JPS5813624A - Preparation of polyglycolic acid - Google Patents
Preparation of polyglycolic acidInfo
- Publication number
- JPS5813624A JPS5813624A JP11232981A JP11232981A JPS5813624A JP S5813624 A JPS5813624 A JP S5813624A JP 11232981 A JP11232981 A JP 11232981A JP 11232981 A JP11232981 A JP 11232981A JP S5813624 A JPS5813624 A JP S5813624A
- Authority
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- Japan
- Prior art keywords
- polyglycolic acid
- alcohol
- weight
- glycolide
- polymerization
- 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.)
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- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は医療外科用に適した高分子状ポリグリコール酸
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polymeric polyglycolic acid suitable for medical and surgical applications.
ポリグリコール酸は固体の生体吸収性及び加水分解性を
有する重合生成物であり重合度の高いポリグリコール酸
は、繊維状物質や自己支持膜等に加工されて、縫合糸、
または結合糸の如き無菌外科手術用材として、あるいは
動物生体内に一定量の薬物を制御しながら連続投与する
ための器具として医学分野において有用な用途が開力）
れて（・る。Polyglycolic acid is a solid bioabsorbable and hydrolyzable polymerization product. Polyglycolic acid with a high degree of polymerization can be processed into fibrous materials, self-supporting membranes, etc., and used as sutures,
It is also useful in the medical field as a sterile surgical material such as a binding thread, or as a device for controlling and continuous administration of a fixed amount of drugs into an animal body.
・ru.
従来、ポリグリコール酸はグリコライドを三弗化アンチ
モンや塩化第一スズの存在下に重合する製造方法が知ら
れているが、これらの触媒＆ま有毒であるためポリマー
中に残存し、使用上問題力ｔあり、そのため無毒性安定
剤として米国のＦＤＡで認可されているオクタン酸第−
スズを触媒として使用する重合方法もまた知られて（・
る。（ポリマ″（ＰＯＬＹＭＥＲ）Ｖｏｔ２０、（１９
７９入１４５９頁）
上記 ポリマ′には、グリコライドなオクタン酸第−ス
ズ０．０３重量係及びラウリルアルコール０、０１重量
係（オクタン酸第−スズに対し０，６重量倍）の存在下
、２２０℃の温度で重合する方法が記載されているが、
本発明者らが追試した結果、得られたポリグリコール酸
は高温重合のため着色が著しく、また着色のない重合物
を得るため、所定量以上のオクタン酸第−スズ触媒を使
用しても２２０℃以下の温度で実施した場合生成物の重
合度が上がらず、紡糸加工などのできる所望の物性を有
するポリグリコール酸が得られないこともわかった。Conventionally, polyglycolic acid has been produced by polymerizing glycolide in the presence of antimony trifluoride or stannous chloride, but these catalysts remain in the polymer because they are toxic, making them difficult to use. Therefore, octanoic acid derivatives have been approved by the US FDA as a non-toxic stabilizer.
Polymerization methods using tin as a catalyst are also known (・
Ru. (POLYMER) Vot20, (19
(79 pages, 1459 pages) In the presence of 0.03 weight part of glycolide stannous octoate and 0.01 weight part of lauryl alcohol (0.6 times the weight of stannous octoate), A method of polymerizing at a temperature of 220°C is described,
As a result of additional experiments by the present inventors, the obtained polyglycolic acid was significantly colored due to high temperature polymerization, and in order to obtain a polymer without coloring, even if a stannous octoate catalyst of more than a specified amount was used, It has also been found that when carried out at temperatures below .degree. C., the degree of polymerization of the product does not increase, and polyglycolic acid having desired physical properties that can be processed by spinning etc. cannot be obtained.
本発明者らは、無害のオクタン酸第−スズを用いたポリ
グリコール酸の製造方法を鋭意研究を重ねた結果、得ら
れるポリマーは無色で、しかも溶融成型が可能な重合度
の高い、ポリグリフール酸を得ることに成功し、本発明
を完成させたものである。As a result of intensive research into a method for producing polyglycolic acid using harmless stannous octoate, the present inventors have discovered that the resulting polymer is colorless and has a high degree of polymerization that allows for melt molding. We succeeded in obtaining the following, and completed the present invention.
即ち、本発明、方法はオクタン酸第−スズの存在下グリ
コライドの重合によるポリグリコール酸の製造法におい
て、グリコライドに対しオクタン酸第−スズを０，０１
〜０，０５５重量部およびオクタ７酸８−スズに対し０
．５〜２ン８重量倍の炭素数１０〜１８の直鎖状脂肪族
アルコールの存在下で、１００〜ｉｓｏ”ｃの温度でグ
リコライドな重合させること、を特徴とするポリグリコ
ール酸の製造方法である。That is, the method of the present invention is a method for producing polyglycolic acid by polymerizing glycolide in the presence of stannous octoate, in which 0.01 stannous octoate is added to the glycolide.
~0,055 parts by weight and 0 for 8-tin octa7ate
．． A method for producing polyglycolic acid, which is characterized by glycolide polymerization at a temperature of 100 to iso''c in the presence of 5 to 2 times by weight of a linear aliphatic alcohol having 10 to 18 carbon atoms. It is.
本発明方法で得られるポリグリコール酸は、重合度１５
０〜１５００を有し、フェノール（１０重量部）とトリ
クロルフェノール（７重量部）の混合溶媒中の温度０．
５ ％−１３０±０，１°Ｃで測定した時少くとも約１
，０以上の固有粘度（〔μ〕）を有する、紡糸などの加
工１に沿したものである。The polyglycolic acid obtained by the method of the present invention has a polymerization degree of 15
0 to 1500, and the temperature in a mixed solvent of phenol (10 parts by weight) and trichlorophenol (7 parts by weight) is 0.
5% - at least about 1 when measured at 130 ± 0,1 °C
, has an intrinsic viscosity ([μ]) of 0 or more, and is in line with processing 1 such as spinning.
本発明方法の特徴）ま、無色の高分子量のポリマーを得
るために、前記文献記載と比較してラウリルアルコール
などの高級脂肪族アルコールの使用−量をオクタン酸第
−スズ触媒に７１シ、多量に用いて、重合温度を低くし
て反応させるものであり、オクタン酸第−スズ触媒の促
進剤と同時に重合調節剤として文献公知のラウリルアル
コールなどの□
高級脂肪族アルコールを、特定範囲で使用される触媒に
対し特定量を特定温度条件下で使用して重合することに
より所如の目的重合物か得られるようになったものであ
る。Characteristics of the method of the present invention) In order to obtain a colorless high-molecular weight polymer, the amount of higher aliphatic alcohol such as lauryl alcohol used in the stannous octoate catalyst was increased by 71 cm compared to that described in the above literature. It is used for reaction at a low polymerization temperature, and a higher aliphatic alcohol such as lauryl alcohol, which is known in the literature, is used as a promoter of the stannous octoate catalyst and as a polymerization regulator in a specified range. By using a specific amount of a catalyst under specific temperature conditions for polymerization, a desired polymer can be obtained.
本発明方法において、触媒であるオクタン酸第−スズは
、市販のものを１３ ｎｓｍＨ９の真空下にて蒸留した
ものを使用するのが好ましく、オクタン酸第−スズの使
用量は、原料であるグリコライドに対し０．０１１重量
部ら０．０５５重量部使用する。In the method of the present invention, it is preferable to use a commercially available product distilled under a vacuum of 13 nsm H9 as the catalyst stannous octoate. Use 0.011 parts by weight to 0.055 parts by weight based on the ride.
触媒が０．０１１重量部り少ないと、重合度が大きくな
らず、０．０５５重量部り多いと反応熱のために反応温
度が上昇し温度コントロールが困難となり、同時に着色
が著しくなる。好ましくは０．０２〜０．０４４重量部
範囲がよい。If the catalyst is less than 0.011 parts by weight, the degree of polymerization will not increase, and if it is more than 0.055 parts by weight, the reaction temperature will rise due to the reaction heat, making temperature control difficult, and at the same time, coloration will become significant. Preferably, the range is 0.02 to 0.044 parts by weight.
本発明方法において使用する炭素数１０〜１８のＩｌ状
フルフールは、’ ｎ−テシルアルコール、ラウリルア
ルコール、ミリスチルアルコール、セチルアルコール、
ステ７リルアルコール等カ使用でき、特定範囲内で用い
る限り、これらを用いた場合所望のポリグリコール酸が
得られる。アルコールは触媒促進剤、重合調節剤として
作用し、目的生成物のポリグリコール酸の末端残基とし
て、ポリマー中に残存するが、これら直鎖状高級アルコ
ールは天然に存在する油脂から還元により容易に入手で
きるものであり、実際上無害である。特にラウリルアル
コールは評価もあり、好ましいフルコールである。The Il-like furfurs having 10 to 18 carbon atoms used in the method of the present invention include 'n-tesyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol,
Steryl alcohol and the like can be used, and as long as they are used within a specific range, the desired polyglycolic acid can be obtained. Alcohol acts as a catalyst promoter and polymerization regulator, and remains in the polymer as a terminal residue of polyglycolic acid, the target product, but these linear higher alcohols can be easily removed from naturally occurring fats and oils by reduction. It is readily available and virtually harmless. In particular, lauryl alcohol has been evaluated and is a preferred furukol.
これら炭素数１０から１８の直鎖アルコールをスズ触媒
１重量倍に対し０．５〜２８倍用いる。特１に１・０〜
２・３倍用いる０が好ま１い・使用量が０．５倍以下で
あると、触媒量を００５重量係程程度多量に用いても得
られるポリマの重合度が小さく粘度が低いので溶融紡糸
等の成型が不可能となる。また、２．８倍以上使用する
場合もアルコールが調節剤として働き重合を過度に制御
するために、重合度を高くできない。この所定範囲内で
用途に合せて、重合温度、触媒量と組合せて適宜選択す
る。These linear alcohols having 10 to 18 carbon atoms are used in an amount of 0.5 to 28 times per weight of the tin catalyst. Special 1 to 1.0~
It is preferable to use 2 to 3 times the amount of 0. If the amount used is 0.5 times or less, the degree of polymerization of the obtained polymer will be small and the viscosity will be low even if the amount of catalyst is as large as 0.05 weight percent. etc. becomes impossible. Further, even when using 2.8 times or more, the degree of polymerization cannot be increased because the alcohol acts as a regulator and controls the polymerization excessively. It is appropriately selected within this predetermined range in combination with the polymerization temperature and catalyst amount depending on the application.
炭素数１２のラウリルアルコールを用いる場合、グリコ
ライドに対し約０．０６重量係程度のオクタン酸第−ス
ズを用いオクタン酸第−スズに対し約２．０倍程度のラ
ウリルフルコールを使用して１８０℃で２時間重合させ
ると、固有粘度１．２１程度の無色のポリグリコール酸
が得られ、紡糸用には最適のものが得られる。When lauryl alcohol having 12 carbon atoms is used, stannous octoate is used at a weight coefficient of about 0.06 relative to glycolide, and lauryl fluorol is used at a weight ratio of about 2.0 times relative to stannous octoate. When polymerized at .degree. C. for 2 hours, a colorless polyglycolic acid having an intrinsic viscosity of about 1.21 is obtained, which is optimal for spinning.
本発明方法において、重合温度は１００〜１８０°Ｃに
維持しておこなう。室温伺近でも重合するが所望の物性
を有するポリグリコール酸は得られない。好ましい温度
は１６ｏから１８０’Ｃの間である。重合温度が１８０
”０より高いと着色が著しい。In the method of the present invention, the polymerization temperature is maintained at 100 to 180°C. Polyglycolic acid polymerizes even at temperatures close to room temperature, but polyglycolic acid with desired physical properties cannot be obtained. Preferred temperatures are between 16o and 180'C. Polymerization temperature is 180
``If it is higher than 0, the coloring is significant.
本発明においては、通常、添加されている安定剤等の添
加剤を加えても良い。また、必要とあれハ、ジ、エチル
カルピトール、ジエチルベンゼン等の反応系に不活性な
非プロトン性高沸点溶媒を希釈剤として加えることも可
能である。In the present invention, additives such as stabilizers that are normally added may be added. Furthermore, if necessary, an inert aprotic high-boiling solvent such as di-ethylcarpitol or diethylbenzene can be added as a diluent to the reaction system.
本発明の原料であるグリコライドは通常公知（例えば、
米国特許第２，６６８，１６２号）の方法でオキシ酢酸
（グリコール酸）より製造される。Glycolide, which is a raw material of the present invention, is generally known (for example,
It is produced from oxyacetic acid (glycolic acid) by the method of U.S. Pat. No. 2,668,162).
本発明方法は、例えば以下のようにして実施できる。The method of the present invention can be carried out, for example, as follows.
グリコライド（ｙａｐ ｓ ５．５〜ａ ４．５℃）
を重合容器に装入し、クロロホルムなどの溶媒に溶かし
たオクタン酸第〜スズ触媒と直鎖状脂肪族アルコールを
添加した後１、−真空で脱気する。アルゴンで置換しア
ルゴン雰囲気下で加熱し、１００から１８０″Ｃの間の
定温で２時間から６時間重合させる。冷却後容器より取
り出し、無色のポリグリコール酸を得る。このようにし
て得られたポリグリコール酸は分子量は約１万から約１
０万の間にあす、フエ／−ル（１０重量部）とトリクロ
ルフェノール（７重量部）の混合溶媒中６０±０，１℃
、濃度０．５係で測定した時、少なくとも約１．０以上
の固有粘度を示し、生体内吸収性ポリマとして、外科用
縫合糸などへの使用に適したものが得られる。また色調
の良好なことより、閤品価値があり他に多（の医学用途
にも適用可能である。Glycolide (yaps 5.5~a 4.5℃)
is charged into a polymerization vessel, and after adding a stannous octoate catalyst and a linear aliphatic alcohol dissolved in a solvent such as chloroform, 1. - degassed in vacuum. The mixture is replaced with argon and heated under an argon atmosphere, and polymerized for 2 to 6 hours at a constant temperature between 100 and 180"C. After cooling, the container is taken out and colorless polyglycolic acid is obtained. Polyglycolic acid has a molecular weight of about 10,000 to about 1
60±0.1℃ in a mixed solvent of phenol (10 parts by weight) and trichlorophenol (7 parts by weight)
The polymer exhibits an intrinsic viscosity of at least about 1.0 or more when measured at a concentration of 0.5, and is suitable for use as a bioabsorbable polymer in surgical sutures and the like. In addition, due to its good color tone, it is valuable as a pharmaceutical product and can be applied to many other medical uses.
次に本発明の実施例を示して、さらに具体的に説明する
。Next, examples of the present invention will be shown and explained in more detail.
なお、実施例中の固有粘度は、重合生成物をフェノール
（１０重量部）とトリクロルフェノール（７重量部）の
混合溶媒に溶解し、ウベローデ、゛・
粘度計を用いて３０．±０．１℃、濃度０．５％で測定
した。In addition, the intrinsic viscosity in the examples was determined by dissolving the polymerization product in a mixed solvent of phenol (10 parts by weight) and trichlorophenol (7 parts by weight) and using an Ubbelohde viscometer. Measurements were made at ±0.1°C and a concentration of 0.5%.
実施例１゜
オキシ酢酸（グリコール酸）より得られたグリコライド
（８′５．５〜８４．５℃）２０ｔを肉厚の円筒型カラ
ス製重合容器（セパラフル式二本体とカバーが分離可能
）に装入し、オクタン酸第−スズ６．０ｍタ （０，０
３重量％、１．５Ｘ１０ モル）のクロロホルムｍｏ
ｏ、６ｖ−ｔ とラウリルアルコール１２．０ ｍＷ
（０，０６重量％、６．５ Ｘ １０ モル、オク
タン酸第−スズ触媒の２．０重量倍）のりＬ：＋ロホル
ム溶液０．５ ｍｔ とを容器中へ添加し、真空（１〜
５ ｍｍＨ？ ） テ２時間脱気した後、アルゴンガス
で置換した。この混合物をアルゴン雰囲気下でミリフン
オイルかスを用いて６時間１８０“Ｃで加熱した。冷却
後、この無色の溶融反応生成物を容器から取り出し１ハ
ンマーで粗粉砕し、小型粉砕機で微粉砕すると、無色の
ポリグリコール酸１９ｔが得られ１こ。このポリグリコ
ール酸の粘度を測定すると固有粘度（１〕ｉｎｈ二１．
２４を示し２４５℃の溶融温度で紡糸した後１７０’Ｏ
の空気中で６倍延伸した結果引張強度５５ ｋｇ／ ｙ
ｒＬｒｎ２の良好な繊維を得た。Example 1゜20 tons of glycolide (8'5.5 to 84.5°C) obtained from oxyacetic acid (glycolic acid) was placed in a thick cylindrical glass polymerization container (separaflu type, two main bodies and cover can be separated) 6.0m of stannous octoate (0,0
3% by weight, 1.5X10 mol) of chloroform mo
o, 6v-t and lauryl alcohol 12.0 mW
(0.06% by weight, 6.5 x 10 mol, 2.0 times the weight of stannous octoate catalyst) glue L: + 0.5 mt of roform solution was added into the container and vacuum
5mmH? ) After degassing for 2 hours, the atmosphere was replaced with argon gas. The mixture was heated at 180"C for 6 hours under an argon atmosphere using a millimeter oil bath. After cooling, the colorless molten reaction product was removed from the container and coarsely ground with a hammer, then finely ground with a small grinder. , 19 tons of colorless polyglycolic acid was obtained.The viscosity of this polyglycolic acid was measured and found to be an intrinsic viscosity (1] inh21.
24 and 170'O after spinning at a melting temperature of 245°C.
Tensile strength: 55 kg/y as a result of stretching 6 times in air.
A good fiber of rLrn2 was obtained.
実施例２〜１１
ラウリルアルコールの邦をグリコライドに対し、ｏ Ｉ
Ｌ１′ｑｂかも０．０９９重量の間に変え、実施例１と
同様０．０３重量％のオクタン酸第−スズの存在下１８
０℃２時間で重合させた。但し、実施例１１、のみ重合
温度を２２０°Ｃで２時間で重合させた。Examples 2 to 11 The ratio of lauryl alcohol to glycolide, o I
L1'qb was also varied between 0.099 and 18% by weight in the presence of 0.03% by weight of stannous octoate as in Example 1.
Polymerization was carried out at 0°C for 2 hours. However, only in Example 11, polymerization was carried out at a polymerization temperature of 220°C for 2 hours.
結果を表１に示す。実施例２．３．１０，１１は比較例
として示したものであり、実施例２．６．１０で得られ
たポリグリコール酸は２４成での溶融粘度が低く、紡糸
の際、糸切れを生じ延伸不可能であった。また実施例１
１で得れたポリグリコール酸は着色（濃かっ色）が著し
かった。The results are shown in Table 1. Examples 2.3.10 and 11 are shown as comparative examples, and the polyglycolic acid obtained in Example 2.6.10 has a low melt viscosity at 24 compositions, and does not cause yarn breakage during spinning. It was impossible to stretch. Also, Example 1
The polyglycolic acid obtained in Step 1 was significantly colored (dark brown).
実施例ふ（２
実施例１に示した製造方法に従い、ステ７リル７ ル＝
＋ −／Ｌ、 （Ｃｌ８Ｈ３７０Ｈ） １２．０ｍｆ（
０，０６重量％、４．４×１０ モル、オクタン酸第−
スズ触媒の２．０重量倍）を使用して、グリコライド２
ＣＩを１８０℃で３時間加熱すると、１９．５ｆの無色
のポリグリコール酸が得られた。このポリマーの固有粘
度は１．１０であった。Example (2) According to the manufacturing method shown in Example 1, the production method was as follows:
+ -/L, (Cl8H370H) 12.0mf (
0.06% by weight, 4.4 x 10 mol, di-octanoic acid
Using 2.0 times the weight of tin catalyst), glycolide 2
Heating CI at 180°C for 3 hours yielded 19.5f of colorless polyglycolic acid. The intrinsic viscosity of this polymer was 1.10.
Claims (1)
によるポリグリコール酸の製造法において、グリフライ
ドに対しオクタン酸第−スズを０．０１〜０．０５重量
係、およびオクタン酸第−スズに対し０．５〜２．８重
量倍の炭素数１０〜１８の直鎖状脂肪族アルコールの存
在下で、１００〜１８０℃の温度でグリコライドを重合
させること、を特徴とするポリグリコール酸の製造方法
。 ２、 オクタン酸第−スズに対し、炭素数１０〜１８の
直鎖状脂肪族アルコールを１．０〜２．３重量倍使用す
る特許請求の範囲第１項記載の方法。[Claims] 1. A method for producing polyglycolic acid by polymerizing glycolide in the presence of stannous octoate, in which stannous octoate is added in a proportion of 0.01 to 0.05 by weight to glycolide, and It is characterized by polymerizing glycolide at a temperature of 100 to 180°C in the presence of a linear aliphatic alcohol having 10 to 18 carbon atoms in an amount of 0.5 to 2.8 times the weight of stannous octoate. A method for producing polyglycolic acid. 2. The method according to claim 1, wherein the linear aliphatic alcohol having 10 to 18 carbon atoms is used in an amount of 1.0 to 2.3 times the weight of stannous octoate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11232981A JPS5813624A (en) | 1981-07-20 | 1981-07-20 | Preparation of polyglycolic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11232981A JPS5813624A (en) | 1981-07-20 | 1981-07-20 | Preparation of polyglycolic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5813624A true JPS5813624A (en) | 1983-01-26 |
| JPS6231736B2 JPS6231736B2 (en) | 1987-07-10 |
Family
ID=14583947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11232981A Granted JPS5813624A (en) | 1981-07-20 | 1981-07-20 | Preparation of polyglycolic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5813624A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54107674A (en) * | 1978-02-10 | 1979-08-23 | Toshiba Corp | Dry etching unit |
| JPS6142135A (en) * | 1984-08-02 | 1986-02-28 | Agency Of Ind Science & Technol | Plasma etching method |
| JPS62204529A (en) * | 1986-03-05 | 1987-09-09 | Toshiba Corp | Dry etching method |
| EP1440992A1 (en) * | 2003-01-21 | 2004-07-28 | Société de Conseils de Recherches et d'Applications Scientifiques ( S.C.R.A.S.) | Catalyst composition for (co)polymerisation of lactide and glycolide |
| FR2867698A1 (en) * | 2004-03-16 | 2005-09-23 | Beaufour Ipsen S C R A S | CATALYTIC SYSTEM FOR (CO) OLIGOMERIZATION OF LACTIDE AND GLYCOLIDE |
| JP2022509214A (en) * | 2018-11-27 | 2022-01-20 | エボニック オペレーションズ ゲーエムベーハー | A method for producing absorbent polyester as a granule or powder by bulk polymerization. |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02114707U (en) * | 1989-02-28 | 1990-09-13 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4862899A (en) * | 1971-11-22 | 1973-09-01 |
-
1981
- 1981-07-20 JP JP11232981A patent/JPS5813624A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4862899A (en) * | 1971-11-22 | 1973-09-01 |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54107674A (en) * | 1978-02-10 | 1979-08-23 | Toshiba Corp | Dry etching unit |
| JPS6339095B2 (en) * | 1978-02-10 | 1988-08-03 | Tokyo Shibaura Electric Co | |
| JPS6142135A (en) * | 1984-08-02 | 1986-02-28 | Agency Of Ind Science & Technol | Plasma etching method |
| JPS62204529A (en) * | 1986-03-05 | 1987-09-09 | Toshiba Corp | Dry etching method |
| AU2004207648B2 (en) * | 2003-01-21 | 2009-11-12 | Centre National De La Recherche Scientifique (C.N.R.S.) | Lactide and glycolide (co)polymerization catalytic system |
| WO2004067602A1 (en) * | 2003-01-21 | 2004-08-12 | Societe De Conseils De Recherche Et D'applications Scientifiques (S.C.R.A.S.) | Lactide and glycolide (co)polymerization catalytic system |
| EP1440992A1 (en) * | 2003-01-21 | 2004-07-28 | Société de Conseils de Recherches et d'Applications Scientifiques ( S.C.R.A.S.) | Catalyst composition for (co)polymerisation of lactide and glycolide |
| FR2867698A1 (en) * | 2004-03-16 | 2005-09-23 | Beaufour Ipsen S C R A S | CATALYTIC SYSTEM FOR (CO) OLIGOMERIZATION OF LACTIDE AND GLYCOLIDE |
| WO2005100439A1 (en) * | 2004-03-16 | 2005-10-27 | Societe De Conseils De Recherches Et D'applications Scientifiques (S.C.R.A.S.) | Use of a catalytic system for lactide and glycolide (co)oligomerization |
| JP2007529480A (en) * | 2004-03-16 | 2007-10-25 | ソシエテ ド コンセイユ ド ルシェルシェ エ ダアップリカーション シャンティフィック（エス．セー．エール．アー．エス．） | Use of catalyst system for (co) oligopolymerization of lactide and glycolide |
| US8389668B2 (en) | 2004-03-16 | 2013-03-05 | Ipsen Pharma S.A.S. | Use of a catalytic system for lactide and glycolide (co) oligomerization |
| NO340223B1 (en) * | 2004-03-16 | 2017-03-20 | Ipsen Pharma Sas | Use of a catalytic system for lactide and glycolide (co) oligomerization |
| JP2022509214A (en) * | 2018-11-27 | 2022-01-20 | エボニック オペレーションズ ゲーエムベーハー | A method for producing absorbent polyester as a granule or powder by bulk polymerization. |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6231736B2 (en) | 1987-07-10 |
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