JP2000224996A - Production optically active polyester - Google Patents
Production optically active polyesterInfo
- Publication number
- JP2000224996A JP2000224996A JP11029513A JP2951399A JP2000224996A JP 2000224996 A JP2000224996 A JP 2000224996A JP 11029513 A JP11029513 A JP 11029513A JP 2951399 A JP2951399 A JP 2951399A JP 2000224996 A JP2000224996 A JP 2000224996A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- chiral carbon
- lactone
- hydrolase
- active polyester
- 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.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 150000002596 lactones Chemical class 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 102000004157 Hydrolases Human genes 0.000 claims abstract description 19
- 108090000604 Hydrolases Proteins 0.000 claims abstract description 19
- DQGSJTVMODPFBK-UHFFFAOYSA-N oxacyclotridecan-2-one Chemical compound O=C1CCCCCCCCCCCO1 DQGSJTVMODPFBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 108090001060 Lipase Proteins 0.000 claims abstract description 14
- 102000004882 Lipase Human genes 0.000 claims abstract description 14
- 239000004367 Lipase Substances 0.000 claims abstract description 14
- 235000019421 lipase Nutrition 0.000 claims abstract description 14
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 11
- 102000004190 Enzymes Human genes 0.000 abstract description 13
- 108090000790 Enzymes Proteins 0.000 abstract description 13
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 abstract description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 229920002988 biodegradable polymer Polymers 0.000 abstract description 3
- 239000004621 biodegradable polymer Substances 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229940088598 enzyme Drugs 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- NYBXFCLDEATPCM-UHFFFAOYSA-N 3-methyloxetan-2-one Chemical compound CC1COC1=O NYBXFCLDEATPCM-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 241000589516 Pseudomonas Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010701 ester synthesis reaction Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- SYTBZMRGLBWNTM-SNVBAGLBSA-N (R)-flurbiprofen Chemical compound FC1=CC([C@H](C(O)=O)C)=CC=C1C1=CC=CC=C1 SYTBZMRGLBWNTM-SNVBAGLBSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 2
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 2
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 2
- 108010060309 Glucuronidase Proteins 0.000 description 2
- 102000053187 Glucuronidase Human genes 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MVOSYKNQRRHGKX-UHFFFAOYSA-N 11-Undecanolactone Chemical compound O=C1CCCCCCCCCCO1 MVOSYKNQRRHGKX-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ZIIUUSVHCHPIQD-UHFFFAOYSA-N 2,4,6-trimethyl-N-[3-(trifluoromethyl)phenyl]benzenesulfonamide Chemical compound CC1=CC(C)=CC(C)=C1S(=O)(=O)NC1=CC=CC(C(F)(F)F)=C1 ZIIUUSVHCHPIQD-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- ULKFLOVGORAZDI-UHFFFAOYSA-N 3,3-dimethyloxetan-2-one Chemical compound CC1(C)COC1=O ULKFLOVGORAZDI-UHFFFAOYSA-N 0.000 description 1
- ZOMPBXWFMAJRRU-UHFFFAOYSA-N 3-ethyloxiran-2-one Chemical compound CCC1OC1=O ZOMPBXWFMAJRRU-UHFFFAOYSA-N 0.000 description 1
- JFVQYQDTHWLYHG-UHFFFAOYSA-N 6-ethyloxan-2-one Chemical compound CCC1CCCC(=O)O1 JFVQYQDTHWLYHG-UHFFFAOYSA-N 0.000 description 1
- -1 8-octonolide Chemical compound 0.000 description 1
- 108010013043 Acetylesterase Proteins 0.000 description 1
- 241000590020 Achromobacter Species 0.000 description 1
- 241000588986 Alcaligenes Species 0.000 description 1
- 102000004400 Aminopeptidases Human genes 0.000 description 1
- 108090000915 Aminopeptidases Proteins 0.000 description 1
- 101100316860 Autographa californica nuclear polyhedrosis virus DA18 gene Proteins 0.000 description 1
- 108010051152 Carboxylesterase Proteins 0.000 description 1
- 102000013392 Carboxylesterase Human genes 0.000 description 1
- 108090000317 Chymotrypsin Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VLSVVMPLPMNWBH-UHFFFAOYSA-N Dihydro-5-propyl-2(3H)-furanone Chemical compound CCCC1CCC(=O)O1 VLSVVMPLPMNWBH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical group CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 102000005486 Epoxide hydrolase Human genes 0.000 description 1
- 108020002908 Epoxide hydrolase Proteins 0.000 description 1
- 108010088842 Fibrinolysin Proteins 0.000 description 1
- 108010093031 Galactosidases Proteins 0.000 description 1
- 102000002464 Galactosidases Human genes 0.000 description 1
- 108010056771 Glucosidases Proteins 0.000 description 1
- 102000004366 Glucosidases Human genes 0.000 description 1
- 108010013563 Lipoprotein Lipase Proteins 0.000 description 1
- 102000017055 Lipoprotein Lipase Human genes 0.000 description 1
- 241001661345 Moesziomyces antarcticus Species 0.000 description 1
- 102000005398 Monoacylglycerol Lipase Human genes 0.000 description 1
- 108020002334 Monoacylglycerol lipase Proteins 0.000 description 1
- 102100036617 Monoacylglycerol lipase ABHD2 Human genes 0.000 description 1
- 241000235395 Mucor Species 0.000 description 1
- 108010019160 Pancreatin Proteins 0.000 description 1
- 108030001966 Phloretin hydrolases Proteins 0.000 description 1
- 108010064785 Phospholipases Proteins 0.000 description 1
- 102000015439 Phospholipases Human genes 0.000 description 1
- 241000235527 Rhizopus Species 0.000 description 1
- 101000693619 Starmerella bombicola Lactone esterase Proteins 0.000 description 1
- 108010055297 Sterol Esterase Proteins 0.000 description 1
- 102000000019 Sterol Esterase Human genes 0.000 description 1
- 108090000787 Subtilisin Proteins 0.000 description 1
- 108090000631 Trypsin Proteins 0.000 description 1
- 102000004142 Trypsin Human genes 0.000 description 1
- 108010027199 Xylosidases Proteins 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960002376 chymotrypsin Drugs 0.000 description 1
- FYTRVXSHONWYNE-UHFFFAOYSA-N delta-octanolide Chemical compound CCCC1CCCC(=O)O1 FYTRVXSHONWYNE-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002340 glycosyl compounds Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BTLSLHNLDQCWKS-UHFFFAOYSA-N oxocan-2-one Chemical compound O=C1CCCCCCO1 BTLSLHNLDQCWKS-UHFFFAOYSA-N 0.000 description 1
- 229940055695 pancreatin Drugs 0.000 description 1
- 108020004410 pectinesterase Proteins 0.000 description 1
- 229940012957 plasmin Drugs 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 108010038851 tannase Proteins 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 229960001322 trypsin Drugs 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光学活性ポリエス
テルの製造方法に関する。更に詳しくは、簡便且つ穏和
な条件で安価に光学活性ポリエステルを製造する方法に
関する。[0001] The present invention relates to a method for producing an optically active polyester. More specifically, the present invention relates to a method for producing an optically active polyester at low cost under simple and mild conditions.
【０００２】[0002]
【従来の技術】光学活性ポリエステルは生分解性高分子
として有用であることが知られている。とくに、種々の
微生物が生産するポリ（Ｒ−３−ヒドロキシアルカノエ
ート）は、高分子材料としての優れた物性や容易な生分
解性から注目されている。一方、酵素触媒による穏和な
条件下でラクトン類の開環重合が進行することが知られ
ており、当該手法を用いて光学活性ポリエステルを合成
する試みが成されている。例えばＭａｃｒｏｍｏｌｅｃ
ｕｌｅｓ，２９巻、４５９１ページ（１９９６年）で
は、ラセミ体のα−メチル−β−プロピオラクトンをリ
パーゼ触媒を用いて開環重合を進行させることにより、
Ｓ体富化の光学活性ポリエステルであるポリ（α-メチ
ル−β−プロピオラクトン）を合成する方法が示されて
いる。しかしながら、当該方法で得られるポリエステル
は単独重合体であり、従ってポリエステルの物性は限定
され、コスト的にも問題点があった。更に、キラル炭素
を有するラクトンとキラル炭素を有さないラクトンとを
加水分解酵素存在下に反応させることを特徴とする光学
活性ポリエステルの製造方法の報告例はなかった。2. Description of the Related Art Optically active polyesters are known to be useful as biodegradable polymers. In particular, poly (R-3-hydroxyalkanoate) produced by various microorganisms has attracted attention because of its excellent physical properties as a polymer material and easy biodegradability. On the other hand, it is known that ring-opening polymerization of lactones proceeds under mild conditions catalyzed by an enzyme, and attempts have been made to synthesize optically active polyesters using this technique. For example, Macromolec
ules, vol. 29, p. 4591 (1996), by proceeding ring-opening polymerization of racemic α-methyl-β-propiolactone using a lipase catalyst.
A method for synthesizing an S-enriched optically active polyester, poly (α-methyl-β-propiolactone), is disclosed. However, the polyester obtained by this method is a homopolymer, and thus the physical properties of the polyester are limited, and there is a problem in cost. Furthermore, there has been no report on a method for producing an optically active polyester, which comprises reacting a lactone having a chiral carbon with a lactone having no chiral carbon in the presence of a hydrolase.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、簡便
且つ穏和な条件で安価にかつ物性の設計が容易な種々の
光学活性ポリエステルを提供することである。SUMMARY OF THE INVENTION It is an object of the present invention to provide various optically active polyesters which are simple, easy to use under mild conditions, inexpensive, and easy in designing physical properties.
【０００４】[0004]
【課題を解決するための手段】即ち本発明は、キラル炭
素を有するラクトンとキラル炭素を有さないラクトンと
を加水分解酵素存在下に反応させることを特徴とする光
学活性ポリエステルの製造方法に関する。That is, the present invention relates to a method for producing an optically active polyester, which comprises reacting a lactone having a chiral carbon with a lactone having no chiral carbon in the presence of a hydrolase.
【０００５】更に本発明は、キラル炭素を有するラクト
ンが、ラセミ体である上記光学活性ポリエステルの製造
方法に関する。Further, the present invention relates to a method for producing the above-mentioned optically active polyester, wherein the lactone having a chiral carbon is in a racemic form.
【０００６】更に本発明は、キラル炭素を有さないラク
トンが、12-ドデカノリドおよびε−カプロラクトンで
ある上記光学活性ポリエステルの製造方法に関する。Further, the present invention relates to a method for producing the above-mentioned optically active polyester, wherein the lactone having no chiral carbon is 12-dodecanolide and ε-caprolactone.
【０００７】更に本発明は、加水分解酵素が、リパーゼ
である上記光学活性ポリエステルの製造方法に関する。Further, the present invention relates to a method for producing the above optically active polyester, wherein the hydrolase is lipase.
【０００８】[0008]
【０００９】本発明において用いられるキラル炭素を有
するラクトンは、加水分解酵素と反応するものであれば
特に制限はないが、例えば、β−ブチロラクトン、α−
メチル−プロピオラクトン、γ−カプロラクトン、γ−
ヘプタノラクトン、γ−バレロラクトン、ε−ヘプタノ
ラクトン、ε−オクタノラクトン等が挙げられる。The lactone having a chiral carbon used in the present invention is not particularly limited as long as it reacts with a hydrolase, and examples thereof include β-butyrolactone and α-butyrolactone.
Methyl-propiolactone, γ-caprolactone, γ-
Heptanolactone, γ-valerolactone, ε-heptanolactone, ε-octanolactone and the like can be mentioned.
【００１０】本発明において用いられるキラル炭素を有
さないラクトンは、加水分解酵素と反応するものであれ
ば特に制限はないが、例えば、β−プロピオラクトン、
γ-ブチロラクトン、δ-バレロラクトン、ε-カプロラ
クトン、7-ヘプタノリド、8-オクトノリド、11-ウンデ
カノリド、12-ドデカノリド、15-ペンタデカノリド、16
-ヘキサドデカノリド、α、α−ジメチル−β−プロピ
オラクトン等が挙げられる。[0010] The lactone having no chiral carbon used in the present invention is not particularly limited as long as it reacts with a hydrolase. For example, β-propiolactone,
γ-butyrolactone, δ-valerolactone, ε-caprolactone, 7-heptanolide, 8-octonolide, 11-undecanolide, 12-dodecanolide, 15-pentadecanolide, 16
-Hexadodecanolide, α, α-dimethyl-β-propiolactone and the like.
【００１１】本発明は、加水分解酵素が触媒するエステ
ル合成反応とエナンチオ選択性とを利用することを特徴
としている。従って、本発明で用いる加水分解酵素は、
ラセミ体モノマーと反応してエステル合成反応を触媒
し、エナンチオ選択性を示すものであればとくに制限は
ない。例えばカルボキシエステラーゼ、リパーゼ、ホス
ホリパーゼ、アセチルエステラーゼ、ペクチンエステラ
ーゼ、コレステロールエステラ ーゼ、タンナーゼ、モ
ノアシルグリセロールリパーゼ、ラクトナーゼ、リポプ
ロテイ ンリパーゼ等のＥＣ（酵素番号）３．１群（丸
尾・田宮監修「酵素ハンドブック」朝 倉書店（１９８
２）等参照）に分類されるエステラーゼ、グルコシダー
ゼ、ガラクトシダーゼ、グルクロニダーゼ、キシロシダ
ーゼ等のグリコシル化合物に作用するＥＣ３．２群に分
類される加水分解酵素、エポキシドヒドラーゼ等のＥＣ
３．３群に分類される加水分解酵素、アミノペプチダー
ゼ、キモトリプシン、トリプシン、プラスミン、ズブチ
リシン等のペプチド結合に作用するＥＣ３．４群に分類
される加水分解酵素、フロレチンヒドラーゼ等のＥＣ
３．７群に分類される加水分解酵素等を挙げることがで
きる。The present invention is characterized by utilizing an ester synthesis reaction catalyzed by a hydrolase and enantioselectivity. Therefore, the hydrolase used in the present invention is:
There is no particular limitation as long as it reacts with the racemic monomer to catalyze the ester synthesis reaction and shows enantioselectivity. For example, EC (enzyme number) 3.1 group of carboxylesterase, lipase, phospholipase, acetylesterase, pectin esterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase, lipoprotein lipase, etc. (Enzyme Handbook supervised by Maruo and Tamiya) Asakura Shoten (198
2) etc.) ECs acting on glycosyl compounds such as esterases, glucosidases, galactosidases, glucuronidases, glucuronidases, xylosidases classified as EC3.2, ECs classified as hydrolytic enzymes and epoxide hydrolases classified into the group 3.2.
ECs acting on peptide bonds such as hydrolases, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin, etc. classified into group 3.3 Hydrolases, ECs such as phloretin hydrolase classified into group 3.4
Hydrolytic enzymes classified into the 3.7 group can be exemplified.
【００１２】上記エステラーゼのうち、グリセロールエ
ステルを加水分解し脂肪酸を遊離する酵素をとくにリパ
ーゼと呼ぶが、リパーゼは収率良くエステル合成反応を
触媒し、さらに安価に入手できるなどの利点がある。従
って、本発明のポリエステルの製造方法においてもリパ
ーゼを用いることが好ましい。Among the above esterases, the enzyme that hydrolyzes glycerol esters to release fatty acids is particularly called a lipase. Lipases have the advantages of catalyzing the ester synthesis reaction with high yield and being available at a low cost. Therefore, it is preferable to use lipase also in the method for producing the polyester of the present invention.
【００１３】リパーゼには種々の起源のものを使用でき
るが、好ましいものとして、シュードモナス（Pseudomo
nas）属、アルカリゲネス（Alcaligenes）属、アクロモ
バクター（Achromobacter）属、カンジダ（Candida）
属、アスペルギルス（Aspergillus）属、リゾプス（Rhi
zopus）属、ムコール（Mucor）属等の微生物から得られ
るリパーゼ、植物種子から得られるリパーゼ、動物組織
から得られるリパーゼ、さらに、パンクレアチン、ステ
アプシン等を挙げることができる。このうち、シュード
モナス属、カンジダ属、アスペルギルス属の微生物由来
のリパーゼを用いることが望ましい。本発明において
は、２種類以上の加水分解酵素を混合して用いても良
く、また、酵素の安定化や反応後の回収を容易にするた
めに、公知の方法で固定化した酵素を用いることも可能
である。Although lipases of various origins can be used, Pseudomonas (Pseudomo
nas), Alcaligenes, Achromobacter, Candida
Genus, Aspergillus, Rhizopus (Rhi
Examples include lipase obtained from microorganisms such as genus zopus and Mucor, lipase obtained from plant seeds, lipase obtained from animal tissues, and pancreatin and stearpsin. Among them, it is desirable to use a lipase derived from microorganisms of the genera Pseudomonas, Candida and Aspergillus. In the present invention, two or more types of hydrolases may be used as a mixture, and an enzyme immobilized by a known method is used in order to stabilize the enzyme and facilitate recovery after the reaction. Is also possible.
【００１４】本発明の上記ラクトンと加水分解酵素との
反応において、必要に応じて溶媒を用いることができ
る。溶媒としては加水分解酵素の活性を妨げないものが
好ましいが、例えば、ヘキサン、シクロヘキサン、イソ
オクタン、ヘプタン、ベンゼン、トルエン、ジオキサ
ン、テトラヒドロフラン、イソプロパノール、ｔ−アミ
ルアルコール、アセトニトリル、酢酸エチル、エーテ
ル、イソプロピルエーテルが挙げられる。特に好ましい
溶媒として、イソオクタン、ヘプタンが挙げられる。In the reaction of the lactone with the hydrolase of the present invention, a solvent can be used if necessary. As the solvent, those which do not hinder the activity of the hydrolase are preferable, for example, hexane, cyclohexane, isooctane, heptane, benzene, toluene, dioxane, tetrahydrofuran, isopropanol, t-amyl alcohol, acetonitrile, ethyl acetate, ether, isopropyl ether Is mentioned. Particularly preferred solvents include isooctane and heptane.
【００１５】本発明の製造方法において、キラル炭素を
有するラクトンおよびキラル炭素を有さないラクトンが
固体または液体の状態を維持し、且つ、固体である加水
分解酵素と分散状態を維持していても何ら問題はない。In the production method of the present invention, the lactone having a chiral carbon and the lactone having no chiral carbon can be maintained in a solid or liquid state and in a dispersed state with a solid hydrolase. There is no problem at all.
【００１６】本発明において、キラル炭素を有するラク
トン１モルに対してキラル炭素を有さないラクトンは、
０．００１〜１０００モル％使用するのが好ましく、さ
らに好ましくは０．０１〜１００モル％使用することが
望ましい。反応温度は酵素の失活しない範囲である−１
０〜１２０ ℃が好ましく、特に好ましくは２０〜８０
℃が望ましい。In the present invention, the lactone having no chiral carbon per mole of the lactone having chiral carbon is
It is preferably used in an amount of 0.001 to 1000 mol%, more preferably 0.01 to 100 mol%. The reaction temperature is within a range where the enzyme is not deactivated-1.
The temperature is preferably from 0 to 120 ° C, particularly preferably from 20 to 80 ° C.
C is desirable.
【００１７】本発明において、加水分解酵素の添加量
は、用いる加水分解酵素のエステル合成能により適宜加
減すれば良いが、好ましくはキラル炭素を有するラクト
ンの量に対し０．０１〜１０００重量％、さらに好まし
くは０．１〜１００重量％とすれば良い。このとき、
酵素を大量に使用しても副反応は生じず、得られるポリ
エステルの精製操作に支障を来たすことはない。In the present invention, the amount of the hydrolase added may be appropriately adjusted depending on the ester synthesizing ability of the hydrolase used, but is preferably 0.01 to 1000% by weight based on the amount of the lactone having a chiral carbon. More preferably, it may be 0.1 to 100% by weight. At this time,
Even if a large amount of the enzyme is used, no side reaction occurs, and the operation of purifying the obtained polyester is not hindered.
【００１８】本発明において得られるポリエステルの数
平均分子量は、ＧＰＣより求めたポリスチレン換算の分
子量で３００〜３００，０００、通常は５００〜１０
０，０００の範囲である。The number average molecular weight of the polyester obtained in the present invention is 300 to 300,000 in terms of polystyrene equivalent molecular weight determined by GPC, usually 500 to 10
It is in the range of 0000.
【００１９】通常、光学活性ポリマーの合成方法は、ラ
セミ体原料からキラルなモノマーを得、このものを重合
する方法と、ラセミ体モノマーから光学活性ポリマーを
直接得る方法の２つがある。本発明は、酵素が有するエ
ナンチオ選択性を利用するものであり、ラセミ体モノマ
ーであるキラル炭素を有するラクトンから一段階で光学
活性ポリマーであるポリエステルを得ることができる。
さらに本発明では、重合反応に関与しなかった未反応の
キラル炭素を有するラクトンの光学純度は１００％であ
ることから、ラセミ体であるキラル炭素を有するラクト
ンの光学分割方法としても有用である。In general, there are two methods for synthesizing an optically active polymer: a method of obtaining a chiral monomer from a racemic material and polymerizing the same, and a method of directly obtaining an optically active polymer from a racemic monomer. The present invention utilizes the enantioselectivity possessed by the enzyme, and can obtain a polyester which is an optically active polymer in one step from a lactone having a chiral carbon which is a racemic monomer.
Furthermore, in the present invention, the lactone having an unreacted chiral carbon which did not participate in the polymerization reaction has an optical purity of 100%, and thus is also useful as an optical resolution method for a lactone having a racemic chiral carbon.
【００２０】[0020]
【実施例】以下、本発明を実施例により詳細に説明する
が、本発明はこれらに限定されるものではない。 （実施例１）ラセミ体のβ−ブチロラクトン（ｅｅ値0
％）1ミリモル（0.086グラム）、１２−ドデカノリド1
ミリモル（0.20グラム）にCandida antarctica由来のリ
パーゼ50ミリグラム、イソオクタン５mLを加えた。この
ものを６０℃で６時間加熱した。その後クロロホルムを
30mL加え、濾過により酵素を除去し、濾液を減圧下に濃
縮し、ポリマーを真空下乾燥した。収量0.26グラム。ポ
リスチレン換算で求めた数平均分子量はGPCより１５０
０であった。１２−ドデカノリド、β−ブチロラクトン
の転化率をガスクロマトグラフィーにより求めたとこ
ろ、１２−ドデカノリドの転化率は１００％、β−ブチ
ロラクトンの転化率は６７％であった。未反応β−プチ
ロラクトンの光学純度を光学活性カラムを装着したガス
クロマトグラフィーにより求めたところ、ｅｅ値は１０
０％であり、絶対配置はＲ体であった。得られたポリマ
ーの比旋光度を室温下、クロロホルム溶媒にて365nmの
波長で測定したところ、+４．３（ｃ＝５．０）であっ
た（かっこ内のｃはg/dL）。また、13Ｃ−ＮＭＲ分析よ
り、得られたポリマーはランダム共重合体であることが
判った。The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 Racemic β-butyrolactone (ee value 0
%) 1 mmol (0.086 g), 12-dodecanolide 1
To 50 milligrams (0.20 grams) of lipase from Candida antarctica and 5 mL of isooctane were added. This was heated at 60 ° C. for 6 hours. Then chloroform
30 mL was added, the enzyme was removed by filtration, the filtrate was concentrated under reduced pressure, and the polymer was dried under vacuum. Yield 0.26 grams. The number average molecular weight determined in terms of polystyrene is 150 from GPC.
It was 0. When the conversion of 12-dodecanolide and β-butyrolactone was determined by gas chromatography, the conversion of 12-dodecanolide was 100% and the conversion of β-butyrolactone was 67%. When the optical purity of unreacted β-butyrolactone was determined by gas chromatography equipped with an optically active column, the ee value was 10
0%, and the absolute configuration was R-form. The specific rotation of the obtained polymer was measured at room temperature with a chloroform solvent at a wavelength of 365 nm, and was +4.3 (c = 5.0) (c in parentheses is g / dL). From 13 C-NMR analysis, it was found that the obtained polymer was a random copolymer.
【００２１】（実施例２）イソオクタンの代わりに、ヘ
プタンを用いた以外は実施例１と同様に実験を行った。
収量0.27グラム。数平均分子量はGPC より１７００であ
った。１２−ドデカノリドの転化率は１００％、β−ブ
チロラクトンの転化率は76％、未反応β−プチロラクト
ンの光学純度（ｅｅ値）は１００％（絶対配置は Ｒ
体）であった。また、得られたポリマーの比旋光度は、
+3．３（ｃ＝５．３） であった。Example 2 An experiment was conducted in the same manner as in Example 1 except that heptane was used instead of isooctane.
Yield 0.27 grams. The number average molecular weight was 1,700 from GPC. The conversion of 12-dodecanolide is 100%, the conversion of β-butyrolactone is 76%, the optical purity (ee value) of unreacted β-butyrolactone is 100% (absolute configuration is R
Body). The specific rotation of the obtained polymer is
+3.3 (c = 5.3).
【００２２】（実施例３）１２−ドデカノリドの代わり
に、ε−カプロラクトン0.11グラムを用いた以外は実施
例１と同様に実験を行った。収量0.17グラム。数平均分
子量はGPCより２３００であった。ε−カプロラクトン
の転化率は１００％、β−プチロラクトンの転化率は７
１％、未反応β−プチロラクトンの光学純度（ｅｅ値）
は１００％（絶対配置はＲ体）であった。また、得られ
たポリマーの比旋光度は、+８．２（ｃ＝２ ．６）であ
った。Example 3 An experiment was carried out in the same manner as in Example 1 except that 0.11 g of ε-caprolactone was used instead of 12-dodecanolide. Yield 0.17 grams. The number average molecular weight was 2,300 from GPC. The conversion of ε-caprolactone is 100%, and the conversion of β-butyrolactone is 7%.
1%, optical purity of unreacted β-butyrolactone (ee value)
Was 100% (the absolute configuration was R-form). The specific rotation of the obtained polymer was +8.2 (c = 2.6).
【００２３】[0023]
【発明の効果】安価で様々な物性を有するキラル炭素を
有さないラクトンを用いることにより、簡便且つ穏和な
条件で安価でかつ様々な物性を有する光学活性ポリエス
テルが製造することができた。As described above, the use of inexpensive and non-chiral carbon-free lactones having various physical properties makes it possible to produce inexpensive optically active polyesters having various physical properties under simple and mild conditions.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4B064 AD83 CB26 CB30 CC30 CD08 DA16 DA20 4J029 AA02 AB04 AC02 AD01 AE04 EG02 EG04 EG05 EG06 EG07 EG08 EG09 EG10 JE011 KB05 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4B064 AD83 CB26 CB30 CC30 CD08 DA16 DA20 4J029 AA02 AB04 AC02 AD01 AE04 EG02 EG04 EG05 EG06 EG07 EG08 EG09 EG10 JE011 KB05
Claims (4)
を有さないラクトンとを加水分解酵素存在下に反応させ
ることを特徴とする光学活性ポリエステルの製造方法。1. A process for producing an optically active polyester, comprising reacting a lactone having a chiral carbon with a lactone having no chiral carbon in the presence of a hydrolase.
である請求項１記載の光学活性ポリエステルの製造方
法。2. The method for producing an optically active polyester according to claim 1, wherein the lactone having a chiral carbon is in a racemic form.
デカノリドまたはε−カプロラクトンである請求項１ま
たは２記載の光学活性ポリエステルの製造方法。3. The process for producing an optically active polyester according to claim 1, wherein the lactone having no chiral carbon is 12-dodecanolide or ε-caprolactone.
〜３のいずれか記載の光学活性ポリエステルの製造方
法。4. The method according to claim 1, wherein the hydrolase is a lipase.
4. The method for producing an optically active polyester according to any one of items 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11029513A JP2000224996A (en) | 1999-02-08 | 1999-02-08 | Production optically active polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11029513A JP2000224996A (en) | 1999-02-08 | 1999-02-08 | Production optically active polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000224996A true JP2000224996A (en) | 2000-08-15 |
Family
ID=12278190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11029513A Pending JP2000224996A (en) | 1999-02-08 | 1999-02-08 | Production optically active polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000224996A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012189772A (en) * | 2011-03-10 | 2012-10-04 | Ricoh Co Ltd | Toner, two-component developer, image formation method, image formation device and process cartridge |
-
1999
- 1999-02-08 JP JP11029513A patent/JP2000224996A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012189772A (en) * | 2011-03-10 | 2012-10-04 | Ricoh Co Ltd | Toner, two-component developer, image formation method, image formation device and process cartridge |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Matsumura | Enzyme‐catalyzed synthesis and chemical recycling of polyesters | |
| Patil et al. | Enzymatic synthesis of a sucrose‐containing linear polyester in nearly anhydrous organic media | |
| Matsumura | Enzymatic synthesis of polyesters via ring-opening polymerization | |
| Nobes et al. | Lipase-catalyzed ring-opening polymerization of lactones: a novel route to poly (hydroxyalkanoate) s | |
| CA2734893C (en) | Method for preparing long-chain hydroxyacids, diacids and oligomers and polymers thereof | |
| Khmelnitsky et al. | Biocatalysis in nonaqueous solvents | |
| Chaudhary et al. | Biocatalytic solvent‐free polymerization to produce high molecular weight polyesters | |
| Gross et al. | Polyester and polycarbonate synthesis by in vitro enzyme catalysis | |
| Linko et al. | Lipase-catalyzed synthesis of poly (1, 4-butyl sebacate) from sebacic acid or its derivatives with 1, 4-butanediol | |
| Pastorino et al. | Lipase-catalyzed degradation of poly (ε-caprolactone) | |
| Rodríguez-Contreras et al. | Enzymatic degradation of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) by commercial lipases | |
| Santos et al. | Polyester hydrolytic and synthetic activity catalyzed by the medium-chain-length poly (3-hydroxyalkanoate) depolymerase from Streptomyces venezuelae SO1 | |
| Ohara et al. | Lipase-catalyzed oligomerization and hydrolysis of alkyl lactates: direct evidence in the catalysis mechanism that enantioselection is governed by a deacylation step | |
| Kobayashi et al. | In vitro polyester synthesis via enzymatic polymerization | |
| US6924129B2 (en) | Enzyme-catalyzed esterification of pendant carboxylic acid groups | |
| Gumel et al. | Single‐step lipase‐catalyzed functionalization of medium‐chain‐length polyhydroxyalkanoates | |
| Kumar et al. | Poly (3-hydroxybutyrate)-depolymerase from Pseudomonas lemoignei: catalysis of esterifications in organic media | |
| Santos et al. | Poly (3-hydroxyoctanoate) depolymerase from Pseudomonas fluorescens GK13: Catalysis of ester-forming reactions in non-aqueous media | |
| Wallace et al. | Resolution of a chiral ester by lipase-catalyzed transesterification with polyethylene glycol in organic media | |
| Ohya et al. | Polycondensation of α-hydroxy acids by enzymes or PEG-modified enzymes in organic media | |
| Li et al. | Highly efficient ring-opening polymerization of ɛ-caprolactone catalyzed by a recombinant Escherichia coli whole-cell biocatalyst | |
| JP2000224996A (en) | Production optically active polyester | |
| Wang et al. | Lipase-catalyzed polyester synthesis | |
| Shimizu et al. | Optical resolution of pantolactone by a novel fungal enzyme, lactonohydrolase | |
| JP3690028B2 (en) | Polyester manufacturing method |