JPH07138253A - Production of lactide - Google Patents
Production of lactideInfo
- Publication number
- JPH07138253A JPH07138253A JP31258893A JP31258893A JPH07138253A JP H07138253 A JPH07138253 A JP H07138253A JP 31258893 A JP31258893 A JP 31258893A JP 31258893 A JP31258893 A JP 31258893A JP H07138253 A JPH07138253 A JP H07138253A
- Authority
- JP
- Japan
- Prior art keywords
- lactic acid
- lactide
- stage
- optical purity
- oligomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【0001】[0001]
【産業上の利用分野】本発明は光学純度の高いL−また
は、D−ラクチドの製造法に関する。TECHNICAL FIELD The present invention relates to a method for producing L- or D-lactide having high optical purity.
【0002】[0002]
【従来の技術および課題】ラクチドは乳酸二分子が脱水
して生じた環状ジエステルであり、ポリ乳酸の原料とな
る。ラクチドの製造法として、例えば特開昭63−101378
号公報には、まず乳酸を脱水、濃縮して中間体であるオ
リゴマー得て、これにスズ系触媒を加えて高真空中にて
200℃程度に加熱して分解、環状二量化してラクチド
を留去する製法が記載されている。2. Description of the Related Art Lactide is a cyclic diester formed by dehydration of two lactic acid molecules and is a raw material for polylactic acid. As a method for producing lactide, for example, JP-A-63-101378 is used.
In the gazette, first, lactic acid is dehydrated and concentrated to obtain an intermediate oligomer, which is added with a tin-based catalyst and heated at about 200 ° C. in a high vacuum for decomposition and cyclic dimerization to give lactide. The manufacturing method of distilling off is described.
【0003】[0003]
【化1】 しかしながら、このような製法では反応液中に環状二量
体であるラクチドのほか、低重合度の直鎖オリゴマーが
多量に含まれる。このため、ラクチドの留出時にこれら
オリゴマーがラクチドと共に留出し、製品ラクチドの光
学純度および収率が低下する。一方、これを防ぐため、
乳酸の脱水、濃縮度を高くすると濃縮時に乳酸が留出し
ラクチドの収率が低下し、光学純度も低下する。[Chemical 1] However, in such a production method, in addition to lactide which is a cyclic dimer, the reaction solution contains a large amount of a linear oligomer having a low degree of polymerization. Therefore, when distilling lactide, these oligomers distill together with lactide, and the optical purity and yield of the product lactide decrease. On the other hand, to prevent this,
When the degree of dehydration and concentration of lactic acid is increased, lactic acid is distilled out at the time of concentration, the yield of lactide is reduced, and the optical purity is also reduced.
【0004】本発明の目的は光学純度の高いラクチドを
高収率で製造する方法を提供することにある。An object of the present invention is to provide a method for producing lactide with high optical purity in high yield.
【0005】[0005]
【課題を解決するための手段】本発明は下記の(i)〜
(iii)の工程: (i)乳酸を加熱、濃縮する工程、(ii)前記の濃縮さ
れた乳酸を還流しながら脱水し乳酸オリゴマーを生成す
る工程、および(iii)前記の乳酸オリゴマーを触媒の
存在下に解重合して留去する工程を含むことを特徴とす
るラクチドの製造法を提供するものである。つぎにこれ
ら各工程について詳細に説明する。Means for Solving the Problems The present invention includes the following (i) to
Step (iii): (i) heating and concentrating lactic acid, (ii) dehydrating the concentrated lactic acid while refluxing to produce a lactic acid oligomer, and (iii) using the lactic acid oligomer as a catalyst. The present invention provides a method for producing lactide, which comprises a step of depolymerizing in the presence and distilling off. Next, each of these steps will be described in detail.
【0006】(i) 濃縮工程 本発明の第1の工程においては、乳酸を濃縮してオリゴ
マーの生成を行う。用いられる乳酸はL−乳酸、D−乳
酸のいずれであってもよい。このような乳酸は従来公知
の方法により製造されたものがいずれも用いられるが、
特に発酵法により製造した純度80%以上、光学純度9
9%以上のものであるのが好ましい。このような乳酸を
常圧下、温度130〜140℃にて加熱して単蒸留を行
い、ガスが発生しなくなるまで水を留去する。(I) Concentration Step In the first step of the present invention, lactic acid is concentrated to produce an oligomer. The lactic acid used may be either L-lactic acid or D-lactic acid. As such lactic acid, any one produced by a conventionally known method is used.
Especially, the purity of 80% or more produced by the fermentation method and the optical purity of 9
It is preferably 9% or more. Such lactic acid is heated at a temperature of 130 to 140 ° C. under normal pressure to perform simple distillation, and water is distilled off until no gas is generated.
【0007】(ii) 還流工程 前記の工程(ii)で得られた乳酸のオリゴマーを主成分
とする混合液を好ましくは減圧下、脱水しながら全還流
する。減圧は10〜100Torrとするのが好ましい。ま
た還流は温度130〜170℃にて3〜4時間行う。還
流は段階を別けて徐々に昇温するのが好ましい。例え
ば、第1段135±3℃、第2段150±3℃、第3段
160±3℃とするのが好ましい。このような還流によ
り乳酸は6〜10量体の直鎖のオリゴマーとなりラクチ
ドとの沸点の相異が大きくなり、分離が容易となる。還
流工程はさらに多段階化してもよく、また連続的に徐々
に温度上昇を行ない還流しなくなるまで加熱を行っても
よい。なお、ラクチドは融点95〜100℃の針状結晶
であり、還流管、配管の詰まりを防止するため105℃
程度に保温する。(Ii) Refluxing step The mixed solution containing the oligomer of lactic acid obtained in the above step (ii) as a main component is totally refluxed while dehydrating, preferably under reduced pressure. The reduced pressure is preferably 10 to 100 Torr. The reflux is performed at a temperature of 130 to 170 ° C. for 3 to 4 hours. It is preferable that the reflux temperature be gradually raised in stages. For example, it is preferable that the first stage is 135 ± 3 ° C., the second stage is 150 ± 3 ° C., and the third stage is 160 ± 3 ° C. By such refluxing, lactic acid becomes a 6 to 10-mer linear oligomer, and the difference in boiling point from lactide becomes large, which facilitates separation. The refluxing step may be performed in multiple stages, or the temperature may be continuously and gradually increased to perform heating until reflux is stopped. Lactide is a needle-shaped crystal with a melting point of 95 to 100 ° C., and 105 ° C. to prevent clogging of the reflux pipe and the pipe.
Keep it warm.
【0008】(iii) 留出工程 ついで、前記工程(ii)で得られた純度の高いオリゴマー
を環状二量化する。すなわち、環状二量化(エステル交
換反応)触媒を加え、好ましくは減圧下に加熱してラク
チドを留去する。ここで用いる触媒としては、従来公知
のものがいずれも用いることができ、例えばオクチル酸
スズ、三酸化アンチモン、酸化亜鉛などがいずれも用い
られる。加熱は10〜50Torrの減圧下、好ましくは1
90〜210℃にて行う。また、高真空、高温度の装置
を用いることによりさらにラクチドの収率が向上する。(Iii) Distillation step Next, the highly pure oligomer obtained in step (ii) is subjected to cyclic dimerization. That is, a cyclic dimerization (transesterification reaction) catalyst is added, and the mixture is preferably heated under reduced pressure to distill off lactide. As the catalyst used here, any conventionally known catalyst can be used, and for example, tin octylate, antimony trioxide, zinc oxide or the like can be used. Heating is performed under reduced pressure of 10 to 50 Torr, preferably 1
Perform at 90-210 ° C. Further, the yield of lactide is further improved by using a high vacuum and high temperature apparatus.
【0009】このように、従来の乳酸濃縮およびラクチ
ドの留出の2工程の間に所定の温度で還流を行い脱水す
る工程を加えると重合度の高いオリゴマー量が多くなり
ラクチドの単離が容易となった。本発明では乳酸を濃
縮、還流することによって乳酸の留出が防止でき、ラク
チドの光学純度が低下せず、ラクチドの収率が向上す
る。As described above, if a process of refluxing at a predetermined temperature and dehydration is added between the conventional two processes of lactic acid concentration and lactide distillation, the amount of oligomers having a high degree of polymerization increases and the lactide can be easily isolated. Became. In the present invention, distilling lactic acid can be prevented by concentrating and refluxing lactic acid, the optical purity of lactide does not decrease, and the yield of lactide improves.
【0010】[0010]
【実施例】つぎに本発明を実施例にもとづきさらに具体
的に説明する。EXAMPLES Next, the present invention will be described more specifically based on examples.
【0011】[実施例1]光学純度の99%以上のL−
乳酸(90重量%)からL−ラクチドを以下のようにして
合成した。[Example 1] L- of 99% or more of optical purity
L-lactide was synthesized from lactic acid (90% by weight) as follows.
【0012】ガラス製反応器(50L)に原料35kgを投
入し、原料乳酸を液温度135℃に加熱し、常圧で単蒸
留を行い30分間濃縮した。ついで、減圧下(13〜7
0Torr)にて全還流を行った。液温度設定を以下の3段
階で行い、各段階に収まり次第つぎの段階に進んだ。35 kg of the raw material was put into a glass reactor (50 L), the raw material lactic acid was heated to a liquid temperature of 135 ° C., and simple distillation was carried out under normal pressure to concentrate for 30 minutes. Then, under reduced pressure (13-7
Total reflux was performed at 0 Torr). The liquid temperature was set in the following three stages, and the process proceeded to the next stage as soon as it reached each stage.
【0013】第1段階:液温度135℃設定 第2段階:液温度150℃設定 第3段階:液温度160℃設定 ついで、オクチル酸スズを触媒を投入し減圧下(10〜
35Torr)で液温度200℃で単蒸留によりラクチドを
留出させた。配管詰まり防止のためコンデンサー温度は
105℃とした。以上の操作中、300rpmの撹拌を続
けた。結果を表1に示す。First stage: Liquid temperature set at 135 ° C. Second stage: Liquid temperature set at 150 ° C. Third stage: Liquid temperature set at 160 ° C. Then, tin octylate was added to the catalyst under reduced pressure (10 to 10 ° C.).
The lactide was distilled off by simple distillation at a liquid temperature of 200 ° C. at 35 Torr). The condenser temperature was set to 105 ° C. to prevent pipe clogging. During the above operation, stirring at 300 rpm was continued. The results are shown in Table 1.
【0014】[実施例2]光学純度の99%以上のL−
乳酸(90重量%)からL−ラクチドを以下のようにして
合成した。[Example 2] L- with 99% or more of optical purity
L-lactide was synthesized from lactic acid (90% by weight) as follows.
【0015】ガラス製反応器(50L)に原料35kgを投
入し、原料乳酸を液温度135℃に加熱し、常圧で単蒸
留を行い30分間濃縮した。ついで、減圧下(20〜7
0Torr)液温度を200℃に設定して全還流を行った。
ついで、オクチル酸スズを触媒を投入し減圧下(10〜
25Torr)で液温度200℃で単蒸留によりラクチドを
留出させた。配管詰まり防止のためコンデンサー温度は
105℃とした。以上の操作中、300rpmの撹拌を続
けた。結果を表1に示す。35 kg of the raw material was put into a glass reactor (50 L), the raw material lactic acid was heated to a liquid temperature of 135 ° C., and simple distillation was carried out under normal pressure to concentrate for 30 minutes. Then, under reduced pressure (20-7
(0 Torr) The liquid temperature was set to 200 ° C. to carry out total reflux.
Then, the catalyst was added with tin octylate under reduced pressure (10-
Lactide was distilled off by simple distillation at a liquid temperature of 200 ° C. at 25 Torr). The condenser temperature was set to 105 ° C. to prevent pipe clogging. During the above operation, stirring at 300 rpm was continued. The results are shown in Table 1.
【0016】[実施例3]光学純度の99%以上のL−
乳酸(90重量%)からL−ラクチドを以下のようにして
合成した。[Example 3] L- with 99% or more of optical purity
L-lactide was synthesized from lactic acid (90% by weight) as follows.
【0017】ガラス製反応器(50L)に原料35kgを投
入し、原料乳酸を液温度135℃に加熱し、常圧で単蒸
留を行い30分間濃縮した。ついで、減圧下(30〜6
0Torr)液温度を160℃に設定して全還流を行った。
ついで、オクチル酸スズを触媒を投入し減圧下(10〜
20Torr)で液温度200℃で単蒸留によりラクチドを
留出させた。配管詰まり防止のためコンデンサー温度は
105℃とした。以上の操作中、300rpmの撹拌を続
けた。結果を表1に示す。35 kg of the raw material was put into a glass reactor (50 L), the raw material lactic acid was heated to a liquid temperature of 135 ° C., and simple distillation was carried out under normal pressure to concentrate for 30 minutes. Then, under reduced pressure (30-6
(0 Torr) The liquid temperature was set to 160 ° C. to carry out total reflux.
Then, the catalyst was added with tin octylate under reduced pressure (10-
The lactide was distilled off by simple distillation at a liquid temperature of 200 ° C. at 20 Torr). The condenser temperature was set to 105 ° C. to prevent pipe clogging. During the above operation, stirring at 300 rpm was continued. The results are shown in Table 1.
【0018】 [表1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 試験No 純度(%) 収率(%) 光学純度(%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 実施例1 80.4 77.7 99.1 〃 2 85.9 82.9 91.7 〃 3 58.5 56.0 99.5 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 表1より明らかなように、本発明の製造法によれば光学
純度99%以上のL−乳酸(90重量%)から光学純度9
9.0%以上のL−ラクチドが、理論収量に対して収率
70%以上の高収率で得られる。[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Test No Purity (%) Yield (%) Optical purity (%) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 80.4 77 .7 99.1 〃 2 85.9 82.9 91.7 〃 3 58.5 56.0 99.5 ━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━ As is clear from Table 1, according to the production method of the present invention, L-lactic acid (90% by weight) having an optical purity of 99% or more was used to obtain an optical purity of 9%.
9.0% or more of L-lactide is obtained in a high yield of 70% or more with respect to the theoretical yield.
【0019】[0019]
【発明の効果】本発明の製造法によれば光学純度の高い
ラクチドが高収率にて得られる。According to the production method of the present invention, lactide having high optical purity can be obtained in high yield.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小原 仁実 京都市中京区西ノ京桑原町1番地 株式会 社島津製作所三条工場内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hitomi Ohara, No. 1 Kuwabara-cho, Nishinokyo, Nakagyo-ku, Kyoto City Stock Company Shimadzu Sanjo Factory
Claims (2)
れた乳酸を還流しながら脱水し乳酸オリゴマーを生成す
る工程、および(iii)前記の乳酸オリゴマーを触媒の
存在下に解重合して留去する工程を含むことを特徴とす
るラクチドの製造法。1. The following steps (i) to (iii): (i) heating and concentrating lactic acid, (ii) dehydrating the concentrated lactic acid while refluxing to produce a lactic acid oligomer, And (iii) a method for producing lactide, which comprises depolymerizing the lactic acid oligomer in the presence of a catalyst and distilling it off.
段階の温度条件にて還流を行う請求項1に記載のラクチ
ドの製造法。 第1段階:液温度135±3℃ 第2段階:液温度150±3℃ 第3段階:液温度160±3℃2. The following first to third steps in the step (ii):
The method for producing lactide according to claim 1, wherein the reflux is carried out under stepwise temperature conditions. First stage: Liquid temperature 135 ± 3 ° C Second stage: Liquid temperature 150 ± 3 ° C Third stage: Liquid temperature 160 ± 3 ° C
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5312588A JP2830896B2 (en) | 1993-11-17 | 1993-11-17 | Lactide production method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5312588A JP2830896B2 (en) | 1993-11-17 | 1993-11-17 | Lactide production method |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30694597A Division JPH10114769A (en) | 1997-11-10 | 1997-11-10 | Production of lactide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH07138253A true JPH07138253A (en) | 1995-05-30 |
JP2830896B2 JP2830896B2 (en) | 1998-12-02 |
Family
ID=18031013
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5312588A Expired - Lifetime JP2830896B2 (en) | 1993-11-17 | 1993-11-17 | Lactide production method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2830896B2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0808861A3 (en) * | 1996-05-24 | 1998-10-28 | KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. | Apparatus and method for producing 2-hydroxycarboxylic acid oligomer |
US6313319B1 (en) | 1998-09-25 | 2001-11-06 | Shimadzu Corporation | Method for purifying lactide and lactide for food additives |
WO2002060891A1 (en) * | 2001-01-31 | 2002-08-08 | Toyota Jidosha Kabushiki Kaisha | Process for producing lactide and process for producing polylactic acid starting with fermented lactic acid |
JP2002540090A (en) | 1999-03-22 | 2002-11-26 | ピユラク・バイオケム・ベー・ブイ | How to purify lactic acid on an industrial scale |
WO2010073512A1 (en) * | 2008-12-26 | 2010-07-01 | 株式会社クレハ | Method for producing glycolide |
JP2011173844A (en) * | 2010-02-25 | 2011-09-08 | Teijin Ltd | Method for producing purified lactide |
KR102235919B1 (en) * | 2019-10-28 | 2021-04-08 | 한국생산기술연구원 | Development of polylactic acid polymer with improved thermal and barrier properties |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63101378A (en) * | 1986-09-20 | 1988-05-06 | ベーリンガー インゲルハイム コマンディットゲゼルシャフト | Manufacture of lactide |
-
1993
- 1993-11-17 JP JP5312588A patent/JP2830896B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63101378A (en) * | 1986-09-20 | 1988-05-06 | ベーリンガー インゲルハイム コマンディットゲゼルシャフト | Manufacture of lactide |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0808861A3 (en) * | 1996-05-24 | 1998-10-28 | KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. | Apparatus and method for producing 2-hydroxycarboxylic acid oligomer |
US6313319B1 (en) | 1998-09-25 | 2001-11-06 | Shimadzu Corporation | Method for purifying lactide and lactide for food additives |
JP2002540090A (en) | 1999-03-22 | 2002-11-26 | ピユラク・バイオケム・ベー・ブイ | How to purify lactic acid on an industrial scale |
JP2011074084A (en) * | 1999-03-22 | 2011-04-14 | Purac Biochem Bv | Method of industrial-scale purification of lactic acid |
WO2002060891A1 (en) * | 2001-01-31 | 2002-08-08 | Toyota Jidosha Kabushiki Kaisha | Process for producing lactide and process for producing polylactic acid starting with fermented lactic acid |
US6569989B2 (en) | 2001-01-31 | 2003-05-27 | Toyota Jidosha Kabushiki Kaisha | Process for producing lactide and process for producing polylactic acid from fermented lactic acid employed as starting material |
WO2010073512A1 (en) * | 2008-12-26 | 2010-07-01 | 株式会社クレハ | Method for producing glycolide |
US8722907B2 (en) | 2008-12-26 | 2014-05-13 | Kureha Corporation | Production process of glycolide |
JP5584628B2 (en) * | 2008-12-26 | 2014-09-03 | 株式会社クレハ | Method for producing glycolide |
JP2011173844A (en) * | 2010-02-25 | 2011-09-08 | Teijin Ltd | Method for producing purified lactide |
KR102235919B1 (en) * | 2019-10-28 | 2021-04-08 | 한국생산기술연구원 | Development of polylactic acid polymer with improved thermal and barrier properties |
Also Published As
Publication number | Publication date |
---|---|
JP2830896B2 (en) | 1998-12-02 |
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