction kettle, and said glycol is that mol ratio is butyleneglycol and the terepthaloyl moietie of 1:1; After in reaction kettle, feeding nitrogen replacement oxygen wherein; When stirring reaction kettle is heated to 170 ℃, when aquifer yield reaches theoretical aquifer yield, temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa; Continue reaction 3h; The poly-succinic terepthaloyl moietie succinic acid-butanediol ester oligopolymer that obtains, through gpc analysis, the number-average molecular weight of this oligopolymer is 6000; Through titrimetry, the hydroxyl value of this oligopolymer is 18.1;
Said carbon dioxide-epoxy propane copolymer of 5000g and the said poly-succinic terepthaloyl moietie of 6000g succinic acid-butanediol ester oligopolymer are joined in the reactor drum; Be warming up to 140 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 495g '-diphenylmethane diisocyanate and 6.6g dibutyl tin laurate then, be warming up to 160 ℃ and continue reaction 60min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 98000, and MWD is 1.9;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 47MPa, and elongation at break is 132%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 75%.
Embodiment 9
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g propylene oxide, 12g zinc chloride and potassium cobalticyanide composition and the W 166 of 80mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbon dioxide-epoxy propane copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 5000; Through titrimetry, the hydroxyl value of this multipolymer is 21.8; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 35wt%;
With the 3600g mol ratio is that Succinic Acid and glycol and the 8g stannous octoate of 1:1.6 joins in the 5L polymerization reaction kettle, and said glycol is that mol ratio is butyleneglycol and the Ucar 35 of 1:1; After in reaction kettle, feeding nitrogen replacement oxygen wherein; When stirring reaction kettle is heated to 170 ℃, when aquifer yield reaches theoretical aquifer yield, temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa; Continue reaction 3h; The poly-succinic Ucar 35 succinic acid-butanediol ester oligopolymer that obtains, through gpc analysis, the number-average molecular weight of this oligopolymer is 5000; Through titrimetry, the hydroxyl value of this oligopolymer is 21.9;
Said carbon dioxide-epoxy propane copolymer of 5000g and the said poly-succinic Ucar 35 of 5000g succinic acid-butanediol ester oligopolymer are joined in the reactor drum; Be warming up to 180 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 600g hexamethylene diisocyanate and 9g stannous octoate then, be cooled to 140 ℃ and continue reaction 60min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 89000, and MWD is 2.3;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 45MPa, and elongation at break is 106%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 76%.
Embodiment 10
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g oxyethane, 15g zinc chloride and potassium cobalticyanide composition and the W 166 of 160mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbonic acid gas-ethylene oxide copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 580; Through titrimetry, the hydroxyl value of this multipolymer is 189.6; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 54wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:3.8 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 350; Through titrimetry, the hydroxyl value of this oligopolymer is 318.5;
Said carbonic acid gas-ethylene oxide copolymer of 580g and said poly-succinic fourth two ester oligomers of 3150g are joined in the reactor drum; Be warming up to 160 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 373g tolylene diisocyanate and 3.0g stannous octoate then, be cooled to 140 ℃ and continue reaction 170min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 471000, and MWD is 2.9;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 53MPa, and elongation at break is 255%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 70%.
Embodiment 11
The oxyethane that in the dry polymerization reaction kettle of argon shield, adds the 3200g mol ratio and be 1:1 and epoxy cyclohexane, 8g are that rare-earth ternary catalyst and the 20mL that sec.-propyl zinc, Tricholroacetic Acid yttrium and the glycerine of 30:1.5:10 is formed passes through the W 166 of thorough drying by mol ratio; After stirring 1h; Adding carbonic acid gas makes reaction kettle pressure reach 4MPa; Be warming up to 60 ℃ of reaction 8h, reaction mixture after deposition, separation, drying, is obtained carbonic acid gas-oxyethane-epoxy cyclohexane multipolymer; Adopt gel permeation chromatography (GPC) analysis, the number-average molecular weight of this multipolymer is 15000; Through titrimetry, the hydroxyl value of this multipolymer is 7.1; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 20wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:1.4 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 245 ℃, pressure slowly reduce to 80MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 9500; Through titrimetry, the hydroxyl value of this oligopolymer is 11.1;
4500g institute carbonic acid gas-oxyethane-epoxy cyclohexane multipolymer and said poly-succinic fourth two ester oligomers of 950g are joined in the reactor drum; Be warming up to 160 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 436g tolylene diisocyanate and 5.45g stannous octoate then, be cooled to 140 ℃ and continue reaction 120min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 203000, and MWD is 2.8;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 48MPa, and elongation at break is 190%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 76%.
Embodiment 12
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g propylene oxide, 10g zinc chloride and potassium cobalticyanide composition and the W 166 of 60mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbon dioxide-epoxy propane copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 3500; Through titrimetry, the hydroxyl value of this multipolymer is 31.6; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 30wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:1.6 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 4500; Through titrimetry, the hydroxyl value of this oligopolymer is 23.1;
Said carbon dioxide-epoxy propane copolymer of 10500g and said poly-succinic fourth two ester oligomers of 4500g are joined in the reactor drum; Be warming up to 160 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 1080g dicyclohexyl methane diisocyanate and 7.5g stannous octoate then, be cooled to 140 ℃ and continue reaction 60min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 103000, and MWD is 2.1;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 42MPa, and elongation at break is 150%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 73%.
Embodiment 13
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g propylene oxide, 10g zinc chloride and potassium cobalticyanide composition and the W 166 of 60mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbon dioxide-epoxy propane copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 3500; Through titrimetry, the hydroxyl value of this multipolymer is 31.6; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 30wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:1.6 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 4500; Through titrimetry, the hydroxyl value of this oligopolymer is 23.1;
Said carbon dioxide-epoxy propane copolymer of 3150g and said poly-succinic fourth two ester oligomers of 450g are joined in the reactor drum; Be warming up to 120 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 270g hexamethylene diisocyanate and 0.72g stannous octoate then, be warming up to 150 ℃ and continue reaction 90min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 113000, and MWD is 2.2;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 48MPa, and elongation at break is 82%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 73%.
Embodiment 14
In the dry polymerization reaction kettle of argon shield, add the bimetallic catalyst of 3200g propylene oxide, 10g zinc chloride and potassium cobalticyanide composition and the W 166 of 60mL process thorough drying; After stirring 1h, add carbonic acid gas and make reaction kettle pressure reach 4MPa, be warming up to 90 ℃ of reaction 2h; With reaction mixture after deposition, separation, drying; Obtain carbon dioxide-epoxy propane copolymer, through gpc analysis, the number-average molecular weight of this multipolymer is 3500; Through titrimetry, the hydroxyl value of this multipolymer is 31.6; Through the hydrogen nuclear magnetic resonance spectrum analysis, the ether section content of this multipolymer is 30wt%;
With the 3600g mol ratio is that Succinic Acid and butyleneglycol and the 8g stannous octoate of 1:1.6 joins in the 5L polymerization reaction kettle, in reaction kettle, feed nitrogen replacement oxygen wherein after, in the time of stirring reaction kettle is heated to 170 ℃; When aquifer yield reaches theoretical aquifer yield; Temperature of reaction kettle is risen to 235 ℃, pressure slowly reduce to 100MPa, continue reaction 3h, poly-succinic fourth two ester oligomers that obtain; Through gpc analysis, the number-average molecular weight of this oligopolymer is 4500; Through titrimetry, the hydroxyl value of this oligopolymer is 23.1;
Said carbon dioxide-epoxy propane copolymer of 3500g and said poly-succinic fourth two ester oligomers of 4500g are joined in the reactor drum; Be warming up to 140 ℃ under the nitrogen protection; It is even to be stirred to fusion; Add 320g hexamethylene diisocyanate and 2g stannous octoate then, be warming up to 160 ℃ and continue reaction 150min, obtain the polymkeric substance of biodegradation type.
With the methylene dichloride is solvent, and said biodegradation type polymkeric substance is carried out gpc analysis, and its number-average molecular weight is 25500, and MWD is 2.6;
Polymkeric substance to said biodegradation type carries out Mechanics Performance Testing, and its tensile strength is 56MPa, and elongation at break is 120%;
According to the method that provides among the U.S. ASTM6400 polymkeric substance of said biodegradation type is carried out the compost degraded, degradation time is 90 days, and the biolysis rate that records this polymkeric substance is 78%.
Can be known that by the foregoing description biodegradation type polymkeric substance provided by the invention has higher draw tensile strength and elongation at break, mechanical property is better; Simultaneously, the biolysis rate of biodegradation type polymkeric substance provided by the invention is more than 70%, and biological degradability is better.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (11)
1. the preparation method of a biodegradable polymers comprises:
Carbonic acid gas-the epoxide co-polymer that the molecular chain two ends is hydroxyl mixes with the diprotic acid binary alcohol esters that gathers that the molecular chain two ends are hydroxyl, is heated to molten state, obtains molten mixture; The number-average molecular weight of said carbonic acid gas-epoxide co-polymer is 500 ~ 15000, and said number-average molecular weight of gathering the diprotic acid binary alcohol esters is 300 ~ 10000;
Under protection of inert gas, in said molten mixture, add vulcabond and carry out polyreaction, obtain biodegradable polymers.
2. preparation method according to claim 1 is characterized in that, said carbonic acid gas-epoxide co-polymer and said mol ratio of gathering the diprotic acid binary alcohol esters are 1:0.05 ~ 19.
3. preparation method according to claim 1; It is characterized in that said carbonic acid gas-epoxide co-polymer is carbonic acid gas-ethylene oxide copolymer, carbon dioxide-epoxy propane copolymer, carbonic acid gas-PEP-101, carbonic acid gas-epoxy cyclohexane multipolymer, carbonic acid gas-oxyethane-epoxy cyclohexane multipolymer or carbon dioxide-epoxy propane-epoxy cyclohexane multipolymer.
4. preparation method according to claim 1; It is characterized in that the said diprotic acid binary alcohol esters that gathers is for gathering propanedioic acid second diester, gather the propanedioic acid propylene diester, gather propanedioic acid fourth diester, gather propanedioic acid penta diester, gather the own diester of propanedioic acid, gather propanedioic acid diester in heptan, poly-succinic second diester, poly-succinic propylene diester, poly-succinic fourth diester, poly-succinic penta diester, the own diester of poly-succinic, poly-succinic diester in heptan, gathering pentanedioic acid second diester, gather the pentanedioic acid propylene diester, gather pentanedioic acid fourth diester, gather pentanedioic acid penta diester, gather the own diester of pentanedioic acid, gather pentanedioic acid diester in heptan, gather hexanodioic acid second diester, gather the hexanodioic acid propylene diester, gather hexanodioic acid fourth diester, gather hexanodioic acid penta diester, polyhexamethylene adipate, gather hexanodioic acid diester in heptan, gather pimelic acid second diester, gather the pimelic acid propylene diester, gather pimelic acid fourth diester, gather pimelic acid penta diester, gather the own diester of pimelic acid or gather pimelic acid diester in heptan.
5. preparation method according to claim 1; It is characterized in that; Said vulcabond is hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond or tetramethylxylylene diisocyanate.
6. preparation method according to claim 1 is characterized in that, the quality of said vulcabond be said carbonic acid gas-epoxide co-polymer with gather diprotic acid binary alcohol esters quality and 0.5% ~ 10%.
7. preparation method according to claim 1 is characterized in that, adds catalyzer when in said molten mixture, adding vulcabond.
8. preparation method according to claim 7 is characterized in that, said catalyzer is stannous octoate or two LAURIC ACID 99 MIN diisobutyl tin.
9. preparation method according to claim 7 is characterized in that, the quality of said catalyzer be said carbonic acid gas-epoxide co-polymer with gather diprotic acid binary alcohol esters quality and 0.1 ‰ ~ 10 ‰.
10. according to any biodegradable polymers that described preparation method prepares of claim 1 ~ 9.
11. the preparation method of a biodegradable polymers comprises:
Carbonic acid gas-the epoxide co-polymer that the molecular chain two ends is hydroxyl mixes with the diprotic acid binary alcohol esters that gathers that the molecular chain two ends are hydroxyl, is heated to molten state, obtains molten mixture; The number-average molecular weight of said carbonic acid gas-epoxide co-polymer is 500 ~ 15000, and said number-average molecular weight of gathering the diprotic acid binary alcohol esters is 300 ~ 10000;
Under protection of inert gas, in said molten mixture, add poly methylene poly phenyl poly isocyanate and carry out polyreaction, obtain biodegradable polymers.
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