CN1706878A - Metal-less N-heterocyclic carbone catalyst and its prepn process - Google Patents
Metal-less N-heterocyclic carbone catalyst and its prepn process Download PDFInfo
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- CN1706878A CN1706878A CN 200510050266 CN200510050266A CN1706878A CN 1706878 A CN1706878 A CN 1706878A CN 200510050266 CN200510050266 CN 200510050266 CN 200510050266 A CN200510050266 A CN 200510050266A CN 1706878 A CN1706878 A CN 1706878A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 26
- 150000002460 imidazoles Chemical class 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910000765 intermetallic Chemical class 0.000 claims description 13
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000001246 bromo group Chemical group Br* 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000003107 substituted aryl group Chemical group 0.000 claims description 7
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 7
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000000178 monomer Substances 0.000 abstract description 11
- 150000002596 lactones Chemical class 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 abstract 1
- 125000002723 alicyclic group Chemical group 0.000 abstract 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- -1 alkoxy aluminum compound Chemical class 0.000 description 26
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 12
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 8
- 229920003232 aliphatic polyester Polymers 0.000 description 8
- WJQARFJEPSTEMF-UHFFFAOYSA-N CCCCN1C=CN(C)C1.C1=CN=CN1.Br Chemical class CCCCN1C=CN(C)C1.C1=CN=CN1.Br WJQARFJEPSTEMF-UHFFFAOYSA-N 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 5
- 229920002988 biodegradable polymer Polymers 0.000 description 4
- 239000004621 biodegradable polymer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Chemical group 0.000 description 3
- SGZJDICMAIEXMR-UHFFFAOYSA-N 1,3-dibutyl-2h-imidazole Chemical class CCCCN1CN(CCCC)C=C1 SGZJDICMAIEXMR-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 1
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- QEFSIQOCFSZSOI-UHFFFAOYSA-N CCCCCCN1C=CN(C)C1.C1=CN=CN1.Br Chemical class CCCCCCN1C=CN(C)C1.C1=CN=CN1.Br QEFSIQOCFSZSOI-UHFFFAOYSA-N 0.000 description 1
- UOCSQLJWHZILBI-UHFFFAOYSA-N CCCCN(CN1C)C(Cl)=C1Cl.C1=CN=CN1.Br Chemical class CCCCN(CN1C)C(Cl)=C1Cl.C1=CN=CN1.Br UOCSQLJWHZILBI-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses one kind of metal-less N-heterocyclic carbene catalyst and its preparation process. The catalyst has the general expression shown in I. The catalyst of the present invention is prepared through reaction between substituted imidazolyl onium salt and metal compound. The catalyst may be used in catalyzing the open-cyclic polemerization of lactone, lactide and other cyclic monomer to synthesize biodegradable alicyclic polyester containing no metal element as polymer material.
Description
Technical field
The present invention relates to catalyzer, relate in particular to a kind of metal-less N-heterocyclic carbone catalyst and preparation method thereof.
Background technology
Most of macromolecular materials that use such as polyolefine, polystyrene, polyvinyl chloride etc. are difficult to natural degradation at occurring in nature at present, their waste has caused serious pollution to environment, and the what is called " white pollution " that particularly disposable daily plastic brings is badly in need of finding terms of settlement.Aliphatic polyester is there is ester bond in a class on its macromolecular main chain an aliphatics macromolecular material, under water, enzyme or other microbial process, the ester bond on the macromolecular main chain ruptures, and molecular weight reduces gradually, generate the small molecules product, thereby be the macromolecular material that a class can be degraded fully.If use Biodegradable Polymers to replace macromolecular materials such as polyolefine commonly used,, avoided above-mentioned environmental problem owing to after reaching its work-ing life, can be degraded into the small molecules product of toxicological harmless fully.Aliphatic polyester not only has biodegradable, also has excellent biological compatibility, does not have tangible toxicity and rejection with the living organism of living, and medical materials such as alternative existing metal, pottery and natural polymer are used for the bio-medical field.When reaching its work-ing life, its nontoxic degraded product can participate in the human body metabolic process, thereby is absorbed and excretes, and the problem of having avoided second operation to take out can be widely used in fields such as surgical implant, medicine sustained release and organizational project.
Aliphatic polyester is synthesized by ring-opening polymerization by cyclic monomers such as corresponding lactone, lactides usually.Ring-opening polymerization catalyst commonly used has stannous octoate, alkoxy aluminum compound, rare earth catalyst etc., new catalyst system is also in continuous appearance, existing lot of documents discloses cyclic monomers such as lactone, lactide and has carried out ring-opening polymerization and come the synthesizing biological degradable polymer, for example, United States Patent (USP) 4045418,4057537,3736646,3463158,3620218,3636956,3297033,3284417,3169945,3021309,2890208, Chinese patent CN1164651C, CN1544504A, CN1306019A, CN1175601A etc.But all contain metallic element in the above-mentioned catalyzer, thereby inevitably can more residual metallic elements in its catalysis synthetic polymkeric substance.Studies show that even obtained drugs approved by FDA, most popular stannous octoate catalyst, its tin residual in polymkeric substance also may cause some cytotoxicities, and tin there is very bad influence to child's health.Although there are some nontoxic catalyzer, its catalytic activity is often too low, and polymerization temperature is too high, a little less than the ability of regulation and control to polymer architecture, is difficult to the requirement that reaches practical.The catalytic activity of cyclic monomer such as lactone, lactide ring-opening polymerization catalyst and this contradiction between the security are restricting the development of high-quality biodegradable polymer for a long time, are limiting to further expanding of its Application Areas.On the other hand, the active ring-opening polymerization of cyclic monomers such as realization lactone, lactide is the molecular weight of controlling polymers and the important means of distribution, sequential structure and product quality thereof.Therefore, research and develop not containing metal element, non-toxic efficient, can realize that the catalyzer of active ring-opening polymerization has very important significance to quality and the application security that improves biodegradable polymer.
On the other hand, Cabbeen is a kind of intermediate of the ripple of very living, the survival life-span often is no more than 1 second, be difficult to direct application, thereby the common more stable metal carbene compound of part formation as transition metal, be used for the catalyzed alkene metathesis reaction, as Chinese patent CN1511064A, CN1561261A, CN1518555A, CN1373156A.Thereby be necessary synthetic comparatively stable metal-free pure organic Cabbeen and use it for catalyzed chemical reaction.
Summary of the invention
The invention provides a kind of metal-less N-heterocyclic carbone catalyst stable under inert atmosphere and preparation method thereof.
The general structure of the metal-less N-heterocyclic carbone catalyst described in the present invention is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one.
A kind of preparation method of metal-less N-heterocyclic carbone catalyst: under protection of inert gas such as nitrogen, argon gas; is that 1: 0.001～1: 2 ratio joins in the reactor with substituted imidazole salt and metallic compound in the mol ratio that replaces imidazole salts metallizing thing; stirring mixes it; under 0 ℃～100 ℃ temperature; reacted 1 minute to 10 hours; filter, obtain catalyzer.
The preparation method of another kind of metal-less N-heterocyclic carbone catalyst: at nitrogen; under the protection of inert gas such as argon gas; metallic compound is dissolved in obtains solution of metal compound in the organic solvent; be 1: 0.001～1: 2 ratio adding substituted imidazole salt then in the mol ratio that replaces imidazole salts metallizing thing; be that 1: 0.001～1: 2 ratio joins in the organic solvent in the mol ratio that replaces imidazole salts metallizing thing perhaps with metallic compound and substituted imidazole salt; stirring mixes it; under 0 ℃～100 ℃ temperature; reacted 1 minute to 10 hours; filter, obtain catalyst solution.
The general structure of the substituted imidazole salt described in the present invention is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one; Y
-Be to be selected from following negatively charged ion: Cl
-, Br
-, I
-, BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-, NO
3 -, SO
4 2-, CH
3COO
-, CF
3COO
-, CH
3C
6H
5COO
-, SCN
-In any one.
Metallic compound described in the present invention is selected from any one or its mixture in potassium tert.-butoxide, sodium tert-butoxide, lithium hydride, sodium hydride, potassium hydride KH, the hydrolith.
Organic solvent described in the present invention is selected from tetrahydrofuran (THF), hexanaphthene, hexane, heptane, octane, benzene,toluene,xylene, chloroform, methylene dichloride, ether, acetone, butanone, pimelinketone, dioxane, N, any one or its mixture in the organic solvents such as dinethylformamide, dimethyl sulfoxide (DMSO).
The metal-less N-heterocyclic carbone catalyst that the present invention proposes is a kind of not containing metal element, stable pure organic carbone catalyst under inert atmosphere, have Adjustable structure, preparation is simple, catalytic activity is high, resulting polymers molecular weight and the controlled advantage that distributes thereof, can be used for the aliphatic polyester of the ring-opening polymerization of cyclic ester monomers such as lactone, lactide, be expected to thoroughly solve the metallic element residue problem of biodegradable polymers such as aliphatic polyester with synthesizing biological degradable.
Description of drawings
Accompanying drawing is a substituted imidazole salt 1,3-di-n-butyl imidazolium bromide (bbimBr) and 1,3-di-n-butyl imidazoles Cabbeen and CS
2Adducts (bbimCS
2)
1H NMR spectrogram.
Embodiment
Among the present invention, the general structure of metal-less N-heterocyclic carbone catalyst is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one.
R in the general structure of metal-less N-heterocyclic carbone catalyst among the present invention
1, R
3Be selected from H atom, methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, sec.-propyl, isobutyl-, isopentyl, isohexyl, the tertiary butyl, vinyl, allyl group, alkene butyl, phenyl, benzyl, 4-aminomethyl phenyl, 2,6-3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropyl phenyl, 2,4, any one in the 6-triisopropyl phenyl; R
4, R
5Be selected from H atom, F atom, Cl atom, Br atom, cyano group, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl, the n-hexyl any one.
R in the general structure of metal-less N-heterocyclic carbone catalyst among the present invention
1, R
3Preferentially be selected from methyl, ethyl, normal-butyl, n-hexyl, n-octyl, sec.-propyl, vinyl, allyl group, phenyl, 2,6-3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2, any one in the 6-diisopropyl phenyl; R
4, R
5Preferentially be selected from H atom, Cl atom, Br atom, cyano group, methyl, ethyl, butyl, the hexyl any one.
A kind of preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes; its step is as follows: under protection of inert gas such as nitrogen, argon gas; is that 1: 0.001～1: 2 ratio joins in the reactor with substituted imidazole salt and metallic compound in the mol ratio that replaces imidazole salts metallizing thing; stirring mixes it; under 0 ℃～100 ℃ temperature; reacted 1 minute to 10 hours, and filtered, obtain catalyzer.
The another kind of preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes; its step is as follows: at nitrogen; under the protection of inert gas such as argon gas; metallic compound is dissolved in obtains solution of metal compound in the organic solvent; be 1: 0.001～1: 2 ratio adding substituted imidazole salt then in the mol ratio that replaces imidazole salts metallizing thing; be that 1: 0.001～1: 2 ratio joins in the organic solvent in the mol ratio that replaces imidazole salts metallizing thing perhaps with metallic compound and substituted imidazole salt; stirring mixes it; under 0 ℃～100 ℃ temperature; reacted 1 minute to 10 hours; filter, obtain catalyst solution.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, the general structure of described substituted imidazole salt is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one; Y
-Be to be selected from following negatively charged ion: Cl
-, Br
-, I
-, BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-, NO
3 -, SO
4 2-, CH
3COO
-, CF
3COO
-, CH
3C
6H
5COO
-, SCN
-In any one.
In the general structure of the substituted imidazole salt described in the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, R
1, R
3Preferentially be selected from methyl, ethyl, normal-butyl, n-hexyl, n-octyl, sec.-propyl, vinyl, allyl group, phenyl, 2,6-3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2, any one in the 6-diisopropyl phenyl; R
4, R
5Be selected from H atom, F atom, Cl atom, Br atom, cyano group, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl, the n-hexyl any one.Y
-Preferentially be selected from following negatively charged ion: Cl
-, Br
-, BF
4 -, PF
6 -, CF
3SO
3 -, NO
3 -, SO
4 2-, CH
3COO
-In any one.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, described metallic compound is selected from any one or its mixture in potassium tert.-butoxide, sodium tert-butoxide, lithium hydride, sodium hydride, potassium hydride KH, the hydrolith.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, the mol ratio of described substituted imidazole salt metallizing thing is 1: 0.001～1: 2.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, described organic solvent is selected from tetrahydrofuran (THF), hexanaphthene, hexane, heptane, octane, benzene,toluene,xylene, chloroform, methylene dichloride, ether, acetone, butanone, pimelinketone, dioxane, N, any one or its mixture in the organic solvents such as dinethylformamide, dimethyl sulfoxide (DMSO).
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, described organic solvent preferentially is selected from following organic solvent: tetrahydrofuran (THF), hexanaphthene, toluene, chloroform, methylene dichloride, ether, acetone, dioxane, N, any one in the dinethylformamide or its mixture.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, the ratio that the quality of described organic solvent accounts for the reaction mixture total mass is 0～99.9wt%.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, the ratio that the quality of described organic solvent accounts for the reaction mixture total mass is preferably 20～99wt%.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, the ratio that the quality of described organic solvent accounts for the reaction mixture total mass more preferably is 50～98wt%.
Among the preparation method of the metal-less N-heterocyclic carbone catalyst that the present invention proposes, described temperature of reaction is preferably 20 ℃～60 ℃, and the reaction times is preferably 5 minutes to 2 hours.
The metal-less N-heterocyclic carbone catalyst that the present invention proposes has enough stability, when especially remaining in the solution under the anhydrous and oxygen-free condition of protection of inert gas such as high pure nitrogen, high-purity argon gas.
The metal-less N-heterocyclic carbone catalyst that the present invention proposes with the easily colour developing of sulfurous gas reaction back, generates red adducts under protection of inert gas, can be used to confirm the generation of this catalyzer.
The metal-less N-heterocyclic carbone catalyst that the present invention proposes, the ring-opening polymerization of cyclic ester monomers such as catalysis glycollide efficiently, rac-Lactide, beta-butyrolactone, δ-Wu Neizhi, 6-caprolactone at normal temperatures, synthesizing biological degradable aliphatic polyester.Polymerisation conversion can reach more than 90%, and molecular weight distribution is narrow, and polydispersity index is 1.1～2.5.
The metal-less N-heterocyclic carbone catalyst that the present invention proposes, under inert atmosphere, preserved for 1 to 2 week after, the activity of lactone or lactide monomers ring-opening polymerization is remained unchanged substantially.
The prepared aliphatic polyester of ring-opening polymerization that the metal-less N-heterocyclic carbone catalyst that the present invention proposes is used for cyclic ester monomers such as lactone, lactide is the containing metal element not, is expected to improve simultaneously the quality and the application security of aliphatic polyester.
The embodiment that the invention is further illustrated by the following examples, but be not limited to these embodiment.
Embodiment 1:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; with substituted imidazole salt 1; 3-dibutyl imidazolium bromide (bbimBr) 130mg (0.5mmol) and potassium tert.-butoxide 50mg (0.45mmol) add in the glass reactor of band magnetic agitation; stirring mixes it; reacted 20 minutes down at 25 ℃; filter, obtain 1,3-di-n-butyl imidazoles Cabbeen (bbim) catalyzer.Add tetrahydrofuran (THF) 2ml and dithiocarbonic anhydride 40mg in the catalyzer that obtains, color reaction takes place immediately, solution is by the light yellow redness that becomes.Reaction product is poured in the 10ml normal hexane, had reddish-brown precipitation to separate out.Warp
1H NMR nuclear-magnetism spectrum analysis, this reddish-brown precipitation is 1, the adducts (bbimCS of 3-di-n-butyl imidazoles Cabbeen (bbim) Cabbeen and dithiocarbonic anhydride
2), showing has 1, and 3-di-n-butyl imidazoles Cabbeen (bbim) Cabbeen generates.This adducts and substituted imidazole salt 1,3-dibutyl imidazolium bromide bbimBr's
1H NMR spectrogram is seen accompanying drawing.
Embodiment 2:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 0.5g (4.5mmol) is dissolved in the 5ml tetrahydrofuran (THF); add substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 1.09g (5mmol) then; stirring mixes it; reacted 20 minutes down at 25 ℃; filter, obtain 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution.Color reaction proves the generation of this carbone catalyst.
Embodiment 3:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; substituted imidazole salt 1-n-hexyl-3-Methylimidazole bromide (hmimBr) 1.23g (5mmol) is dissolved in N; among the dinethylformamide 5ml; add potassium tert.-butoxide 0.5g (4.5mmol) then; stirring mixes it; fully reacted 20 minutes down at 25 ℃, filter, obtain 1-n-hexyl-3-Methylimidazole Cabbeen (hmim) catalyst solution.Color reaction proves the generation of this carbone catalyst.
Embodiment 4:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; in the 10ml tetrahydrofuran (THF), add substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 1.09g (5mmol) and tetracol phenixin 2.3g (15mmol); reacted 30 minutes down at 20 ℃; solvents tetrahydrofurane and unreacted tetracol phenixin are removed in underpressure distillation then; obtain substituted imidazole salt 1-normal-butyl-3-methyl-4,5-dichloro-imidazole bromide (Cl
2BmimBr).Add potassium tert.-butoxide 0.5g (4.5mmol) and 5ml tetrahydrofuran (THF) then, stirring mixes it, reacts 20 minutes down at 25 ℃, filters, and obtains 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution.Color reaction proves the generation of this carbone catalyst.
Embodiment 5:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection, potassium tert.-butoxide 0.5g (4.5mmol) is dissolved in the 5ml tetrahydrofuran (THF), add substituted imidazole salt 1-normal-butyl-3-methyl imidazolium tetrafluoroborate (bmimBF then
4) 1.13g (5mmol), stirring mixes it, reacts 20 minutes down at 25 ℃, filters, and obtains 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution.Color reaction proves the generation of this carbone catalyst.
Embodiment 6:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 5mg (0.045mmol) is joined substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 9.8g (45mmol); stirring mixes it; reacted 20 minutes down at 25 ℃; filter, obtain 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyzer.Color reaction proves the generation of this carbone catalyst.
Embodiment 7:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 1.12g (10mmol) is dissolved in the 5ml tetrahydrofuran (THF); add substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 1.09g (5mmol) then; stirring mixes it; reacted 20 minutes down at 25 ℃; filter, obtain 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution.Color reaction proves the generation of this carbone catalyst.
Embodiment 8:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 0.5g (4.5mmol) is dissolved in the 5ml tetrahydrofuran (THF); add substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 1.09g (5mmol) then; stirring mixes it; reacted 10 hours down at 0 ℃; filter, obtain 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution.Color reaction proves the generation of this carbone catalyst.
Embodiment 9:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; potassium tert.-butoxide 0.5g (4.5mmol) is joined among substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 1.09g (5mmol); stirring mixes it; reacted 1 minute down at 100 ℃; filter, obtain 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyzer.Color reaction proves the generation of this carbone catalyst.
Embodiment 10:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; mineral oil dispersion liquid (30wt%) 0.6g (4.5mmol) of potassium hydride KH is joined among substituted imidazole salt 1-normal-butyl-3-Methylimidazole bromide (bmimBr) 1.09g (5mmol); stirring mixes it; reacted 1 minute down at 100 ℃; filter, obtain 1-normal-butyl-3-Methylimidazole Cabbeen (bmim) catalyst solution.Color reaction proves the generation of this carbone catalyst.
Reference example 1:
Under the anhydrous and oxygen-free condition of high purity nitrogen protection; to obtain by embodiment 11, add 5ml tetrahydrofuran (THF), phenylcarbinol 50mg and 6-caprolactone 5ml in 3-di-n-butyl imidazoles Cabbeen (bbim) catalyzer, stir it mixed; add the entry termination reaction in reaction under 25 ℃ after 30 minutes.In resulting polymers solution, add the 10ml tetrahydrofuran (THF) and dilute, after precipitation, filtration and drying, obtain poly-epsilon-caprolactone.Monomer conversion is 99.2%.Recording its number-average molecular weight with GPC is 9960, and polydispersity index is 1.39.
Reference example 2:
With embodiment 1 obtain 1, after 3-di-n-butyl imidazoles Cabbeen (bbim) catalyst solution is preserved the different time shown in the table 1 respectively, be used for the ring-opening polymerization of 6-caprolactone, polymerizing condition and the results are shown in Table 1 with reference example 1 same method.
Table 11, catalysis ε behind 3-di-n-butyl imidazoles Cabbeen (bbim) the catalyst solution placement different time-oneself
The effect of lactone ring opening polymerization
| Shelf time (day) | Reaction times (min) | Monomer conversion (%) | M n，exp | ?? |
| 4 7 | 45 45 | 98.0 70.5 | 9790 9300 | ??1.54 ??1.48 |
Claims (8)
1, a kind of metal-less N-heterocyclic carbone catalyst is characterized in that the general structure of this catalyzer is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one.
2, a kind of preparation method of metal-less N-heterocyclic carbone catalyst as claimed in claim 1; it is characterized in that: under nitrogen, argon gas protection of inert gas; is that 1: 0.001～1: 2 ratio joins in the reactor with substituted imidazole salt and metallic compound in the mol ratio that replaces imidazole salts metallizing thing; stirring mixes it; under 0 ℃～100 ℃ temperature; reacted 1 minute to 10 hours, and filtered, obtain catalyzer.
3, the preparation method of a kind of metal-less N-heterocyclic carbone catalyst as claimed in claim 2 is characterized in that the general structure of described substituted imidazole salt is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one; Y
-Be to be selected from following negatively charged ion: Cl
-, Br
-, I
-, BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-, NO
3 -, SO
4 2-, CH
3COO
-, CF
3COO
-, CH
3C
6H
5COO
-, SCN
-In any one.
4, the preparation method of a kind of metal-less N-heterocyclic carbone catalyst as claimed in claim 2 is characterized in that described metallic compound is selected from any one or its mixture in potassium tert.-butoxide, sodium tert-butoxide, lithium hydride, sodium hydride, potassium hydride KH, the hydrolith.
5; a kind of preparation method of a kind of metal-less N-heterocyclic carbone catalyst as claimed in claim 1; it is characterized in that: at nitrogen; under the argon gas protection of inert gas; metallic compound is dissolved in obtains solution of metal compound in the organic solvent; be 1: 0.001～1: 2 ratio adding substituted imidazole salt then in the mol ratio that replaces imidazole salts metallizing thing; be that 1: 0.001～1: 2 ratio joins in the organic solvent in the mol ratio that replaces imidazole salts metallizing thing perhaps with metallic compound and substituted imidazole salt; stirring mixes it; under 0 ℃～100 ℃ temperature; reacted 1 minute to 10 hours; filter, obtain catalyst solution.
6, the preparation method of a kind of metal-less N-heterocyclic carbone catalyst as claimed in claim 5 is characterized in that the general structure of described substituted imidazole salt is:
Wherein, R
1, R
3Be selected from H atom, C
1～C
20Alkyl, C
3～C
20Branched-chain alkyl, C
5～C
12Cycloalkyl, substituted cycloalkyl, C
1～C
6In thiazolinyl, aryl, substituted aryl, the aralkyl any one; R
4, R
5Be selected from H atom, fluorine atom, Cl atom, Br atom, cyano group, C
1-C
6In the alkyl any one; Y
-Be to be selected from following negatively charged ion: Cl
-, Br
-, I
-, BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-, NO
3 -, SO
4 2-, CH
3COO
-, CF
3COO
-, CH
3C
6H
5COO
-, SCN
-In any one.
7, the preparation method of metal-less N-heterocyclic carbone catalyst as claimed in claim 5 is characterized in that described metallic compound is selected from any one or its mixture in potassium tert.-butoxide, sodium tert-butoxide, lithium hydride, sodium hydride, potassium hydride KH, the hydrolith.
8, the preparation method of metal-less N-heterocyclic carbone catalyst as claimed in claim 5, it is characterized in that described organic solvent is selected from tetrahydrofuran (THF), hexanaphthene, hexane, heptane, octane, benzene,toluene,xylene, chloroform, methylene dichloride, ether, acetone, butanone, pimelinketone, dioxane, N, any one or its mixture in the organic solvents such as dinethylformamide, dimethyl sulfoxide (DMSO).
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