CN110305303A - A kind of preparation method of degradable biological base polyester of the side chain containing double bond functional group - Google Patents
A kind of preparation method of degradable biological base polyester of the side chain containing double bond functional group Download PDFInfo
- Publication number
- CN110305303A CN110305303A CN201910669460.6A CN201910669460A CN110305303A CN 110305303 A CN110305303 A CN 110305303A CN 201910669460 A CN201910669460 A CN 201910669460A CN 110305303 A CN110305303 A CN 110305303A
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- China
- Prior art keywords
- methylene
- gamma
- alpha
- butyrolactone
- highly basic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title abstract description 7
- 125000000524 functional group Chemical group 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title description 10
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene gamma-butyrolactone Chemical compound C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003426 co-catalyst Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- -1 methoxyl group Chemical group 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229950009195 phenylpropanol Drugs 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- NYLOEXLAXYHOHH-UHFFFAOYSA-N 2,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(CO)C1=CC=CC=C1 NYLOEXLAXYHOHH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005808 2,4,6-trimethoxyphenyl group Chemical group [H][#6]-1=[#6](-[#8]C([H])([H])[H])-[#6](-*)=[#6](-[#8]C([H])([H])[H])-[#6]([H])=[#6]-1-[#8]C([H])([H])[H] 0.000 claims description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000003013 cytotoxicity Effects 0.000 abstract description 2
- 231100000135 cytotoxicity Toxicity 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000005311 nuclear magnetism Effects 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000004224 protection Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N 1,3-di(propan-2-yl)urea Chemical compound CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- PSDWMGVIITUJIB-UHFFFAOYSA-N 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylurea Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(NC(=O)NC2CCCCC2)=C1 PSDWMGVIITUJIB-UHFFFAOYSA-N 0.000 description 1
- PASBFQMDQRGJBH-UHFFFAOYSA-N 1-cyclohexyl-3-phenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1CCCCC1 PASBFQMDQRGJBH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
- 125000004171 alkoxy aryl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- PMMYEEVYMWASQN-UHFFFAOYSA-N dl-hydroxyproline Natural products OC1C[NH2+]C(C([O-])=O)C1 PMMYEEVYMWASQN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229960002591 hydroxyproline Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention provides a kind of polymerization of alpha-methylene-gamma-butyrolactone selective opening, the method for preparing poly- (alpha-methylene-gamma-butyrolactone).The ring-opening polymerisation for the binary catalyst system catalysis alpha-methylene-gamma-butyrolactone that the present invention is formed using highly basic and co-catalyst.Method provided by the invention is compared with previously reported method, with following usefulness: 1) highly basic used in and co-catalyst toxicity are low, and it is easy to remove from product, experiments have shown that products therefrom can be used in biomedicine field without obvious cytotoxicity；2) selectivity of catalyst system used in is high, can be realized the selective opening polymerization of alpha-methylene-gamma-butyrolactone, completely retains double bond functional group, and gained polyester product can regulate and control its physicochemical properties by rear modification.
Description
Technical field
The present invention relates to high molecular material and chemical fields, in particular it relates to a kind of poly- (alpha-methylene-
Gamma-butyrolacton) preparation method.
Background technique
Due to petroleum resources it is continuous consumption and environmental pollution is getting worse, renewable polymeric materials are in recent years
Receive the extensive concern of academia and industry.Common renewable polymeric materials include polycaprolactone, polylactic acid, poly- second
Alkyd, polyhydroxyalkanoate etc..Although these renewable polymeric materials, can also be with using natural reproducible biomass as raw material
It degrades in a natural environment, but its degradation generally produces carbon dioxide and water, recycling and reusing can not be carried out to raw material, be pair
The significant wastage of resource.
Solve the problems, such as a kind of means that high molecular material recycles for the recyclable high molecular material of preparation chemistry.Chemistry can
Recycling high molecular material refers to the height that monomer degradable can be obtained under relatively mild reaction condition and lower energy consumption condition
Molecular material.It is still less for the research of this kind of high molecular material at present, this kind of only poly- (γ-fourth of material reported in the literature
Lactone), poly- (trans- hexahydro benzofuran -1 (3H) ketone), poly- (alpha-methylene-gamma-butyrolactone), derived from 4- hydroxy-proline
Several (Nat.Chem.2016,8,42-49 of polysulfide lactones；Science 2018,360,398-403；
J.Am.Chem.Soc.2016,138,14326-14337；J.Am.Chem.Soc.2019,141,4928-4935).Wherein, gather
(alpha-methylene-gamma-butyrolactone) is a kind of important polyester material.Monomer alpha-methylene-gamma-butyrolactone is also referred to as Radix Curcumae
Fragrant spirit A, mass production can obtain from biomass material.On the other hand, compared with existing common polyester material, poly- (α-Asia
Methyl-gamma-butyrolactone) other than with degradable polyester backbone structure, side chain contains double bond functional group, repairs after can passing through
The method of decorations is modified it, regulates and controls physicochemical properties.However, most of document only reports alpha-methylene-γ-at present
Butyrolactone obtains the polymer that main chain is carbon-carbon bond by double bond sudden reaction, and only document report is poly- by open loop
The method of conjunction be prepared main chain be ester bond poly- (alpha-methylene-gamma-butyrolactone) (J.Am.Chem.Soc.2016,138,
14326-14337).Lanthanum or yttrium metal complex catalysts have been used in this method.However, transition-metal catalyst is poly-
Residual in ester products will cause stronger bio-toxicity, to its biomedicine field application be unfavorable.
In view of this, realizing α-methylene the present invention provides the binary catalyst system that a kind of highly basic and co-catalyst form
Base-gamma-butyrolacton selective opening polymerization, prepares the new method of poly- (alpha-methylene-gamma-butyrolactone).Side provided by the invention
Method is compared with previously reported method, and have following usefulness: 1) highly basic used in and co-catalyst bio-toxicity are low, and
And be easy to remove from product, experiments have shown that products therefrom can be used in biomedicine field without obvious cytotoxicity；2) used
Catalyst system selectivity is high, can be realized the selective opening polymerization of alpha-methylene-gamma-butyrolactone, complete to retain double bond function
Group, gained polyester product can regulate and control its physicochemical properties by rear modification.
Summary of the invention
The object of the present invention is to provide a kind of polymerizations of alpha-methylene-gamma-butyrolactone selective opening, prepare poly- (α-methylene
Base-gamma-butyrolacton) method, include the following steps:
(1) initiator, highly basic and co-catalyst are dissolved in organic solvent, at low temperature stirring a period of time；
(2) alpha-methylene-gamma-butyrolactone is added in above-mentioned mixed solution, at a certain temperature reaction a period of time, is added
Enter acidic materials and terminate reaction, precipitating in methanol is added in reaction mixture and obtains poly- (alpha-methylene-gamma-butyrolactone).
In above-mentioned preparation method, shown in the chemical structural formula such as formula (I) of poly- (alpha-methylene-gamma-butyrolactone):
It is characterized in that, n is the natural number more than or equal to 5, R1For hydroxyl, alkoxy or alkoxy aryl, concretely
Hydroxyl, methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, benzyloxy, phenyl ethoxy, phenyl-propoxy, diphenyl methoxy
Base, 2,2- hexichol base oxethyl.
In above-mentioned preparation method, the co-catalyst is at least one of urea or thiocarbamide, and wherein urea is shown in formula (II)
Compound, thiocarbamide are compound shown in formula (III), R3And R4Be respectively and independently selected from alkyl or aryl, specifically may respectively be methyl,
Ethyl, propyl, isopropyl, cyclohexyl, phenyl, 4- chlorphenyl, 4- methoxyphenyl, 4- trifluoromethyl, the bis- (trifluoros of 3,5-
Methyl) phenyl, 2,6- 3,5-dimethylphenyl, 2,4- Dimethoxyphenyl, 2,4,6- trimethoxyphenyl.
According to an embodiment of the invention, the urea or thiocarbamide have one of following structure:
In above-mentioned preparation method, initiator described in step (1) is alcohol, concretely methanol, ethyl alcohol, isopropanol, tertiary fourth
Alcohol, benzylalcohol, benzyl carbinol, phenylpropanol, benzohydrol, 2,2- diphenyl ethyl alcohol, ethylene glycol, 1,4- phenyl dimethanol, glycerine,
Pentaerythrite；The highly basic can be alkali metal, alkali metal compound or organic phosphonitrile base catalyst, concretely sodium, potassium, hydrogenation
Potassium, sodium hydride, six [three (dimethyl amine) phosphorus nitrence] tripolyphosphazene ({ [(NMe2)3P=N]2P=N }3), phosphonitrile ligand uncle P4-
Butyl ([(NMe2)3P=N]3P=NtBu, tert-Bu-P4), phosphonitrile ligand P2- tert-butyl ([(NMe2)3P=N] (NMe2)2P=
NtBu, tert-Bu-P2)；The molar ratio of the highly basic and initiator is 1/3~20/1；The molar ratio of the highly basic and urea
It is 1/1~1/10.
In above-mentioned preparation method, low temperature described in step (1) is -70~-10 DEG C；The mixing time be 10min extremely
30min；The organic solvent can be toluene, tetrahydrofuran, methylene chloride, acetonitrile, N,N-dimethylformamide.
In above-mentioned preparation method, reaction temperature described in step (2) is -70~-20 DEG C；The reaction time be 0.5~
48h, molar concentration of the alpha-methylene-gamma-butyrolactone in system are 4~11mol/L, the initiator and α-methylene
Base-gamma-butyrolacton molar ratio is 1/10~1/3000.
In above-mentioned preparation method, the acidic materials are acetic acid, benzoic acid, hydrochloric acid, sulfuric acid, phosphoric acid, the acidic materials
Molar ratio with highly basic is 1/1~10/1.
Detailed description of the invention
Fig. 1 is alpha-methylene-gamma-butyrolactone polyaddition products obtained in comparative example 11H NMR spectra.
Fig. 2 is poly- (alpha-methylene-gamma-butyrolactone) obtained in embodiment 11H NMR spectra.
Fig. 3 is poly- (alpha-methylene-gamma-butyrolactone) obtained in embodiment 113C NMR spectra.
Fig. 4 is the GPC spectrogram of poly- (alpha-methylene-gamma-butyrolactone) made from embodiment 1 to embodiment 4.
It is 10 DEG C/min that Fig. 5, which is (alpha-methylene-gamma-butyrolactone) poly- made from embodiment 1 to embodiment 4 in sweep speed,
When
DSC spectrogram.
Fig. 6 is poly- (alpha-methylene-gamma-butyrolactone) obtained in embodiment 51H NMR spectra.
Fig. 7 is poly- (alpha-methylene-gamma-butyrolactone) obtained in embodiment 61H NMR spectra.
Fig. 8 is poly- (alpha-methylene-gamma-butyrolactone) obtained in embodiment 71H NMR spectra.
Specific embodiment
The present invention is specifically described in following case study on implementation, but the present invention is not restricted to these case study on implementation.
Material used in following case study on implementation, reagent etc., are commercially available unless otherwise specified.
Comparative example 1
By (0.05mmol, 5.41mg) benzylalcohol, (0.05mmol, 59.9mg) six [three (dimethyl amine) phosphorus nitrence] trimerization phosphorus
Nitrile is dissolved in 0.187mL tetrahydrofuran, is placed in -50 DEG C of low temperature cryostats and is stirred 10min, with syringe by (5mmol, 0.44mL)
Alpha-methylene-gamma-butyrolactone is added in reaction tube.Reaction carries out 4h under nitrogen protection, and 10 drop acetic acid are added and terminate reaction.It will
Reaction mixture is dissolved in 1mL n,N-Dimethylformamide, is poured into 10mL methanol, and centrifuge separation precipitating obtains polymer, core
Magnetic characterizes all double bond addition products of polymer, and nucleus magnetic hydrogen spectrum is as shown in Figure 1.
Embodiment 1
(0.05mmol, 5.41mg) benzylalcohol, (0.05mmol, 59.9mg) six [three (dimethyl amine) phosphorus nitrence] trimerization phosphorus
Nitrile, (0.15mmol, 42.95mg) 1- cyclohexyl -3- (4- trifluoromethyl) urea are dissolved in 0.187mL tetrahydrofuran, be placed in -
10min is stirred in 50 DEG C of low temperature cryostats, reaction tube is added in (5mmol, 0.44mL) alpha-methylene-gamma-butyrolactone with syringe
In.Reaction carries out 4h under -50 DEG C of nitrogen protections, and 10 drop acetic acid are added and terminate reaction.Reaction mixture is dissolved in 3mL chloroform
In, it pours into 10mL methanol, centrifuge separation precipitating obtains polymer, and it is ring opening polymerization product, i.e., poly- (α-that nuclear-magnetism, which characterizes polymer,
Methylene-y-butyrolactone), nucleus magnetic hydrogen spectrum is as shown in Fig. 2, nuclear-magnetism carbon spectrum such as Fig. 3 is indicated.GPC measures number-average molecular weight
5.9kg/mol, molecular weight distribution 1.29, GPC spectrogram is as shown in figure 4, DSC spectrogram is as shown in Figure 5.With 1 phase of comparative example
Compare, obtain being double bond polyaddition products when urea is not added, and urea is added to obtain being ring opening polymerization product later.
Embodiment 2
(0.05mmol, 5.41mg) benzylalcohol, (0.05mmol, 31.7mg) phosphonitrile ligand P4- tert-butyl catalyst,
(0.15mmol, 42.95mg) 1- cyclohexyl -3- (3,5- bis- (trifluoromethyl) phenyl) urea is dissolved in 0.187mL tetrahydrofuran, sets
10min is stirred in -60 DEG C of low temperature cryostats, (7.5mmol, 0.66mL) alpha-methylene-gamma-butyrolactone is added instead with syringe
Ying Guanzhong.Reaction carries out 4h under -60 DEG C of nitrogen protections, and 10mg benzoic acid is added and terminates reaction.Reaction mixture is dissolved in
It in 10mL chloroform, pours into 30mL methanol, centrifuge separation precipitating obtains polymer, and nuclear-magnetism characterizes polymer as ring-opening polymerisation production
Object, i.e., it is poly- (alpha-methylene-gamma-butyrolactone), GPC measure number-average molecular weight be 10.5kg/mol, molecular weight distribution 1.35,
GPC spectrogram is as shown in figure 4, DSC spectrogram is as shown in Figure 5.
Embodiment 3
By (0.4mmol, 54.5mg) phenylpropanol, (1.6mmol, 588mg) phosphonitrile ligand P2- tert-butyl, (6.4mmol,
1.36g) 1,3- diphenyl urea and 3mL tetrahydrofuran are added in reaction tube, are placed in -50 DEG C of low temperature cryostats and stir 10min, with note
(80mmol, 7mL) alpha-methylene-gamma-butyrolactone is added in reaction tube emitter.Reaction carries out under -50 DEG C of nitrogen protections
12h is added 1mL hydrochloric acid and terminates reaction.Reaction mixture is dissolved in 50mL methylene chloride, is poured into 200mL methanol, centrifugation point
Polymer is obtained from precipitating, it is ring opening polymerization product that nuclear-magnetism, which characterizes polymer, i.e., poly- (alpha-methylene-gamma-butyrolactone), GPC is surveyed
Number average molecular weight is 15.5kg/mol, and molecular weight distribution 1.31, GPC spectrogram is as shown in figure 4, DSC spectrogram is as shown in Figure 5.
Embodiment 4
By (0.5mmol, 69mg) Isosorbide-5-Nitrae-phenyl dimethanol, (0.75mmol, 30mg) hydrofining, (1.5mmol,
360.6mg) 1,3- dicyclohexyl thiourea and 2mL tetrahydrofuran are added in reaction tube, are placed in -40 DEG C of low temperature cryostats and stir
(150mmol, 13.2mL) alpha-methylene-gamma-butyrolactone is added in reaction tube with syringe by 10min.Reaction is in -40 DEG C of nitrogen
8h is carried out under gas shielded, and 5mL hydrochloric acid is added and terminates reaction.Reaction mixture is dissolved in 50mL methylene chloride, 200mL first is poured into
In alcohol, centrifuge separation precipitating obtains polymer, and it is ring opening polymerization product, i.e., poly- (alpha-methylene-γ-fourth that nuclear-magnetism, which characterizes polymer,
Lactone), it is 25.5kg/mol that GPC, which measures number-average molecular weight, and molecular weight distribution 1.29, GPC spectrogram is as shown in figure 4, DSC spectrogram
As shown in Figure 5.
Embodiment 5
By (0.05mmol, 3.51mg) potassium methoxide, (0.15mmol, 21.6mg) 1,3- diisopropyl urea and 0.187mL second
Nitrile is added in reaction tube, is placed in -40 DEG C of low temperature cryostats and stirs 10min, with syringe by (5mmol, 0.44mL) alpha-methylene -
Gamma-butyrolacton is added in reaction tube.Reaction carries out 2h under -40 DEG C of nitrogen protections, and 1mL hydrochloric acid is added and terminates reaction.It will reaction
Mixture is dissolved in 10mL methylene chloride, is poured into 50mL methanol, and centrifuge separation precipitating obtains polymer, and nuclear-magnetism characterizes polymer
For ring opening polymerization product, i.e., poly- (alpha-methylene-gamma-butyrolactone), it is 6.6kg/mol, molecular weight point that GPC, which measures number-average molecular weight,
Cloth is 1.05, and nucleus magnetic hydrogen spectrum is as shown in Figure 6.
Embodiment 6
By (0.05mmol, 9.21mg) benzohydrol, (0.1mmol, 2.3mg) sodium and (0.3mmol, 84.1mg) 1- benzene
Base -3- (4- trifluoromethyl) urea, 0.2mL n,N-Dimethylformamide are added in reaction tube, are placed in -40 DEG C of low temperature cryostats
(5mmol, 0.44mL) alpha-methylene-gamma-butyrolactone is added in reaction tube with syringe by middle stirring 10min.Reaction is -40
It carries out for 24 hours, 1mL sulfuric acid being added and terminates reaction under DEG C nitrogen protection.Reaction mixture is dissolved in 10mL methylene chloride, is poured into
In 50mL methanol, centrifuge separation precipitating obtains polymer, and it is ring opening polymerization product, i.e., poly- (alpha-methylene-that nuclear-magnetism, which characterizes polymer,
Gamma-butyrolacton), it is 8.6kg/mol that GPC, which measures number-average molecular weight, and molecular weight distribution 1.15, nucleus magnetic hydrogen spectrum is as shown in Figure 7.
Embodiment 7
(0.5mmol, 30mg) isopropanol, (0.5mmol, 600mg) six [three (dimethyl amine) phosphorus nitrence] tripolyphosphazene,
(1.5mmol, 429.5mg) 1- cyclohexyl -3- (4- trifluoromethyl) urea is dissolved in 1.87mL tetrahydrofuran, is placed in -50 DEG C
10min is stirred in low temperature cryostat, (50mmol, 4.4mL) alpha-methylene-gamma-butyrolactone is added in reaction tube with syringe.Instead
6h should be carried out under -50 DEG C of nitrogen protections, and 5mL sulfuric acid is added and terminates reaction.Reaction mixture is dissolved in 20mL chloroform, is poured into
In 100mL methanol, centrifuge separation precipitating obtains polymer, and it is ring opening polymerization product, i.e., poly- (α-methylene that nuclear-magnetism, which characterizes polymer,
Base-gamma-butyrolacton), nucleus magnetic hydrogen spectrum is as shown in Figure 8.It is 5.4kg/mol that GPC, which measures number-average molecular weight, and molecular weight distribution is
1.28。
Embodiment 8
(0.1mmol, 10.8mg) benzylalcohol, (0.1mmol, 63.4mg) phosphonitrile ligand P4- tert-butyl catalyst,
(0.3mmol, 70.3mg) 1- cyclohexyl -3- phenylthiourea is dissolved in 0.187mL tetrahydrofuran, is placed in -60 DEG C of low temperature cryostats
10min is stirred, (300mmol, 26.3mL) alpha-methylene-gamma-butyrolactone is added in reaction tube with syringe.Reaction is -60
48h is carried out under DEG C nitrogen protection, and 1mL phosphoric acid is added and terminates reaction.Reaction mixture is dissolved in 100mL chloroform, 500mL is poured into
In methanol, centrifuge separation precipitating obtains polymer, and it is ring opening polymerization product, i.e., poly- (alpha-methylene-γ-that nuclear-magnetism, which characterizes polymer,
Butyrolactone), it is 254kg/mol, molecular weight distribution 1.80 that GPC, which measures number-average molecular weight,.
Claims (7)
1. a kind of alpha-methylene-gamma-butyrolactone selective opening polymerization, the method for preparing poly- (alpha-methylene-gamma-butyrolactone),
Include the following steps:
(1) initiator, highly basic and co-catalyst are dissolved in organic solvent, at low temperature stirring a period of time；
(2) alpha-methylene-gamma-butyrolactone is added in above-mentioned mixed solution, at a certain temperature reaction a period of time, acid is added
Property substance terminate reaction, by reaction mixture be added methanol in precipitating obtain poly- (alpha-methylene-gamma-butyrolactone).
2. the method according to claim 1, wherein the chemical structure of poly- (alpha-methylene-gamma-butyrolactone)
Shown in formula such as formula (I):
It is characterized in that, n is the natural number more than or equal to 5, R1Selected from hydroxyl, methoxyl group, ethyoxyl, isopropoxy, tertiary fourth oxygen
Base, benzyloxy, phenyl ethoxy, phenyl-propoxy, diphenylmethyl oxygroup, 2,2- hexichol base oxethyl.
3. according to the method described in claim 1, it is characterized by:
The co-catalyst is at least one of urea or thiocarbamide, and wherein urea is compound shown in formula (II), and thiocarbamide is formula (III) institute
Show compound, R2And R3It is respectively and independently selected from alkyl or aryl, preferably methyl, ethyl, propyl, isopropyl, cyclohexyl, phenyl, 4-
Bis- (trifluoromethyl) phenyl of chlorphenyl, 4- methoxyphenyl, 4- trifluoromethyl, 3,5-, 2,6- 3,5-dimethylphenyl, 2,4- bis-
Methoxyphenyl, 2,4,6- trimethoxyphenyl.
4. urea according to claim 3 or thiocarbamide, which is characterized in that with one of following structure:
5. according to the method described in claim 1, it is characterized by:
The initiator be alcohol, preferably methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, benzylalcohol, benzyl carbinol, phenylpropanol, benzohydrol,
2,2- diphenyl ethyl alcohol, ethylene glycol, 1,4- phenyl dimethanol, glycerine, pentaerythrite；The highly basic is selected from alkali metal, alkali gold
Belong to compound or organic phosphazene base.
Optionally, the alkali metal is selected from sodium or potassium, and the alkali metal compound is selected from hydrofining, sodium hydride, described organic phosphorus
Nitrile alkali is selected from six [three (dimethyl amine) phosphorus nitrence] tripolyphosphazene ({ [(NMe2)3P=N]2P=N }3), the tertiary fourth of phosphonitrile ligand P4-
Base ([(NMe2)3P=N]3P=NtBu, tert-Bu-P4), phosphonitrile ligand P2- tert-butyl ([(NMe2)3P=N] (NMe2)2P=
NtBu, tert-Bu-P2)；
The acidic materials are at least one of acetic acid, benzoic acid, hydrochloric acid, sulfuric acid or phosphoric acid.
6. according to the method described in claim 1, it is characterized by:
The molar ratio of the highly basic and initiator is 1/3~20/1；The molar ratio of the highly basic and urea is 1/1~1/10；
The molar ratio of the initiator and alpha-methylene-gamma-butyrolactone is 1/10~1/3000；The acidic materials and highly basic rub
Your ratio is 1/1~10/1.
7. according to the method described in claim 1, it is characterized by:
Described a period of time of stirring at low temperature refers to 10~30min of stirring at -70~-10 DEG C；The organic solvent is selected from
Toluene, tetrahydrofuran, methylene chloride, acetonitrile, N,N-dimethylformamide；The reaction temperature is -70~-20 DEG C；It is described anti-
It is 0.5~48h between seasonable；Molar concentration of the alpha-methylene-gamma-butyrolactone in system is 4~11mol/L.
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| CN114369232B (en) * | 2022-01-26 | 2023-10-20 | 青岛科技大学 | Renewable degradable thermoplastic elastomer and preparation method thereof |
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