JPH08231688A - Production of polylactic acid - Google Patents
Production of polylactic acidInfo
- Publication number
- JPH08231688A JPH08231688A JP3482395A JP3482395A JPH08231688A JP H08231688 A JPH08231688 A JP H08231688A JP 3482395 A JP3482395 A JP 3482395A JP 3482395 A JP3482395 A JP 3482395A JP H08231688 A JPH08231688 A JP H08231688A
- Authority
- JP
- Japan
- Prior art keywords
- polylactic acid
- lactide
- polymerization
- temperature
- pellets
- 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
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- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は固形の高分子量ポリ乳酸
の製造法に関する。本発明の製造法にて得られたポリ乳
酸は高分子量であり、粒状、ペレット状、板状など種々
の形態をなす。The present invention relates to a method for producing solid high molecular weight polylactic acid. The polylactic acid obtained by the production method of the present invention has a high molecular weight and has various forms such as a granular form, a pellet form and a plate form.
【０００２】[0002]
【従来の技術】ポリ乳酸は生体安全性が高く、しかも分
解物である乳酸は生体内で吸収される。このようにポリ
乳酸は生体安全性の高い高分子化合物であり、手術用縫
合糸、ドラッグデリバリー（徐放性カプセル）、骨折時
の補強材など医療用にも用いられ、自然環境下で分解す
るため分解性プラスチックとしても注目されている。ま
た、一軸、二軸延伸フィルムや繊維、放出成形品などと
して種々の用途にも用いられている。2. Description of the Related Art Polylactic acid has high biosafety, and lactic acid, which is a decomposition product, is absorbed in vivo. As described above, polylactic acid is a highly biosafe polymer compound, and is also used for medical purposes such as surgical sutures, drug delivery (sustained release capsules), and reinforcing materials for fractures, and decomposes in natural environments. Therefore, it is attracting attention as a degradable plastic. It is also used for various applications as uniaxially and biaxially stretched films, fibers, release molded products and the like.
【０００３】このようなポリ乳酸の製造法には、乳酸を
直接脱水縮合して目的物を得る直接法と、乳酸から一旦
環状ラクチド（二量体）を合成し、晶析法などにより精
製を行い、ついで開環重合を行う方法がある。ラクチド
の合成、精製及び重合操作は、例えば米国特許第４，０
５７，５３７号明細書：公開欧州特許出願第２６１，５
７２号明細書：Polymer Bulletin,14,491-495(1985);及
びMakromol.Chem.,187,1611-1628(1986)のような化学文
献で様々に記載されている。また、特公昭５６−１４６
８８号公報には２分子の環状ジエステルを中間体とし、
これをオクチル酸錫、ラウリルアルコールを触媒として
重合し、ポリ乳酸を製造することが開示されている。こ
のようにして得られたポリ乳酸は、成形加工の工程にお
ける取り扱い性を容易にするため、あらかじめ米粒大か
ら豆粒程度の大きさの球状、立方体、円柱状、破砕状等
のペレット状の製品とされる。[0003] Such a method for producing polylactic acid includes a direct method for directly dehydrating and condensing lactic acid to obtain a desired product, and a method in which a cyclic lactide (dimer) is once synthesized from lactic acid and purified by a crystallization method or the like. Then, ring-opening polymerization is performed. Lactide synthesis, purification and polymerization procedures are described, for example, in US Pat.
57,537: Published European Patent Application No. 261,5
72: Polymer Bulletin, 14,491-495 (1985); and Makromol. Chem., 187, 1611-1628 (1986). In addition, Japanese Patent Publication Sho-56-146
In JP-A-88, two molecules of cyclic diester are used as intermediates,
It is disclosed that polylactic acid is produced by polymerizing this using tin octylate and lauryl alcohol as catalysts. The polylactic acid thus obtained is used in advance in order to facilitate the handling in the molding process, and in advance, spherical, cubic, columnar, crushed and other pellet-shaped products having a size of about rice grains to bean grains. Is done.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、分子量
１０万〜５０万の高分子量のポリ乳酸の融点は１７５〜
２００℃と高く、従来このようなポリ乳酸の最終重合物
を溶融状態で反応器から取り出し、これを融点以上に加
熱すると、ポリ乳酸の分解や着色を生じた。さらにこの
様な温度においては、多量のラクチドがポリマー中に発
生した。また、ラクチドや分解物はポリマーのガラス転
移点温度および、溶融粘度を低下させ、成形加工性、熱
安定性をいちぢるしく劣下させていた。これらはこの様
な温度においてはポリマーとラクチドの平衡がラクチド
側に傾くためと思われる。However, the melting point of high molecular weight polylactic acid having a molecular weight of 100,000 to 500,000 is 175 to 175.
Conventionally, such a final polymer of polylactic acid was taken out of the reactor in a molten state at a high temperature of 200 ° C., and when it was heated to a temperature equal to or higher than the melting point, polylactic acid was decomposed or colored. Furthermore, at such temperatures, large amounts of lactide were generated in the polymer. In addition, lactide and decomposed products lowered the glass transition temperature and melt viscosity of the polymer, and considerably deteriorated the moldability and heat stability. This is probably because the equilibrium between the polymer and lactide is inclined toward the lactide side at such a temperature.
【０００５】そこで、本件出願人は、かかる課題を解決
するため、ポリ乳酸の重合において、最終生成物を得る
前に融点より低い温度で第１段の溶融重合を行い、ポリ
乳酸をペレット状に成型し、それをさらに第２段の固相
重合で最終重合物とする方法を提案している（特願平６
−２２１６５号）。Therefore, in order to solve such a problem, the applicant of the present invention, in the polymerization of polylactic acid, conducts the first stage melt polymerization at a temperature lower than the melting point before obtaining the final product, and transforms the polylactic acid into pellets. We have proposed a method in which it is molded and then made into the final polymer by the second-stage solid-state polymerization (Japanese Patent Application No. 6-83242).
22165).
【０００６】本発明は、更に改良を加え、固相重合の際
残っていた未反応のモノマーを除去する工程をも付加し
た高分子量のポリ乳酸を製造する方法を提供することを
目的とする。[0006] It is an object of the present invention to provide a method for producing high molecular weight polylactic acid, which is further improved and additionally includes a step of removing unreacted monomers remaining during solid phase polymerization.
【０００７】[0007]
【課題を解決するための手段】本発明者らは前記の課題
について鋭意研究を行った結果、ポリ乳酸の重合過程に
おいて未だ反応せずに残存するモノマーを昇華すること
により、ポリ乳酸の物性を改善することを見出だし、本
発明をなすに至った。Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have succeeded in improving the physical properties of polylactic acid by sublimating the monomer which remains unreacted in the polymerization process of polylactic acid. The inventors have found that they are improved and have completed the present invention.
【０００８】すなわち、本発明は、ラクチドを主原料と
し、溶融重合により固形のポリ乳酸を得る第１工程と、
第１工程で重合し成形した固形のポリ乳酸をペレット状
に成形する第２工程と、第２工程で得たポリ乳酸ペレッ
トをその融点より低い温度で固相重合をする第３工程
と、第３工程の重合で未反応のモノマーを昇華する第４
工程とからなるポリ乳酸の製造法を提供する。That is, the present invention comprises a first step of obtaining solid polylactic acid by melt polymerization using lactide as a main raw material,
A second step in which solid polylactic acid polymerized and molded in the first step is molded into pellets, a third step in which the polylactic acid pellet obtained in the second step is solid-phase polymerized at a temperature lower than its melting point, Fourth sublimation of unreacted monomer by three-step polymerization
A method for producing polylactic acid comprising the steps of:
【０００９】本発明のポリ乳酸の製造法では、まず第１
工程で分解や着色の伴わない比較的低温で１段目の重合
反応を行い、目的の重合度の５０〜９５％のプレポリマ
ーを重合する。１段目の反応温度は１００〜１９０℃、
好ましくは１４０〜１７０℃であり、平均分子量５万〜
２０万、ラクチド含量２〜２０重量％、好ましくは３〜
７％のポリ乳酸を得る。第１工程で得られるポリ乳酸は
粘度が１０００〜２０，０００pois、好ましくは３００
０〜７０００poisである。ここで、ラクチド含量の％は
１０／１０のＤＳＣ測定で得られるクロマトグラムの面
積比をいう（以下同様）。In the method for producing polylactic acid of the present invention, firstly,
In the process, the first stage polymerization reaction is carried out at a relatively low temperature without decomposition or coloration to polymerize a prepolymer having a desired degree of polymerization of 50 to 95%. The reaction temperature in the first step is 100 to 190 ° C,
It is preferably 140 to 170 ° C. and has an average molecular weight of 50,000 to
200,000, lactide content 2 to 20% by weight, preferably 3 to
7% polylactic acid is obtained. The polylactic acid obtained in the first step has a viscosity of 1000 to 20,000 pois, preferably 300.
It is 0-7000 pois. Here,% of the lactide content means the area ratio of the chromatogram obtained by the DSC measurement of 10/10 (the same applies hereinafter).
【００１０】重合に用いる触媒としては、オクチル酸ス
ズなどのスズ系化合物、テトライソプロピルチタネート
などのチタン系化合物、ジルコニウムイソプロポキシド
などのジルコニウム系化合物、三酸化アンチモンなどの
アンチモン系化合物等、いずれも乳酸の重合に従来公知
の触媒が挙げられる。触媒の量としては１〜５００ppm.
好ましくは１０〜１００ppm.である。また、添加する触
媒量によって、最終ポリマーの分子量を調整することも
できる。触媒量が少ないほど反応速度は遅くなるが、分
子量は高くなる。また、核剤（タルク、クレー、酸化チ
タン等）を添加してもよい。Examples of the catalyst used for the polymerization include tin compounds such as tin octylate, titanium compounds such as tetraisopropyl titanate, zirconium compounds such as zirconium isopropoxide, and antimony compounds such as antimony trioxide. Conventionally known catalysts are used for the polymerization of lactic acid. The amount of catalyst is 1 to 500 ppm.
It is preferably 10 to 100 ppm. Further, the molecular weight of the final polymer can be adjusted by adjusting the amount of catalyst added. The lower the amount of catalyst, the slower the reaction rate, but the higher the molecular weight. A nucleating agent (talc, clay, titanium oxide, etc.) may be added.
【００１１】本方法に使用するラクチドはＤ−、Ｌ−、
ＤＬ−またはＤ−、Ｌ−の混合物でよく、ラクトン類、
例えばβ−プロピオラクトン、δ−バレルラクトン、ε
−カプロラクトングリコリド、δ−ブチルラクトンとの
共重合も可能である。またグリセリンなど多価アルコー
ルにより物性をコントロールすることもできる。The lactide used in this method is D-, L-,
DL- or a mixture of D- and L- may be used, lactones,
For example, β-propiolactone, δ-barrellactone, ε
Copolymerization with -caprolactone glycolide and δ-butyl lactone is also possible. Further, the physical properties can be controlled by using a polyhydric alcohol such as glycerin.
【００１２】重合反応は触媒の種類によって異なるがオ
クチル酸スズを用いる場合、ラクチド重量に対して０．
０００１〜０．１重量％、好ましくは０．０５〜０．０
０１重量％の触媒を用い、通常５〜２００時間加熱重合
する。反応は窒素など不活性ガス雰囲気中にて行うのが
好ましい。The polymerization reaction varies depending on the type of catalyst, but when tin octylate is used, it is 0.
0001 to 0.1% by weight, preferably 0.05 to 0.0
Heat polymerization is usually carried out for 5 to 200 hours using 01% by weight of the catalyst. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen.
【００１３】また、第１工程の重合を行う反応器は、原
料のラクチドからプレポリマーまで幅広い粘度で重合を
行うため、それぞれの粘度に応じ１個以上設ける。例え
ば全面翼を持った縦型反応器で、パドル翼を持った縦型
反応器、ヘリカルリボン翼を持った縦型反応器、エクス
クルーダーのような横型反応器と順次流していくように
することができるが、これに限定されない。反応器から
の重合物（ポリ乳酸）の取り出しは、低粘度の場合は窒
素などの不活性ガスによる押し出しにより行い、高粘度
の場合はギヤポンプによる抜き出しにより行う。Further, the reactor for carrying out the polymerization in the first step carries out the polymerization with a wide range of viscosities from the lactide as the raw material to the prepolymer, so one or more reactors are provided depending on the respective viscosities. For example, in a vertical reactor with full blades, a vertical reactor with paddle blades, a vertical reactor with helical ribbon blades, and a horizontal reactor such as an excluder should be used. However, the present invention is not limited to this. The polymer (polylactic acid) is taken out from the reactor by extrusion with an inert gas such as nitrogen when the viscosity is low, and by a gear pump when the viscosity is high.
【００１４】なお、第１工程の重合時に反応が進行し、
粘度が上がりすぎるのを防ぐためラクチドを新たに加え
ても良い。また、連続的にラクチドを加え、同時に重合
物の取り出しを行ってもよい。The reaction proceeds during the polymerization in the first step,
Lactide may be newly added to prevent the viscosity from increasing too much. Alternatively, lactide may be continuously added and the polymer may be taken out at the same time.
【００１５】第１工程で得られたポリ乳酸を第２工程で
ペレットに成形する。成形方法としてはまず、反応器よ
り取り出し冷却する。冷却は水槽などを用いても良い
が、ベルトクーラー、またはドラムクーラーなど水に直
接接触しない冷却方法が好ましい。冷却に際しては、ポ
リ乳酸に水分が付着するのを防ぐため、脱湿空気または
窒素を導入し、冷却面および気相中に水分が５０ ppm以
下にしておくのが好ましい。冷却温度は、１段目の重合
によりできたポリ乳酸の結晶化温度より低くても高くて
も良い。成型は、前記ベルトクーラーやドラムクーラー
の出口側に例えば、直径２〜５ｍｍのダイスよりストラ
ンド状に取り出しペレタイザーで切断しチップとするも
のや、造粒装置によりマーブル状とするもの、シール状
に取り出し、粉砕するものなどを配置しておくことが考
えられるが、これらに限定されない。The polylactic acid obtained in the first step is molded into pellets in the second step. As a molding method, first, it is taken out from the reactor and cooled. A water tank or the like may be used for cooling, but a cooling method such as a belt cooler or a drum cooler that does not come into direct contact with water is preferable. At the time of cooling, it is preferable to introduce dehumidified air or nitrogen so as to prevent water from adhering to the polylactic acid so that the water content is 50 ppm or less on the cooling surface and in the gas phase. The cooling temperature may be lower or higher than the crystallization temperature of the polylactic acid formed by the first stage polymerization. Molding is carried out at the outlet side of the belt cooler or drum cooler, for example, by taking out in a strand form from a die having a diameter of 2 to 5 mm to cut into chips with a pelletizer, making into marble in a granulator, and taking out in a seal form. It is conceivable to arrange things to be crushed, but it is not limited to these.
【００１６】第３工程では、成形されたポリ乳酸ペレッ
トを固相のまま加熱し重合反応を進行させる。この工程
はペレットを結晶化させると同時に重合も進行する。結
晶化したペレットは固相重合時に結晶化熱を発する事が
ないので融着しにくい。結晶化の方法としては予熱後さ
らに温度を上げるのが好ましい。温度はラクチドの融点
以上で、かつ第１工程の重合温度より５℃以上、好まし
くは１０℃以上低く設定するのがよい。したがって、第
３工程の反応温度は８０〜１７５℃、好ましくは１２０
〜１４０℃である。反応時間は６〜９０時間、好ましく
は２０〜４０時間である。また、反応時間を短縮するた
め、重合の進行に伴い、反応温度を上昇させてもよい。
最終的なポリマーの融点は１７０〜１８０℃であるか
ら、１７５℃付近まで昇温できる。なお、この工程は真
空または不活性ガス、乾燥空気中などで行ってもよい
が、ラクチドは昇華しやすいため未反応ラクチドを少し
でも反応させようとするときは、大気圧〜１０ｋｇｆ／
ｃｍ2 で行うのがより好ましい。In the third step, the molded polylactic acid pellets are heated in the solid phase to allow the polymerization reaction to proceed. In this step, the pellets are crystallized, and at the same time, the polymerization proceeds. The crystallized pellets do not generate heat of crystallization during solid-state polymerization, and thus are difficult to fuse. As a crystallization method, it is preferable to further raise the temperature after preheating. The temperature is set to the melting point of lactide or higher and lower than the polymerization temperature in the first step by 5 ° C. or higher, preferably 10 ° C. or higher. Therefore, the reaction temperature in the third step is 80 to 175 ° C., preferably 120.
~ 140 ° C. The reaction time is 6 to 90 hours, preferably 20 to 40 hours. Further, in order to shorten the reaction time, the reaction temperature may be increased as the polymerization proceeds.
Since the final melting point of the polymer is 170 to 180 ° C, the temperature can be raised to around 175 ° C. This step may be carried out in a vacuum, an inert gas, dry air, or the like, however, since lactide easily sublimes, when trying to react unreacted lactide even a little, atmospheric pressure to 10 kgf /
More preferably, it is performed in cm 2 .
【００１７】第３工程の反応器は、縦型又は横型反応器
のいずれでも良い。反応器内では、静置または流動させ
て加熱する。流動させる場合はコニカルドライヤーや窒
素などの不活性ガス雰囲気の吹き上げで行うのが好まし
い。The reactor of the third step may be either a vertical reactor or a horizontal reactor. In the reactor, it is left standing or fluidized and heated. When fluidized, it is preferable to blow it up with a conical dryer or an atmosphere of an inert gas such as nitrogen.
【００１８】第４工程では、未反応モノマーを除去する
ため、昇華させる。ラクチドは昇華しやすい性質である
ので、真空または不活性ガス、乾燥空気中で行うことが
できる。加熱温度はラクチド（融点９０〜９８℃）の融
解が始まるより２〜４０℃低い温度で行うのが好まし
い。但し、本発明で言う「昇華」とは、融点以下のポリ
乳酸ペレット中からのガス化のことを指し、操作温度は
モノマーであるラクチドの融点以上である場合もある。In the fourth step, sublimation is performed in order to remove unreacted monomers. Since lactide has a property of easily sublimating, it can be performed in a vacuum, an inert gas, or dry air. The heating temperature is preferably 2 to 40 ° C. lower than the temperature at which melting of lactide (melting point 90 to 98 ° C.) starts. However, the "sublimation" referred to in the present invention refers to gasification from the inside of the polylactic acid pellet having a melting point or lower, and the operation temperature may be higher than the melting point of lactide which is a monomer.
【００１９】本工程については特別な反応器は要らず、
第３工程の反応器をそのまま使用し、その温度を調整す
るだけで良い。本工程で除去されるモノマーは、ラクチ
ド、乳酸オリゴマーなどの未反応物である。除去された
モノマーは、コンデンサーやサイクロンに回収され、再
び第１工程へ戻すことができる。また、回収されたオリ
ゴマーはラクチド合成の工程へ戻すことができる。No special reactor is required for this step,
It suffices to use the reactor of the third step as it is and adjust its temperature. The monomers removed in this step are unreacted substances such as lactide and lactic acid oligomer. The removed monomer is recovered in a condenser or a cyclone and can be returned to the first step again. Further, the recovered oligomer can be returned to the step of lactide synthesis.
【００２０】[0020]
【作用】本発明では、ポリ乳酸の重合に際して残存した
未反応モノマーを昇華させて除去する。そのため、ガラ
ス転移点温度が、５５℃以上のポリ乳酸ペレットができ
る。In the present invention, the unreacted monomer remaining during the polymerization of polylactic acid is sublimated and removed. Therefore, a polylactic acid pellet having a glass transition temperature of 55 ° C. or higher can be obtained.
【００２１】[0021]
【実施例】本発明の方法を実施する装置の一例を図面に
基づいて説明する。図１が製造装置の一例で、図中Ａが
第１工程を行う反応器、Ｂが第２工程を行う冷却・成型
部、Ｃが第３工程の重合、第４工程の昇華を行う反応器
である。反応器Ａは、中空円筒体の反応タンク１からな
り、反応タンク１には、原料供給口２及び排出口用の開
口３が設けられ、排出口用の開口３には取り出しノズル
５が接続されている。ノズル５には、次の冷却・成型部
Ｂに供給するポリ乳酸量を制御するためのバルブＶが設
けてある。DESCRIPTION OF THE PREFERRED EMBODIMENTS An example of an apparatus for carrying out the method of the present invention will be described with reference to the drawings. FIG. 1 is an example of a manufacturing apparatus, in which A is a reactor for performing the first step, B is a cooling / molding part for performing the second step, C is a reactor for performing polymerization in the third step, and sublimation in the fourth step. Is. The reactor A is composed of a hollow cylindrical reaction tank 1. The reaction tank 1 is provided with an opening 3 for a raw material supply port 2 and a discharge port, and a discharge nozzle 5 is connected to the opening 3 for the discharge port. ing. The nozzle 5 is provided with a valve V for controlling the amount of polylactic acid supplied to the next cooling / molding section B.
【００２２】反応タンク１内にはヘリカルリボン翼４が
収容されており、その駆動源（モータ）Ｍは、反応タン
ク１のもう一つの開口側に設置される。また、反応タン
ク１には、窒素ガス供給配管６が接続され、図示しない
ガスボンベから配管を介して、タンク１内に窒素ガスが
供給される。なお、反応タンク１の周囲には図示しない
が、反応タンク１を加熱する加熱機構（熱媒ジャケッ
ト）が設けられており、また、反応タンク１内の温度は
温度センサ（図示せず）によりモニタされている。A helical ribbon blade 4 is housed in the reaction tank 1, and its drive source (motor) M is installed at the other opening side of the reaction tank 1. A nitrogen gas supply pipe 6 is connected to the reaction tank 1, and nitrogen gas is supplied into the tank 1 from a gas cylinder (not shown) via the pipe. Although not shown around the reaction tank 1, a heating mechanism (heating medium jacket) for heating the reaction tank 1 is provided, and the temperature inside the reaction tank 1 is monitored by a temperature sensor (not shown). Has been done.
【００２３】冷却・成型部Ｂの冷却部は、前述の取り出
しノズル５の下部にドラム７、プレッシャーロール８が
配設されて構成されている。ドラム７とプレッシャーロ
ール８の間に第１工程で重合したプレポリマーが流入す
る。ドラム７とプレッシャーロール８の内部には各々冷
却水スプレが内蔵されており、ドラム７、プレッシャー
ロール８の内面が冷却される。９は耐熱ベルトで、ドラ
ム７とプレッシャーロール８の間に流入したプレポリマ
ーを圧接しながら、成型部１０に送る。耐熱ベルト９の
回転は図示しない回転機構によりローラ１５を回転させ
て行う。ドラム７も図示しないモータにより回転する。
成型部１０は入口部１１、出口部１２と内部に収納され
たシートカッターからなり、送られてきたプレポリマー
（シート状のもの）を切断し、ペレットＰを作製する。The cooling section of the cooling / molding section B is constructed by disposing the drum 7 and the pressure roll 8 under the take-out nozzle 5. The prepolymer polymerized in the first step flows between the drum 7 and the pressure roll 8. Cooling water sprays are built in the drum 7 and the pressure roll 8, respectively, and the inner surfaces of the drum 7 and the pressure roll 8 are cooled. Reference numeral 9 denotes a heat-resistant belt, which sends the prepolymer flowing between the drum 7 and the pressure roll 8 to the molding unit 10 while pressing it. The heat-resistant belt 9 is rotated by rotating the roller 15 by a rotation mechanism (not shown). The drum 7 is also rotated by a motor (not shown).
The molding part 10 is composed of an inlet part 11, an outlet part 12 and a sheet cutter housed inside, and cuts the prepolymer (sheet-shaped) that has been sent to produce pellets P.
【００２４】反応器Ｃは、中空多角形の反応タンク（６
型コニカルドライヤー）１３とそれを支持する支持台１
４とからなり、反応タンク１３には、前述のペレットＰ
の受け口が設けられる。なお、反応タンク１３の周囲に
は図示しないが、反応タンク１３を加熱する加熱機構が
設けられている。また、反応タンク１３内の温度は温度
センサ（図示せず）によりモニタされている。また、反
応タンク１３内には、窒素ガスの吹き付け又は真空引き
のための開口も設けられている。The reactor C is a hollow polygonal reaction tank (6
Type conical dryer) 13 and a supporting stand 1 for supporting it
4 and the reaction tank 13 has the above-mentioned pellet P.
Is provided with a socket. Although not shown, a heating mechanism for heating the reaction tank 13 is provided around the reaction tank 13. The temperature inside the reaction tank 13 is monitored by a temperature sensor (not shown). Further, the reaction tank 13 is also provided with an opening for blowing nitrogen gas or evacuating.
【００２５】以上の構成で、ポリ乳酸を製造するのは次
の様に行う。先ず、Ｌ−ラクチド及び触媒を、原料供給
口２より反応タンク１に入れる。このときバルブＶは閉
められている。原料供給口２を閉栓し、窒素ガス供給口
６より窒素ガスを供給し、加熱機構（図示せず）及びヘ
リカルリボン翼４を作用させ重合を行う。このとき、重
合温度はモニタされており、一定範囲に制御されてい
る。With the above constitution, polylactic acid is produced as follows. First, L-lactide and the catalyst are put into the reaction tank 1 through the raw material supply port 2. At this time, the valve V is closed. The raw material supply port 2 is closed, nitrogen gas is supplied from the nitrogen gas supply port 6, and a heating mechanism (not shown) and the helical ribbon blade 4 act to perform polymerization. At this time, the polymerization temperature is monitored and controlled within a certain range.
【００２６】一定時間経過して第１工程の重合反応が進
めば、バルブＶを開け、ノズル５からドラム７とプレッ
シャーロール８の間に重合物（ポリ乳酸）を供給する。
このときドラム７とプレッシャーロール８は冷却されて
いるので、重合物は冷却される。冷却された重合物はシ
ート状になって成型部１０に入る。成型部１０でペレッ
トに成形された後、ポリ乳酸は反応タンク１３に入る。
反応タンク１３に入ると、加熱機構（図示せず）を作動
させて、窒素ガスを吹き上げながら、第３工程の重合を
行う。所定時間経過すれば、重合物を反応タンク１３に
入れたまま真空ポンプ（図示せず）で減圧にして未反応
ラクチドを昇華させる。なお、昇華は真空中で必ずしも
行う必要はなく、不活性ガス気流中で行ってもよい。When the polymerization reaction in the first step proceeds after a certain period of time, the valve V is opened and the polymer (polylactic acid) is supplied from the nozzle 5 between the drum 7 and the pressure roll 8.
At this time, since the drum 7 and the pressure roll 8 are cooled, the polymer is cooled. The cooled polymer is formed into a sheet and enters the molding unit 10. After being molded into pellets by the molding unit 10, the polylactic acid enters the reaction tank 13.
When it enters the reaction tank 13, a heating mechanism (not shown) is operated to carry out the polymerization in the third step while blowing up nitrogen gas. After a lapse of a predetermined time, the unreacted lactide is sublimated by reducing the pressure with a vacuum pump (not shown) while keeping the polymer in the reaction tank 13. The sublimation does not necessarily have to be performed in vacuum, and may be performed in an inert gas stream.
【００２７】本発明の方法を以下の実験により確かめ
た。 ［実験例１］ （第１工程）神鋼パンテック製ダブルヘリカルリボン翼
を持つ、５０ＬのＳＵＳ３０４製の反応器にラクチド５
０ｋｇを仕込んだ。１６０℃に加熱溶解後、オクチル酸
スズ１０ｐｐｍを添加した。１６０℃にて１２０時間加
熱後、窒素ボンベ１ｋｇｆ／ｃｍ2 の圧をかけ、反応器
より取り出した。The method of the present invention was confirmed by the following experiments. [Experimental Example 1] (First step) A lactide 5 was added to a 50 L SUS304 reactor having a double helical ribbon blade made by Shinko Pantech.
I charged 0 kg. After heating and melting at 160 ° C., 10 ppm of tin octylate was added. After heating at 160 ° C. for 120 hours, a pressure of 1 kgf / cm 2 of nitrogen cylinder was applied and the container was taken out of the reactor.
【００２８】（第２工程）これを三菱化成エンジニアリ
ング製ＤＣ−４５０−０８型ドラムクーラーにてシート
状に冷却し、三菱化成エンジニアリング製シートカッタ
ーで３ｍｍ角、厚さ１ｍｍのペレットに成形した。この
時のガラス転移温度は５２℃、結晶化温度は１２８℃、
融点は１６３℃、ポリマーの分子量は１２万、比率は９
７．１％であった。(Second Step) This was cooled into a sheet by a DC-450-08 type drum cooler manufactured by Mitsubishi Kasei Engineering Co., Ltd., and molded into pellets of 3 mm square and 1 mm thickness by a sheet cutter manufactured by Mitsubishi Kasei Engineering Co., Ltd. At this time, the glass transition temperature is 52 ° C, the crystallization temperature is 128 ° C,
Melting point is 163 ° C, molecular weight of polymer is 120,000, ratio is 9
It was 7.1%.
【００２９】（第３工程）ペレット２０ｋｇを神鋼パン
テック製６型コニカルドライヤーに入れ、１３５℃で６
５時間、結晶化固相重合を行った。この時容器内は０．
２ｋｇｆ／ｃｍ2の陽圧であった。得られたペレット
は、ガラス転移温度は５７℃、結晶化温度は１３０℃、
融点は１６６℃、ポリマーの分子量は１３万、比率は９
９．０％であった。(Third step) 20 kg of pellets were put into a 6-type conical dryer manufactured by Shinko Pantech and placed at 135 ° C. for 6 hours.
Crystallization solid phase polymerization was carried out for 5 hours. At this time, the inside of the container is 0.
The positive pressure was 2 kgf / cm 2 . The obtained pellets have a glass transition temperature of 57 ° C, a crystallization temperature of 130 ° C,
The melting point is 166 ° C, the molecular weight of the polymer is 130,000, and the ratio is 9
It was 9.0%.
【００３０】（第４工程）これをコニカルドライヤーに
入れたまま真空ポンプで２０時間減圧した。得られたペ
レットはガラス転移温度は５８℃、結晶化温度は１３１
℃、融点は１６７℃、ポリマーの分子量は１３万、比率
は９９，５％であった。(Fourth step) While this was placed in a conical dryer, the pressure was reduced by a vacuum pump for 20 hours. The obtained pellet has a glass transition temperature of 58 ° C. and a crystallization temperature of 131.
C., the melting point was 167.degree. C., the molecular weight of the polymer was 130,000, and the ratio was 99.5%.
【００３１】［実験例２］第１工程から第３工程までは
上記実験例と同じ方法で行った。[Experimental Example 2] From the first step to the third step, the same method as in the above experimental example was performed.
【００３２】（第４工程）窒素ボンベより窒素をコニカ
ルドライヤーに流入させ、蓋を少しゆるめ排出した。１
３５℃で１６時間この工程を行った。得られたペレット
は、ガラス転移温度は５８℃、結晶化温度は１３１℃、
融点は１６６℃、ポリマーの分子量は１３万、比率は９
９．５％であった。(Fourth step) Nitrogen was introduced into the conical dryer from the nitrogen cylinder, the lid was loosened a little, and the conical dryer was discharged. 1
This step was performed at 35 ° C. for 16 hours. The obtained pellets have a glass transition temperature of 58 ° C, a crystallization temperature of 131 ° C,
The melting point is 166 ° C, the molecular weight of the polymer is 130,000, and the ratio is 9
It was 9.5%.
【００３３】［実験例３］ （第１工程）神鋼パンテック製ダブルヘリカルリボン翼
を持つ、５０ＬのＳＵＳ３０４製の反応器にラクチド３
０ｋｇを仕込んだ。１６０℃に加熱溶解後、オクチル酸
スズ１０ｐｐｍを添加した。１６０℃にて７０時間、１
７０℃にて２０時間加熱後、窒素ボンベ１ｋｇｆ／ｃｍ
2 の圧をかけ、反応器より取り出した。[Experimental Example 3] (First step) A lactide 3 was added to a 50 L SUS304 reactor having a double helical ribbon blade made by Shinko Pantech.
I charged 0 kg. After heating and melting at 160 ° C., 10 ppm of tin octylate was added. 70 hours at 160 ℃, 1
After heating at 70 ° C for 20 hours, nitrogen cylinder 1kgf / cm
A pressure of 2 was applied and the product was taken out of the reactor.
【００３４】（第２工程）これを三菱化成エンジニアリ
ング製ＤＣ−４５０−０８型ドラムクーラーにてシート
状に冷却し、三菱化成エンジニアリング製シートカッタ
ーで３ｍｍ角、厚さ１ｍｍのペレットに成形した。この
時のガラス転移温度は５１℃、結晶化温度は１２５℃、
融点は１６６℃、ポリマーの分子量は１３万、比率は９
１．０％であった。(Second step) This was cooled into a sheet by a DC-450-08 type drum cooler manufactured by Mitsubishi Kasei Engineering Co., Ltd., and formed into a pellet of 3 mm square and 1 mm thickness by a sheet cutter manufactured by Mitsubishi Kasei Engineering Co., Ltd. At this time, the glass transition temperature was 51 ° C, the crystallization temperature was 125 ° C,
The melting point is 166 ° C, the molecular weight of the polymer is 130,000, and the ratio is 9
It was 1.0%.
【００３５】（第３工程）ペレット２０ｋｇを神鋼パン
テック製６型コニカルドライヤーに入れ、８０℃で６時
間、１００℃で４０時間、１２０℃で７０時間、結晶化
固相重合を行った。この時容器内は０．１８ｋｇｆ／ｃ
ｍ2 の陽圧であった。得られたペレットは、ガラス転移
温度は５４℃、結晶化温度は１２４℃、融点は１６９
℃、ポリマーの分子量は１３万、比率は９６．０％であ
った。(Third Step) 20 kg of pellets were placed in a Shinko Pantech 6-type conical dryer and subjected to crystallization solid phase polymerization at 80 ° C. for 6 hours, 100 ° C. for 40 hours, and 120 ° C. for 70 hours. At this time, the inside of the container is 0.18 kgf / c
It was a positive pressure of m 2 . The obtained pellets have a glass transition temperature of 54 ° C, a crystallization temperature of 124 ° C and a melting point of 169.
C., the molecular weight of the polymer was 130,000, and the ratio was 96.0%.
【００３６】（第４工程）これをコニカルドライヤーに
入れたまま真空ポンプで２０時間減圧した。得られたペ
レットはガラス転移温度は５８℃、結晶化温度は１２８
℃、融点は１７０℃、ポリマーの分子量は１３万、比率
は９９，０％であった。(Fourth step) While this was placed in a conical dryer, the pressure was reduced by a vacuum pump for 20 hours. The obtained pellet has a glass transition temperature of 58 ° C. and a crystallization temperature of 128.
C., the melting point was 170.degree. C., the molecular weight of the polymer was 130,000, and the ratio was 99.0%.
【００３７】なお、実験例１〜３の分析条件は下記の通
りである。 ＜ＧＰＣ測定＞ （株）島津製作所製 検出器； RID-6A ポンプ； LC-9A カラムオーブン； CTO-6A カラム；Shim-pack GPC-801C,-804C,-806C,-8025C を直
列 分析条件 溶媒；クロロフォルム 流速；１ml/min サンプル量； 200μl（サンプル0.5w/w％をクロロフォ
ルムに溶かした。） カラム温度； 40℃ ＜ＤＳＣ測定＞ （株）島津製作所製 DSC-50 昇温速度； 10℃/min サンプル量； 6〜7mgThe analytical conditions of Experimental Examples 1 to 3 are as follows. <GPC measurement> Shimadzu Corporation detector; RID-6A pump; LC-9A column oven; CTO-6A column; Shim-pack GPC-801C, -804C, -806C, -8025C in series Analysis conditions Solvent; Chloroform Flow rate: 1 ml / min Sample amount: 200 μl (0.5 w / w% sample was dissolved in chloroform) Column temperature: 40 ° C <DSC measurement> Shimadzu Corporation DSC-50 heating rate: 10 ° C / min Sample amount: 6-7mg
【００３８】[0038]
【発明の効果】本発明の製造法によれば、着色、分解物
のない分子量２０万〜５０万の高分子量のポリ乳酸成形
品（ペレット）を製造することができる。According to the production method of the present invention, it is possible to produce a polylactic acid molded article (pellet) having a high molecular weight of 200,000 to 500,000, which is free from coloring and decomposition products.
【図１】本発明の方法を実施する装置の概略図FIG. 1 is a schematic diagram of an apparatus for carrying out the method of the present invention.
Ａ：第１工程を行う反応器 Ｂ：第２工程を行う冷
却・成型部 Ｃ：第３工程の重合、第４工程の昇華を行う反応器 １：反応タンク ７：ドラム １０：成型部 １３：反応タンクA: Reactor for the first step B: Cooling / molding section for the second step C: Reactor for polymerization in the third step and sublimation in the fourth step 1: Reaction tank 7: Drum 10: Molding section 13: Reaction tank
Claims (1)
固形のポリ乳酸を得る第１工程と、第１工程で重合し成
形した固形のポリ乳酸をペレット状に成形する第２工程
と、第２工程で得たポリ乳酸ペレットをその融点より低
い温度で固相重合をする第３工程と、第３工程の重合で
未反応のモノマーを昇華する第４工程とからなるポリ乳
酸の製造法。1. A first step of obtaining solid polylactic acid by melt polymerization using lactide as a main raw material, a second step of molding solid polylactic acid polymerized and molded in the first step into pellets, and a second step. A method for producing polylactic acid, which comprises a third step of solid-phase polymerization of the polylactic acid pellet obtained in the step at a temperature lower than its melting point, and a fourth step of sublimating unreacted monomer in the polymerization of the third step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7034823A JP3055422B2 (en) | 1995-02-23 | 1995-02-23 | Polylactic acid production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7034823A JP3055422B2 (en) | 1995-02-23 | 1995-02-23 | Polylactic acid production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08231688A true JPH08231688A (en) | 1996-09-10 |
| JP3055422B2 JP3055422B2 (en) | 2000-06-26 |
Family
ID=12424926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7034823A Expired - Lifetime JP3055422B2 (en) | 1995-02-23 | 1995-02-23 | Polylactic acid production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3055422B2 (en) |
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