CN105199084A - Method for preparing polylactone - Google Patents
Method for preparing polylactone Download PDFInfo
- Publication number
- CN105199084A CN105199084A CN201510700813.6A CN201510700813A CN105199084A CN 105199084 A CN105199084 A CN 105199084A CN 201510700813 A CN201510700813 A CN 201510700813A CN 105199084 A CN105199084 A CN 105199084A
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- CN
- China
- Prior art keywords
- preparation
- solvent
- valerolactone
- alcohol
- resorcinol
- Prior art date
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- -1 nanoreactor Substances 0.000 claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 42
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 235000019253 formic acid Nutrition 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- YKVIWISPFDZYOW-UHFFFAOYSA-N 6-Decanolide Chemical compound CCCCC1CCCCC(=O)O1 YKVIWISPFDZYOW-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
- 229960004217 benzyl alcohol Drugs 0.000 claims description 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 claims description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OALYTRUKMRCXNH-UHFFFAOYSA-N (R)- Dihydro-5-pentyl-2(3H)-furanone Natural products CCCCCC1CCC(=O)O1 OALYTRUKMRCXNH-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 claims description 2
- WHYHCPIPOSTZRU-UHFFFAOYSA-N 6-azidohexan-1-ol Chemical compound OCCCCCCN=[N+]=[N-] WHYHCPIPOSTZRU-UHFFFAOYSA-N 0.000 claims description 2
- FRTMRFCNTDDSOB-UHFFFAOYSA-N 7-Hexyl-2-oxepanone Chemical compound CCCCCCC1CCCCC(=O)O1 FRTMRFCNTDDSOB-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- FTXUQEKXCJSWMO-UHFFFAOYSA-N Nonanolactone Chemical compound O=C1CCCCCCCCO1 FTXUQEKXCJSWMO-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- ZYDGQQTXLBNSGJ-UHFFFAOYSA-N oxonan-2-one Chemical compound O=C1CCCCCCCO1 ZYDGQQTXLBNSGJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 claims description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229920001610 polycaprolactone Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 abstract 2
- 239000003937 drug carrier Substances 0.000 abstract 1
- 238000006362 organocatalysis Methods 0.000 abstract 1
- 239000004632 polycaprolactone Substances 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- 150000002596 lactones Chemical class 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SRVJKTDHMYAMHA-WUXMJOGZSA-N thioacetazone Chemical compound CC(=O)NC1=CC=C(\C=N\NC(N)=S)C=C1 SRVJKTDHMYAMHA-WUXMJOGZSA-N 0.000 description 1
- 229960003231 thioacetazone Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 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 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of polylactone and belongs to the technical field of organocatalysis and high polymer materials. By the use of a catalyst (gamma-resorcylic acid) which is natural and safe, is not sensitive to the environment, is commercially available and is cheap and has an ideal catalytic effect, polyvalerolactone and polycaprolactone are prepared at 0-200 DEG C in the presence or in the absence of a solvent, so as to obtain a high polymer biodegradable material having large molecular weight and narrow dispersity and containing no metal impurities. Thus, defects of a catalyst commonly used in industry in aspects of safety, price, sensitivity to the environment and catalytic effect are overcome, and a simple, mild, effective and cheap polymerization method is provided. A high polymer material prepared by the method can be applied in fields of drug carrier, nanoreactor, film, material interface and the like, has biodegradability and is an environmentally-friendly material.
Description
Technical field
The invention belongs to organic catalysis and technical field of polymer materials, be specifically related to the method using catalyst to synthesize lactone cheap and easy to get.
Background technology
Since eighties of last century the '30s starts, it is important that high molecular synthesis and application have become more.At present, macromolecular material loses nowhere in our life, as polystyrene, polyolefine, polyvinyl chloride etc.But these common macromolecular materials are but difficult to degraded at occurring in nature, and its waste even causes serious pollution to environment.Therefore, the research of biodegradable macromolecular material has its profound significance.
Aliphatic polyester series macromolecular compound is a class Biodegradable polymer material of current most study; it can degrade gradually in water, enzyme or microbial environment; help to solve current day by day serious environmental problem; and the micromolecular compound obtained of degrading can recycle and reuse, and alleviates the crisis of world energy sources scarcity.Aliphatic polyester has good bio-compatibility, does not have overt toxicity and rejection to organism, can be advantageously applied to bio-medical field.
Prepare the method existing large quantifier elimination at present of aliphatic polyester.Wherein carrying out ring-opening polymerization with annular lactone is study a kind of more method.In ring-opening polymerization, usual use is containing the organic catalyst of the metals such as aluminium, tin, zinc, yttrium, conventional has stannous octoate and aluminum alkoxide etc., open source literature and the patent report of this respect are more, and much technique has been applied to polymkeric substance preparation (Kato, M. etc., Biomacromolecules, 2007,8,3590-3596; OlivierCoulembier etc., ProgressinPolymerScience, 2006,31,723-747; CN1544504, US5235031, US5696219).But use this kind of metal catalyst, extremely easily cause residual on gained polymerisate of metal, thus limit its application in biology, medicine, microelectronics etc.
In order to make up the defect of metal catalyst in ring-opening polymerization, organic catalyst is normally used as the substitute of metal catalyst gradually.Since calendar year 2001 Hedrick reported first after the ring-opening polymerization of DMAP (DMAP) as organic catalyst catalysis rac-Lactide, the ring-opening polymerization kind of organic catalyst catalyzing lactone becomes increasing, common are Cabbeen, phosphonitrile, difunctional Amithiozone, guanidine, bronsted acid etc.
Bronsted acid is as the report of catalyzer (Endo etc., Macromolecules, 2000,33,4316-4320 on the low side; S.Magnet etc., Macromolecules, 2008,41,3782-3784; ZhenjiangLi etc., PolymerChemistry, 2014,5,3098-3106), common are sulphonic acids, phosphoric acid class and carboxylic-acid.This type of catalyzer generally has superpower acidity, corrodibility and toxicity.Some catalyzer is for the unsatisfactory (Endo etc. of ring-opening polymerization effect of lactone, Macromolecules, 2000, 33, 4316-4320), (the ToyojiKakuchi etc. on the high side of some catalyzer, Macromolecules, 2011, 44, 1999-2005), some is for the moisture-sensitive (ToyojiKakuchi etc. in air, Macromolecules, 2010, 43, 7090-7094), too high and the undesirable (ArmandoCo ' rdova etc. of effect of condition that some catalyzer uses, AdvancedSynthesis & Catalysis, 2004, 346, 1087-1089).
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of catalyst preparing polylactone of natural cheapness, prepares that molecular weight is large, dispersity is narrow, the high-molecular biologic degradation material of not metal impurities.Overcome general catalyzer in safety, price, to the deficiency of environment sensitive degree and catalytic effect aspect.Provide a kind of simple, gentle, effectively, the polymerization process of cheap and Be very effective.
For solving above-mentioned technical problem, the present invention utilizes natural product γ-resorcinol formic acid (2,6-DHBA) as catalyzer.
Technical scheme of the present invention is: a kind of method of catalyst preparing polylactone of natural cheapness, with δ-valerolactone, fourth position caprolactone, fourth position caprylolactone, fourth position decalactone, fourth position nonalactone, fourth position dodecalactone, 3-methyl-5-valerolactone, 6-caprolactone, ε-decalactone or ε-dodecalactone are monomer, with such as formula γ shown in (I) ?resorcinol formic acid for catalyzer, take alcohol compound as initiator, temperature of reaction is 0 ~ 200 DEG C, have solvent or solvent-free under, monomer generation ring-opening polymerization generates corresponding polylactone.
Preferred monomers is δ-valerolactone, fourth position caprolactone, fourth position dodecalactone, ε-decalactone or 6-caprolactone.
Described preparation method adopts has solvent or without solution polymerization, described when having a solvent, solvent comprises acetone, pimelinketone, dioxane, tetrahydrofuran (THF), benzene,toluene,xylene, methylene dichloride, trichloromethane, tetrachloromethane, N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide, acetonitrile.
Preferred solvent is tetrahydrofuran (THF), toluene, methylene dichloride, trichloromethane, DMF.
Described alcohol compound is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, phenylcarbinol, phenylethyl alcohol, ethylene glycol, condensed ethandiol, tetramethylolmethane, propiolic alcohol, 6-azido--1-hexanol, N-(2-hydroxyethyl) maleimide, 5-hexen-1-ol, water.
The mol ratio of above-mentioned internal ester monomer and catalyzer γ-resorcinol formic acid is 1-10000; The mol ratio of initiator and catalyzer γ-resorcinol formic acid is 0.01-1000.
Described preparation method completes under vacuum or rare gas element, and vacuum tightness is the pressure of 1 ~ 500 handkerchief or rare gas element is 100-101325 handkerchief.
Above-mentioned reaction in the solution, the initial reaction concentration of described monomer is 0.1mol/L ~ 100mol/L.
At the end of also comprising reaction, add terminator, described terminator is triethylamine.
Described preparation method adds precipitating solvent again or directly adds precipitating solvent after adding terminator, and described precipitating solvent is methyl alcohol, ethanol, ether, normal hexane or Skellysolve A.
Beneficial effect:
γ-resorcinol formic acid is a kind of natural organic monoacid.Two hydroxyls and the carboxyl that are in carboxyl ortho position form two intramolecular hydrogen bonds, greatly strengthen the ability of carboxylic acid proton ionization, the acidity of γ-resorcinol formic acid is strengthened.With the catalyzer that γ-resorcinol formic acid is ring-opening polymerization, reaction conditions is gentle, and reaction preference is high and polymerization velocity fast, and the polymer molecular weight obtained is accurate and dispersed low.In the process, γ-resorcinol formic acid is insensitive to environment, greatly strengthen the technological feasibility of reaction, and can recycle and reuse after the completion of reaction.Can obtain and cheap catalyzer as a kind of business, the cost in industrial production can be reduced.
Accompanying drawing explanation
Below, describe embodiments of the invention in detail by reference to the accompanying drawings, wherein:
Fig. 1: the poly-δ-valerolactone obtained as catalyst preparing with γ-resorcinol formic acid
1hNMR spectrogram;
Fig. 2: the poly-epsilon-caprolactone obtained as catalyst preparing with γ-resorcinol formic acid
1hNMR spectrogram;
Fig. 3: the spectrogram of poly-valerolactone in Size Exclusion Chromatograph SEC is analyzed obtained for catalyst preparing with γ-resorcinol formic acid.
Embodiment
Can further illustrate the present invention by the following example, embodiment is unrestricted of the present invention in order to illustrate.Any those of ordinary skill of this area can both be understood these embodiments and not limit the present invention in any way, and can make suitable amendment and data transformation and without prejudice to essence of the present invention with depart from scope of the present invention to it.
Embodiment 1
By γ-resorcinol formic acid (0.0154g; 0.1mmol; 1.0equiv), δ-valerolactone (0.27ml; 3.0mmol; 30equiv) with phenylcarbinol (10.3 μ L; 0.1mmol, 1.0equiv) add in reaction flask, dissolve with the methylene dichloride of 1.0ml; under argon shield; after stirring at room temperature reacts 18 hours, pour in methyl alcohol after reactant is concentrated, sedimentation and filtration is also dried to constant weight; obtain the poly-valerolactone product of white; transformation efficiency is 94% (proton nmr spectra, 400MHz, CDCl
3), the number-average molecular weight M of poly-valerolactone
nfor 3090gmol
-1(proton nmr spectra, 400MHz, CDCl
3), dispersity PDI is 1.08 (molecular-exclusion chromatography, Waterscolumn:5mm, 300 × 7.8mm, tetrahydrofuran (THF) moving phase, 0.7mLmin
-1, polystyrene is standard specimen),
1hNMR (300MHz, CDCl
3): δ (ppm) 1.68 (m, 2H × n, (– CH
2cH
2cH
2o –)
n), 1.70 (m, 2H × n, (– COCH
2– CH
2cH
2–)
n), 2.34 (t, 2H × n, J=6.8Hz, (– OCOCH
2cH
2–)
n), 3.65 (t, 2H, J=6.1Hz ， – CH
2cH
2oH), 4.08 (t, 2H × n, J=5.5Hz, (– CH
2cH
2o-)
n), 5.12 (s, 2H, ArCH
2o), 7.32 – 7.39 (m, 5H, aromatic).Poly-δ-valerolactone
1hNMR spectrogram is shown in Fig. 1.The poly-spectrogram of valerolactone in Size Exclusion Chromatograph SEC analysis is shown in Fig. 3.
Embodiment 2:
By γ-resorcinol formic acid (0.0154g; 0.1mmol; 1.0equiv), 6-caprolactone (0.33ml; 3.0mmol; 30equiv) with propiolic alcohol (5.8 μ L; 0.1mmol; 1.0equiv) add in reaction flask, dissolve, under argon shield with the toluene of 1.0ml; after stirring at room temperature reacts 24 hours; pour in ethanol after reactant is concentrated, sedimentation and filtration is also dried to constant weight, obtains the poly-valerolactone product of white; transformation efficiency is 93%, the number-average molecular weight M of poly-valerolactone
nfor 4320gmol
-1, dispersity PDI is 1.06,
1hNMR (300MHz, CDCl
3): δ (ppm), 1.39 (m, 2H × n, (– CH
2cH
2cH
2cH
2cH
2–)
n), 1.63 (m, 2H × n, (– CH
2cH
2cH
2o –)
n), 1.68 (m, 2H × n, (– COCH
2cH
2cH
2–)
n), 2.31 (t, 2H × n, J=7.3Hz, (– OCOCH
2cH
2–)
n), 3.65 (t, 2H, J=6.6Hz, CH
2cH
2oH), 4.06 (t, 2H × n, J=6.6Hz, (– CH
2cH
2o –)
n), 5.12 (s, 2H, ArCH
2o), 7.23 – 7.39 (m, 5H, aromatic); Poly-epsilon-caprolactone
1hNMR spectrogram is shown in Fig. 2.
Embodiment 3:
By γ-resorcinol formic acid (0.0154g; 0.1mmol; 1.0equiv), fourth position caprolactone (3.3ml; 30.0mmol; 300equiv) with N-(2-hydroxyethyl) maleimide (14.112g; 0.1mmol; 1.0equiv) add in reaction flask, dissolve, under argon shield with the tetrahydrofuran (THF) of 2.0ml; after stirring at room temperature reacts 48 hours; pour in ether after reactant is concentrated, sedimentation and filtration is also dried to constant weight, obtains the poly-valerolactone product of white; transformation efficiency is 82%, the number-average molecular weight M of poly-fourth position caprolactone
nfor 20800gmol
-1, dispersity PDI is 1.18.
Embodiment 4:
By γ-resorcinol formic acid (1.540g; 10.0mmol; 100.0equiv), fourth position dodecalactone (5.949g; 30.0mmol; 300equiv) with 5-hexen-1-ol (12.0 μ L; 0.1mmol; 1.0equiv) add in reaction flask, dissolve, under argon shield with the trichloromethane of 3.0ml; after stirring at room temperature reacts 24 hours; pour in normal hexane after reactant is concentrated, sedimentation and filtration is also dried to constant weight, obtains the poly-valerolactone product of white; transformation efficiency is 80%, the number-average molecular weight M of poly-fourth position dodecalactone
nfor 46700gmol
-1, dispersity PDI is 1.21.
Embodiment 5:
By γ-resorcinol formic acid (0.0154g; 0.1mmol; 1.0equiv), ε-decalactone (0.52ml; 3.0mmol; 30equiv) with phenylcarbinol (10.3 μ L; 0.1mmol, 1.0equiv) add in reaction flask, with the N of 3.0ml; dinethylformamide dissolves; under argon shield, 80 DEG C of stirring reactions, after 10 hours, are poured in normal hexane after reactant is concentrated; sedimentation and filtration is also dried to constant weight; obtain the poly-valerolactone product of white, transformation efficiency is 92%, the number-average molecular weight M of poly-ε-decalactone
nfor 4780gmol
-1, dispersity PDI is 1.23.
Embodiment 6:
By γ-resorcinol formic acid (0.0154g; 0.01mmol; 1.0equiv), δ-valerolactone (0.91ml; 10.0mmol; 1000equiv) with tetramethylolmethane (58.2 μ L; 1.0mmol; 100.0equiv) add in reaction flask, dissolve, under argon shield with the methylene dichloride of 1.0ml; 120 DEG C of stirring reactions are after 1 hour; pour in Skellysolve A after reactant is concentrated, sedimentation and filtration is also dried to constant weight, obtains the poly-valerolactone product of white; transformation efficiency is 93%, the number-average molecular weight M of poly-valerolactone
nfor 370gmol
-1, dispersity PDI is 1.21.
Embodiment 7:
By γ-resorcinol formic acid (0.0154g; 0.1mmol; 1.0equiv), δ-valerolactone (9.1ml; 100.0mmol; 1000equiv) with phenylcarbinol (10.3 μ L; 0.1mmol; 1.0equiv) add in reaction flask, do not add solvent, under argon shield; at 200 DEG C, stirring reaction is after 6 hours; pour in methyl alcohol after reactant is concentrated, sedimentation and filtration is also dried to constant weight, obtains the poly-valerolactone product of white; transformation efficiency is 91%, the number-average molecular weight M of poly-valerolactone
nfor 90200gmol
-1, dispersity PDI is 1.3.
Claims (10)
1. prepare a method for polylactone, it is characterized in that:
With δ-valerolactone, fourth position caprolactone, fourth position caprylolactone, fourth position decalactone, fourth position nonalactone, fourth position dodecalactone, 3-methyl-5-valerolactone, 6-caprolactone, ε-decalactone or ε-dodecalactone are monomer, with such as formula the γ shown in (I)-resorcinol formic acid for catalyzer, take alcohol compound as initiator, temperature of reaction is 0 ~ 200 DEG C, have solvent or solvent-free under, monomer generation ring-opening polymerization generates corresponding polylactone.
2. method according to claim 1, is characterized in that: described monomer is δ-valerolactone, fourth position caprolactone, fourth position dodecalactone, ε-decalactone or 6-caprolactone.
3. preparation method according to claim 1, it is characterized in that: described preparation method adopts has solvent or without solution polymerization, described when having a solvent, solvent comprises acetone, pimelinketone, dioxane, tetrahydrofuran (THF), benzene,toluene,xylene, methylene dichloride, trichloromethane, tetrachloromethane, N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide, acetonitrile.
4. preparation method according to claim 3, is characterized in that: described solvent is tetrahydrofuran (THF), toluene, methylene dichloride, trichloromethane, DMF.
5. preparation method according to claim 1, is characterized in that: described alcohol compound is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, phenylcarbinol, phenylethyl alcohol, ethylene glycol, condensed ethandiol, tetramethylolmethane, propiolic alcohol, 6-azido--1-hexanol, N-(2-hydroxyethyl) maleimide, 5-hexen-1-ol, water.
6. according to any one preparation method described in claim 1 to 5, it is characterized in that: the mol ratio of described monomer and catalyzer γ-resorcinol formic acid is 1-1000; The mol ratio of initiator and organic catalyst γ-resorcinol formic acid is 0.01-100.
7. according to any one preparation method described in claim 1 to 5, it is characterized in that: described preparation method completes under vacuum or rare gas element, vacuum tightness is 1 ~ 500 handkerchief, and rare gas element is.
8. according to any one preparation method described in claim 1 to 5, it is characterized in that: the initial reaction concentration of described monomer is 0.1mol/L ~ 100mol/L.
9. according to any one preparation method described in claim 1 to 5, it is characterized in that: at the end of described preparation method also comprises reaction, add terminator, described terminator is triethylamine.
10. the preparation method according to claim 1 or 9, is characterized in that: described preparation method adds precipitating solvent again or directly adds precipitating solvent after adding terminator, and described precipitating solvent is methyl alcohol, ethanol, ether, normal hexane or Skellysolve A.
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Cited By (7)
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| CN106832243A (en) * | 2017-02-15 | 2017-06-13 | 中山大学惠州研究院 | A kind of method that polycaprolactone is prepared without metal catalytic |
| CN107417899A (en) * | 2017-05-25 | 2017-12-01 | 南京工业大学 | A kind of method of cyclic compound ring-opening polymerisation |
| WO2018196730A1 (en) * | 2017-04-28 | 2018-11-01 | 南京工业大学 | Preparation method for polyester |
| CN109575249A (en) * | 2018-12-26 | 2019-04-05 | 大连大学 | A kind of polycaprolactone/nano hydroxyapatite composite material and preparation method thereof |
| WO2023068345A1 (en) * | 2021-10-22 | 2023-04-27 | 株式会社クラレ | Β-METHYL-δ-VALEROLACTONE POLYMER |
| WO2023068346A1 (en) * | 2021-10-22 | 2023-04-27 | 株式会社クラレ | Β-METHYL-δ-VALEROLACTONE POLYMER |
| CN117362605A (en) * | 2023-11-08 | 2024-01-09 | 武汉中科先进材料科技有限公司 | Bio-based polycaprolactone polyol and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832243A (en) * | 2017-02-15 | 2017-06-13 | 中山大学惠州研究院 | A kind of method that polycaprolactone is prepared without metal catalytic |
| WO2018196730A1 (en) * | 2017-04-28 | 2018-11-01 | 南京工业大学 | Preparation method for polyester |
| US11015021B2 (en) | 2017-04-28 | 2021-05-25 | Nanjing Tech University | Method for preparation of a polyester |
| CN107417899A (en) * | 2017-05-25 | 2017-12-01 | 南京工业大学 | A kind of method of cyclic compound ring-opening polymerisation |
| CN109575249A (en) * | 2018-12-26 | 2019-04-05 | 大连大学 | A kind of polycaprolactone/nano hydroxyapatite composite material and preparation method thereof |
| CN109575249B (en) * | 2018-12-26 | 2021-05-14 | 大连大学 | Polycaprolactone/nano-hydroxyapatite composite material and preparation method thereof |
| WO2023068345A1 (en) * | 2021-10-22 | 2023-04-27 | 株式会社クラレ | Β-METHYL-δ-VALEROLACTONE POLYMER |
| WO2023068346A1 (en) * | 2021-10-22 | 2023-04-27 | 株式会社クラレ | Β-METHYL-δ-VALEROLACTONE POLYMER |
| CN117362605A (en) * | 2023-11-08 | 2024-01-09 | 武汉中科先进材料科技有限公司 | Bio-based polycaprolactone polyol and preparation method thereof |
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Inventor after: Guo Kai Inventor after: Xu Jiaxi Inventor after: Li Zhenjiang Inventor after: Hu Xin Inventor after: Zhu Ning Inventor after: Liu Jingjing Inventor after: Xu Songquan Inventor after: Pan Xianfu Inventor after: Liu Jiaqi Inventor before: Guo Kai Inventor before: Xu Jiaxi Inventor before: Li Zhenjiang Inventor before: Liu Jingjing Inventor before: Xu Songquan Inventor before: Pan Xianfu Inventor before: Liu Jiaqi |