JPH06345856A - Method for producing aliphatic polyester - Google Patents
Method for producing aliphatic polyesterInfo
- Publication number
- JPH06345856A JPH06345856A JP13487893A JP13487893A JPH06345856A JP H06345856 A JPH06345856 A JP H06345856A JP 13487893 A JP13487893 A JP 13487893A JP 13487893 A JP13487893 A JP 13487893A JP H06345856 A JPH06345856 A JP H06345856A
- Authority
- JP
- Japan
- Prior art keywords
- aliphatic polyester
- germanium
- molecular weight
- acid
- producing
- 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
- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- 150000002291 germanium compounds Chemical class 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 10
- -1 sutures Substances 0.000 description 10
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 235000014655 lactic acid Nutrition 0.000 description 7
- 239000004310 lactic acid Substances 0.000 description 7
- 229920000747 poly(lactic acid) Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 6
- 239000004626 polylactic acid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- WXYNMTGBLWPTNQ-UHFFFAOYSA-N tetrabutoxygermane Chemical compound CCCCO[Ge](OCCCC)(OCCCC)OCCCC WXYNMTGBLWPTNQ-UHFFFAOYSA-N 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- 229940119177 germanium dioxide Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 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 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 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
- 239000003337 fertilizer Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- MIGSIHRFJAJEDQ-UHFFFAOYSA-N hexylgermanium Chemical compound CCCCCC[Ge] MIGSIHRFJAJEDQ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
(57)【要約】
【構成】 オキシ酸を脱水重縮合することにより、脂肪
族ポリエステルを製造する方法において、有機ゲルマニ
ウム化合物の存在下で脱水重縮合する脂肪族ポリエステ
ルの製造方法。
【効果】 高分子量であってかつ色調が良好の脂肪族ポ
リエステルを直接重縮合反応により容易に製造できる。(57) [Summary] [Structure] A method for producing an aliphatic polyester by dehydration polycondensation of an oxy acid, wherein the dehydration polycondensation is performed in the presence of an organic germanium compound. [Effect] An aliphatic polyester having a high molecular weight and good color tone can be easily produced by direct polycondensation reaction.
Description
【０００１】[0001]
【産業上の利用分野】本発明はオキシ酸の直接重縮合に
より脂肪族ポリエステルを製造する方法に関する。詳し
くは高分子量の脂肪族ポリエステルをオキシ酸から一段
反応で製造する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing an aliphatic polyester by direct polycondensation of an oxy acid. More specifically, it relates to a method for producing a high molecular weight aliphatic polyester from an oxyacid by a one-step reaction.
【０００２】[0002]
【従来の技術】ポリ乳酸、ポリグリコール酸あるいはこ
れらの共重合体などのオキシ酸からの脂肪族ポリエステ
ルは生分解性の高分子として注目され、例えば、縫合糸
等の医用材料、医薬、農薬、肥料等の徐放性材料等多方
面に利用されている。これらの用途のためには一般的に
機械的物性が高いことが好ましい。そのため、高分子量
のこれらポリマーを得るために、従来は乳酸、グリコー
ル酸からラクチド、グリコリドを製造し、これらを開環
重合して高分子量のポリラクチド、ポリグリコリドを製
造していた。この方法では高分子量のポリマーが得られ
るが２段反応であり、ラクチド、グリコリドを得るため
に多大の労力がかかり、経済的とは言えなかった。一
方、乳酸、グリコール酸を直接重縮合させる方法は、経
済的であるが、その反面、高分子量化できないという欠
点があり、工業化されてない。例えば、高分子量化の試
みとして重縮合触媒としてスズ化合物を用い、重合時に
流動パラフィンを添加させる方法（特開昭６２−６４８
２３）等も提案されているが、この例では約１万程度の
数平均分子量であり、工業的利用を考えた場合には充分
な分子量とはいえない。またＧｅＯ2 などの無機ゲルマ
ニウム化合物を用いた例（特開平５−４３６６５）も報
告されているが、得られるポリマーの色調及び分子量の
点で必らずしも充分とは言えなかった。2. Description of the Related Art Aliphatic polyesters derived from oxyacids such as polylactic acid, polyglycolic acid or copolymers thereof have attracted attention as biodegradable polymers. For example, medical materials such as sutures, pharmaceuticals, agricultural chemicals, It is used in various fields such as controlled release materials such as fertilizers. For these purposes, it is generally preferable that the mechanical properties are high. Therefore, in order to obtain these high molecular weight polymers, conventionally, lactide and glycolide were produced from lactic acid and glycolic acid, and these were subjected to ring-opening polymerization to produce high molecular weight polylactide and polyglycolide. Although a high molecular weight polymer can be obtained by this method, it is a two-step reaction, and it takes a lot of labor to obtain lactide and glycolide, which is not economical. On the other hand, the method of directly polycondensing lactic acid and glycolic acid is economical, but on the other hand, it has the drawback that it cannot be made into a high molecular weight compound and has not been industrialized. For example, in an attempt to increase the molecular weight, a tin compound is used as a polycondensation catalyst, and liquid paraffin is added at the time of polymerization (JP-A-62-648).
23) and the like have also been proposed, but in this example, the number average molecular weight is about 10,000, and it cannot be said that the molecular weight is sufficient when considering industrial use. An example using an inorganic germanium compound such as GeO 2 (Japanese Patent Laid-Open No. 43436/1993) has also been reported, but it was not necessarily sufficient in terms of color tone and molecular weight of the obtained polymer.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、すぐ
れた機械的物性を有する高分子量のポリ乳酸を始めとす
る脂肪族ポリエステルを直接重縮合反応により容易に得
る製造方法を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a production method for easily obtaining an aliphatic polyester such as a high molecular weight polylactic acid having excellent mechanical properties by direct polycondensation reaction. is there.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記目的を
達成するために鋭意研究の結果、通常のポリエチレンテ
レフタレート、ポリブチレンテレフタレート等のポリエ
ステル重縮合触媒、あるいはラクチド類の開環重合触媒
を使用した場合には充分な重合度を得ることが困難であ
るにも関わらず、ゲルマニウムアルコキシド等の有機ゲ
ルマニウム化合物を使用した場合には、意外にも高分子
量のポリ乳酸を得ることができることを見い出し、本発
明を完成するに至った。Means for Solving the Problems As a result of earnest studies for achieving the above object, the present inventors have found that ordinary polyester polycondensation catalysts such as polyethylene terephthalate and polybutylene terephthalate, or ring-opening polymerization catalysts of lactides are used. Despite the difficulty in obtaining a sufficient degree of polymerization when used, it was surprisingly found that when an organic germanium compound such as germanium alkoxide is used, high molecular weight polylactic acid can be obtained. The present invention has been completed.
【０００５】即ち、本発明の要旨はオキシ酸を脱水重縮
合することにより、脂肪酸ポリエステルを製造する方法
において、有機ゲルマニウム化合物の存在下で脱水重縮
合することを特徴とする脂肪族ポリエステルの製造方法
に存する。以下本発明について詳細に説明する。本発明
において使用するモノマーであるオキシ酸は乳酸、グリ
コール酸、４−ヒドロキシ酪酸等が挙げられるが以下乳
酸を代表例として説明する。That is, the gist of the present invention is a method for producing a fatty acid polyester by dehydration polycondensation of an oxy acid, wherein the dehydration polycondensation is carried out in the presence of an organic germanium compound. Exist in. The present invention will be described in detail below. Examples of the oxyacid that is a monomer used in the present invention include lactic acid, glycolic acid, 4-hydroxybutyric acid, and the like, and lactic acid will be described below as a representative example.
【０００６】乳酸としては特に限定なく使用でき、Ｄ，
Ｌ−またはラセミ体でも使用することができる。また、
所望に応じ、通常使用されるグリコール酸、ラクトンお
よびその開環重合物などの共重合成分等を使用すること
も可能である。反応は溶融状態で行うことが好ましく、
そのため乳酸濃度が９２％以上好ましくは９５％以上の
濃縮オキシ酸を用いることがより好ましい。As lactic acid, it can be used without particular limitation.
It is also possible to use the L- or racemic form. Also,
If desired, it is possible to use commonly used copolymerization components such as glycolic acid, lactone and ring-opening polymer thereof. The reaction is preferably carried out in the molten state,
Therefore, it is more preferable to use a concentrated oxyacid having a lactic acid concentration of 92% or more, preferably 95% or more.
【０００７】本発明で使用する触媒としてはゲルマニウ
ムアルコキシドであれば特に限定されないが、下記一般
式（１） Ｇｅ（ＯＲ）4 （１） （式（１）中Ｒは炭素数２ないし１０のアルキル基であ
り、直鎖であっても分岐であってもよい。）で表わされ
るものが好ましい。The catalyst used in the present invention is not particularly limited as long as it is a germanium alkoxide, but the following general formula (1) Ge (OR) 4 (1) (wherein R in the formula (1) is an alkyl having 2 to 10 carbon atoms) Group, which may be linear or branched) is preferred.
【０００８】ゲルマニウムアルコキシドの具体例として
は、例えばテトラエトキシゲルマニウム、テトラｎ−ブ
トキシゲルマニウム、テトラｎ−ヘキシルゲルマニウム
等のゲルマニウムアルコキシドが挙げられ、特にテトラ
ｎ−ブトキシゲルマニウムが好ましい。ゲルマニウムア
ルコキシド、とくにテトラｎ−ブトキシゲルマニウムは
他のゲルマニウム化合物、たとえば二酸化ゲルマニウ
ム、金属ゲルマニウム、四塩化ゲルマニウム等の無機ゲ
ルマニウム化合物を用いた場合に比較して高分子量の脂
肪族ポリエステルが得られ、さらに色調の良好なものが
得られやすい。Specific examples of the germanium alkoxide include germanium alkoxides such as tetraethoxy germanium, tetra n-butoxy germanium, tetra n-hexyl germanium, etc., and tetra n-butoxy germanium is particularly preferable. Germanium alkoxides, especially tetra-n-butoxy germanium, give higher molecular weight aliphatic polyesters than other germanium compounds such as germanium dioxide, metal germanium, and germanium tetrachloride. It is easy to obtain a good product.
【０００９】触媒の反応系への添加は、重縮合以前の段
階で添加することが好ましく、例えば原料し込み時、あ
るいは乳酸溶液で減圧時に添加することもできる。触媒
の使用量は使用するモノマー量に対し、Ｇｅ換算量で
０．００５〜３重量％、好ましくは０．０１〜１重量
％、より好ましくは０．０１〜０．５重量％である。触
媒濃度が高い程、より短時間に高分子量の脂肪族ポリエ
ステルが得られるが着色しやすくなる。即ち触媒濃度が
０．００５重量％以下では触媒効果が少なく、また３重
量％以上であるとポリマーの着色や劣化などが起りやす
い。The catalyst is preferably added to the reaction system at a stage before polycondensation. For example, the catalyst can be added at the time of charging the raw materials or at the time of reducing the pressure with a lactic acid solution. The amount of the catalyst used is 0.005 to 3% by weight, preferably 0.01 to 1% by weight, and more preferably 0.01 to 0.5% by weight, in terms of Ge, based on the amount of the monomer used. The higher the catalyst concentration, the more quickly the high molecular weight aliphatic polyester can be obtained, but the more easily it becomes colored. That is, when the catalyst concentration is 0.005% by weight or less, the catalytic effect is small, and when it is 3% by weight or more, the polymer is likely to be colored or deteriorated.
【００１０】反応の条件としては通常のポリエステル重
縮合の反応条件でよく、例えば、真空あるいは窒素ガス
などの不活性ガスの減圧雰囲気下で行うのが好ましい。
反応温度は１５０〜２６０℃好ましくは１８０〜２３０
℃の範囲であるが、反応温度が高い程、より短時間に高
分子量の脂肪族ポリエステルが得られるが着色しやすく
なる。反応時間としては２時間以上、重合度を上げるた
めにはより長時間、例えば１０時間以上が好ましい。た
だしより長時間で行うとポリマーの着色の問題が生じる
ため、４〜１５時間が好ましい。The reaction conditions may be ordinary polyester polycondensation reaction conditions, for example, vacuum or a reduced pressure atmosphere of an inert gas such as nitrogen gas is preferred.
The reaction temperature is 150 to 260 ° C., preferably 180 to 230.
Although the temperature is in the range of 0 ° C., the higher the reaction temperature, the higher the molecular weight of the aliphatic polyester can be obtained in a shorter time, but the more easily it becomes colored. The reaction time is preferably 2 hours or longer, and longer for increasing the degree of polymerization, for example, 10 hours or longer. However, if it is carried out for a longer time, a problem of coloring of the polymer occurs, so that 4 to 15 hours is preferable.
【００１１】[0011]
【発明の効果】本発明方法に従って脂肪族ポリエステル
を製造することにより、高分子量であって色調の良好な
脂肪族ポリエステルを直接重縮合反応により容易に製造
できるという利点が得られる。By producing the aliphatic polyester according to the method of the present invention, the advantage that the aliphatic polyester having a high molecular weight and good color tone can be easily produced by direct polycondensation reaction is obtained.
【００１２】[0012]
【実施例】以下に本発明を実施例により具体的に説明す
るが、本発明はその要旨を越えない限り以下の実施例に
限定されるものではない。実施例における各特性値は以
下の方法により測定した。 還元粘度（ηSP／ｃ）；ポリマー０．１２５ｇをフェノ
ール／テトラクロロエタン（１／１ｗｔ％）混合溶媒２
５ｍｌに溶解し、３０℃で測定した。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Each characteristic value in the examples was measured by the following methods. Reduced viscosity (η SP / c); 0.125 g of polymer in phenol / tetrachloroethane (1/1 wt%) mixed solvent 2
It was dissolved in 5 ml and measured at 30 ° C.
【００１３】〔実施例１〕攪拌装置、窒素導入管を備え
た反応容器に、Ｌ−乳酸（９０％水溶液）をあらかじめ
脱水処理し、水分量を１％以下とした濃縮Ｌ−乳酸８５
ｇおよびテトラｎ−ブトキシゲルマニウム６７μｌ（濃
縮Ｌ−乳酸に対して０．０８重量％、Ｇｅ換算量で０．
０１６重量％）を仕込み、窒素置換を行った後、窒素気
流下、１８０℃、２時間、常圧で攪拌し、その後１時間
かけて２０ｍｍＨｇまで減圧し、２時間攪拌反応させ
た。続いて１時間かけて昇温、減圧を行い、２２０℃、
２ｍｍＨｇの条件で４時間重縮合反応させた。得られた
ポリマーは透明であって淡黄色をしており、還元粘度は
０．３７であった。[Example 1] Concentrated L-lactic acid 85 having a water content of 1% or less was prepared by previously dehydrating L-lactic acid (90% aqueous solution) in a reaction vessel equipped with a stirrer and a nitrogen introducing tube.
g and tetra n-butoxy germanium 67 μl (0.08 wt% with respect to concentrated L-lactic acid, Ge equivalent: 0.
(016% by weight) was charged, and the atmosphere was replaced with nitrogen. Then, the mixture was stirred under a nitrogen stream at 180 ° C. for 2 hours at normal pressure, and after that, the pressure was reduced to 20 mmHg over 1 hour and the reaction was performed for 2 hours with stirring. Subsequently, the temperature is raised and the pressure is reduced over a period of 1 hour to 220 ° C.
The polycondensation reaction was carried out for 4 hours under the condition of 2 mmHg. The obtained polymer was transparent and had a pale yellow color, and had a reduced viscosity of 0.37.
【００１４】〔実施例２〕触媒の添加量を変えた以外は
実施例１と同様の操作でポリ乳酸の合成を行った。その
結果を表１に示す。Example 2 Polylactic acid was synthesized in the same manner as in Example 1 except that the amount of catalyst added was changed. The results are shown in Table 1.
【００１５】〔比較例１〜２〕触媒、添加量を変えた以
外は実施例１と同様の操作でポリ乳酸の合成を行った。
但し、二酸化ゲルマニウムが濃縮Ｌ−乳酸に溶解しにく
いため、あらかじめ、脱水処理前のＬ−乳酸（９０％水
溶液）に二酸化ゲルマニウムを１重量％均一溶解させた
ものを原料に添加した。結果を表１に示す。[Comparative Examples 1 and 2] Polylactic acid was synthesized in the same manner as in Example 1 except that the catalyst and the addition amount were changed.
However, germanium dioxide is difficult to dissolve in concentrated L-lactic acid, so 1% by weight of germanium dioxide was previously dissolved in L-lactic acid (90% aqueous solution) before dehydration treatment was added to the raw material. The results are shown in Table 1.
【００１６】〔比較例３〜８〕触媒、添加量を変えた以
外は実施例１と同様の操作でポリ乳酸の合成を行った。
その結果を表１に示す。[Comparative Examples 3 to 8] Polylactic acid was synthesized in the same manner as in Example 1 except that the catalyst and the addition amount were changed.
The results are shown in Table 1.
【００１７】[0017]
【表１】 [Table 1]
Claims (2)
脂肪族ポリエステルを製造する方法において、有機ゲル
マニウム化合物の存在下で脱水重縮合することを特徴と
する脂肪族ポリエステルの製造方法。1. By dehydration polycondensation of an oxy acid,
A method for producing an aliphatic polyester, which comprises dehydration polycondensation in the presence of an organic germanium compound.
（１）で表される有機ゲルマニウム化合物であることを
特徴とする請求項１に記載の脂肪族ポリエステルの製造
方法。 Ｇｅ（ＯＲ）4 （１） （但し、Ｒは炭素数２ないし１０のアルキル基であり、
直鎖であっても分岐であってもよい。）2. The method for producing an aliphatic polyester according to claim 1, wherein the organic germanium compound is an organic germanium compound represented by the following general formula (1). Ge (OR) 4 (1) (wherein R is an alkyl group having 2 to 10 carbon atoms,
It may be linear or branched. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13487893A JPH06345856A (en) | 1993-06-04 | 1993-06-04 | Method for producing aliphatic polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13487893A JPH06345856A (en) | 1993-06-04 | 1993-06-04 | Method for producing aliphatic polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06345856A true JPH06345856A (en) | 1994-12-20 |
Family
ID=15138613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13487893A Pending JPH06345856A (en) | 1993-06-04 | 1993-06-04 | Method for producing aliphatic polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06345856A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0792901A1 (en) * | 1995-08-30 | 1997-09-03 | Mitsubishi Chemical Corporation | Production of aliphatic copolyesters |
| JP2008063358A (en) * | 2006-09-04 | 2008-03-21 | Mitsubishi Chemicals Corp | Polyester and production method thereof, and polyester block copolymer |
-
1993
- 1993-06-04 JP JP13487893A patent/JPH06345856A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0792901A1 (en) * | 1995-08-30 | 1997-09-03 | Mitsubishi Chemical Corporation | Production of aliphatic copolyesters |
| JP2008063358A (en) * | 2006-09-04 | 2008-03-21 | Mitsubishi Chemicals Corp | Polyester and production method thereof, and polyester block copolymer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0937116B1 (en) | Process for the preparation of polyhydroxy acids | |
| JP2011111461A (en) | Method for producing polylactic acid | |
| JPH06345856A (en) | Method for producing aliphatic polyester | |
| CN102869655B (en) | Improved process for the preparation of l-lactide of high chemical yield and optical purity | |
| JPH11116666A (en) | Production of polyglycolic acid | |
| JP6298545B2 (en) | Polyester manufacturing method | |
| CN109705159B (en) | Preparation method and application of phosphorus-nitrogen-containing ligand alkyl aluminum compound | |
| JPH0543665A (en) | Production of aliphatic polyester | |
| JP3374530B2 (en) | Method for producing aliphatic polyester copolymer | |
| JP3248597B2 (en) | Method for producing aliphatic polyester | |
| JP2000034341A (en) | Polycondensation for polyester using lithium titanyloxalate catalyst | |
| JP3409441B2 (en) | Method for producing aliphatic polyester | |
| JPH10287735A (en) | Polylactic acid composition, production thereof, and molded article prepared therefrom | |
| JP3520609B2 (en) | Method for producing aliphatic polyester | |
| JPH06293707A (en) | Hydroxyethyl dibenzoic acid | |
| JPH05287056A (en) | Production of aliphatic polyester | |
| JP4321918B2 (en) | Polyester production method | |
| JPH1160713A (en) | Production of aliphatic polyester | |
| CN107955030B (en) | Chiral aluminum complex containing acetylacetone derivative, and preparation method and application thereof | |
| JP2008063420A (en) | Polylactic acid and method for producing the same | |
| JP3248595B2 (en) | Production method of aliphatic polyester | |
| Zhu et al. | Functional Polylactides Achieved by Iron‐Catalyzed (Co) Polymerization of Different Lactides | |
| JPH08295726A (en) | Aliphatic polyester and its production | |
| JP3353853B2 (en) | Polylactic acid having ester-blocked substantially all terminal hydroxyl groups and process for producing the same | |
| US3299004A (en) | Process for the manufacture of linear polyesters with metal imide salt catalysts |