JPH05320326A - Biodegradable aliphatic polyester polymer and its production - Google Patents

Biodegradable aliphatic polyester polymer and its production

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Publication number
JPH05320326A
JPH05320326A JP12476492A JP12476492A JPH05320326A JP H05320326 A JPH05320326 A JP H05320326A JP 12476492 A JP12476492 A JP 12476492A JP 12476492 A JP12476492 A JP 12476492A JP H05320326 A JPH05320326 A JP H05320326A
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polymer
polyester polymer
aliphatic polyester
present invention
formula
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JP12476492A
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JPH0713129B2 (en )
Inventor
Michio Ishioka
Atsushi Iyoda
Yoshie Kida
Noriyuki Miyoshi
Atsuyoshi Nakayama
Kazuhisa Takii
Noboru Yamamoto
徳享 三好
敦好 中山
惇 伊与田
襄 山本
吉重 木田
和久 瀧井
道男 石岡
Original Assignee
Agency Of Ind Science & Technol
Okamura Seiyu Kk
岡村製油株式会社
工業技術院長
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Abstract

PURPOSE:To obtain a polyester polymer free from pollution having a specific structural recurring units, excellent in mechanical properties, having biodegradability, completely degradable in soil and sea and free from environmental pollution. CONSTITUTION:A substantially linear aliphatic polyester polymer having recurring units expressed by formula I (R1 and R2 are hydrogen and hydroxyl group; m and n are integer of 0-50) and 3000-100000 number-average molecular weight. This polymer is produced by reacting a dicarboxylic acid expressed by formula II with a diglycidyl ester expressed by formula III. This reaction is carried out at 90-130 deg.C in argon.

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、生分解性脂肪族ポリエステル重合体及びその製造法に関する。 The present invention relates to a biodegradable aliphatic polyester polymer and its production method.

【0002】 [0002]

【従来技術とその課題】近年、医療分野、農林水産分野及び包装材料等ディスポーザブル日用品分野に利用すべく、それらの廃棄物処理の容易さという観点から生分解性という新しい機能を有する合成高分子の研究開発が行われている。 [Its Problems with the prior art In recent years, in order to use the medical field, agriculture, forestry and fisheries and packaging materials disposable daily necessities art, from the viewpoint of their waste ease of synthetic polymers having a new feature called biodegradable research and development is being carried out.

【0003】脂肪族ポリエステルが生分解性を有していることは既に公知である。 [0003] It is already known that the aliphatic polyester has biodegradability. また該ポリエステルの側鎖に水酸基を導入することにより親水性を向上させたり、また官能基を有する有機低分子又は高分子化合物を該ポリエステルと共有結合させることにより、新しい機能を備えた高分子誘導体を合成することも可能である。 The polymeric derivatives or improve the hydrophilicity and by causing the organic low-molecular or polymer compound having a functional group covalently bound to the polyester, with a new function by introducing a hydroxyl group in the side chain of the polyester it is also possible to synthesize.

【0004】しかしながら、今日までに開発されている側鎖に水酸基やカルボキシル基のような官能基を有する脂肪族ポリエステルは、分子量が充分に大きいものではなく、また側鎖に官能基の数を増加させれば生分解性が向上する反面、該ポリエステルの機械的性質が低下するのを避けられないものである。 However, aliphatic polyesters having a functional group such as hydroxyl group or carboxyl group in the side chain has been developed to date, not the molecular weight is sufficiently large, also increase the number of functional groups in the side chain although the improved biodegradability when brought into, in which the mechanical properties of the polyester are unavoidable from lowering. 而して、機械的性質に優れ、しかも生分解性を有する高分子量の脂肪族ポリエステルは、未だ開発されていない。 And Thus, excellent mechanical properties, yet high molecular weight aliphatic polyester having biodegradability has not been developed yet.

【0005】 [0005]

【課題を解決するための手段】本発明の目的は、機械的性質に優れ、しかも生分解性を有する高分子量の脂肪族ポリエステルを提供することにある。 Means for Solving the Problems The object of the present invention is excellent in mechanical properties, yet to provide a high molecular weight aliphatic polyester having biodegradability.

【0006】即ち、本発明は、下記一般式 [0006] That is, the present invention is represented by the following general formula

【0007】 [0007]

【化4】 [Of 4]

【0008】[式中R 1及びR 2は、同一又は異なって、水素原子又は水酸基を示す。 [0008] [wherein R 1 and R 2 are the same or different, represent a hydrogen atom or a hydroxyl group. m及びnは、同一又は異なって、0又は1〜50の整数を示す。 m and n are the same or different and are each an integer of 0 or 1 to 50. ]で表わされる繰返し単位を有し、数平均分子量が3000〜100 Has a repeating unit represented by, a number average molecular weight of from 3,000
000である、実質的に線状な生分解性脂肪族ポリエステル重合体に係る。 000., substantially according to the linear biodegradable aliphatic polyester polymer.

【0009】本発明の生分解性脂肪族ポリエステル重合体は、例えば一般式 [0009] Biodegradable aliphatic polyester polymer of the present invention, for example, the general formula

【0010】 [0010]

【化5】 [Of 5]

【0011】[式中R 1 、R 2及びnは前記に同じ。 [0011] [wherein R 1, R 2 and n are as defined above. ]
で表わされるジカルボン酸と一般式 In the dicarboxylic acid represented with general formula

【0012】 [0012]

【化6】 [Omitted]

【0013】[式中mは前記に同じ。 [0013] [m in the formula is the same as above. ]で表わされるジグリシジルエステルとを反応させることにより製造される。 A diglycidyl ester represented by] is prepared by reacting. 該反応は、液体又は固体のジカルボン酸(2)とジグリシジルエステル(3)とを適宜の割合で混合溶融させた後、不活性ガス、例えばアルゴン気流中で90〜1 The reaction, after the liquid or solid dicarboxylic acid (2) and a diglycidyl ester (3) was melt mixed at an appropriate ratio, inert gas, for example in a stream of argon 1:90
30℃程度に加熱することにより進行し、斯くして目的とする生分解性脂肪族ポリエステル重合体が容易に製造される。 Proceed by heating to about 30 ° C., the biodegradable aliphatic polyester polymer is readily manufactured for the purpose by thus.

【0014】本発明の重合体は、土壌、海水中等の自然環境下で完全に生分解されるものである。 [0014] The polymer of the present invention is one in which the soil, that is completely biodegradable in the natural environment of seawater moderate. また本発明の重合体は、都市ごみや下水処理場の余剰汚泥等の処理法として知られている好気的条件下での急速堆肥処理でも速やかに生分解させ得ることは勿論、リパーゼ生産菌、 The polymers of the present invention, of course be obtained promptly biodegrade in rapid composting process under aerobic conditions known as the processing method such as excess sludge municipal waste and sewage treatment plants, lipase producing bacteria ,
リパーゼ含有物等によっても分解され得る。 It may be degraded by lipase-containing products and the like. 従って、本発明の重合体を土中に埋めた場合にはなんらの残渣を生ずることなく完全に分解され、また仮に海中に流出した場合でも同様に分解され、非分解性プラスチックに見られるような公害問題を生ずることはない。 Thus, the polymers of the present invention is completely degraded without causing any of the residues when buried in soil, also be similarly decomposed even when temporarily flows out into the sea, as seen in non-degradable plastic never cause a pollution problem.

【0015】斯かる特性を有する本発明の重合体は、単独で又は他の生分解性高分子とブレンドすることにより、繊維やフィルムに150℃以下の成形温度で加工され得、農林業分野では例えば植林用の鉢やマルチフィルム等に、医薬分野ではその生分解性を利用して徐放性医薬の支持体等に、日用品や工業品分野では本発明重合体単独で又はポリエステル、ポリエチレンフィルムに適量混合し、崩壊性フィルム材料の添加剤等に、それぞれ利用することができる。 The polymers of the present invention having such properties, by blending with alone or in combination with other biodegradable polymers, obtained are processed at a molding temperature of 0.99 ° C. or less to fibers and films, in the agriculture and forestry field for example, pots and multi films for planting, in the pharmaceutical field by utilizing the biodegradable support sustained release pharmaceutical such as daily necessities and the industrial products sector in the invention polymer alone or a polyester, a polyethylene film an appropriate amount is mixed, additives such as disintegrating film materials can be used respectively.

【0016】 [0016]

【発明の効果】本発明の重合体は、機械的性質に優れ、 Polymers of the present invention exhibits excellent mechanical properties,
しかも生分解性を有するものである。 Moreover those having biodegradability. また、本発明の方法によれば、本発明重合体を100℃前後の温度で無溶媒且つ無触媒で容易に製造できる。 Further, according to the method of the present invention, the present invention polymers can be easily produced without solvent and without catalyst in around 100 ° C. temperature. 更に本発明の方法によれば、R 1 、R 2 、m及びnを変えて上記一般式(1)で表わされる本発明重合体の単位ユニット中の水酸基の数やエステル含量を適宜調節することができる。 Further according to the method of the present invention, by appropriately adjusting the number and ester content of hydroxyl groups in basic unit of the present invention the polymer represented by the above general formula (1) by changing the R 1, R 2, m and n can.

【0017】 [0017]

【実施例】以下実施例を掲げて本発明をより一層明らかにするが、本発明はこれら実施例になんら限定されるものではない。 EXAMPLES further clarify the present invention working examples below, but the present invention should not be construed as being limited to these examples.

【0018】実施例1 ビス〔2,3−エポキシプロピル〕−1,18−オクタデカンジカルボキシラート(商品名:SL−20G、一般式(3)においてm=18のジグリシジルエステル、 [0018] Example 1 Bis [2,3-epoxypropyl] 1,18 octadecane carboxylate (trade name: SL-20G, diglycidyl ester of m = 18 in the general formula (3),
岡村製油(株)製、エポキシ当量296.1)12.0 Okamura Oil Co., Ltd., epoxy equivalent 296.1) 12.0
g(0.02モル)及びアジピン酸(分子量146) g (0.02 moles) and adipic acid (molecular weight 146)
2.92g(0.02モル)を四つ口フラスコに同時に入れる。 2.92g (0.02 mol) Add concurrently neck flask. 窒素ガスを通じて空気を系内より追い出した後、内容物を融解させ、100〜105℃で10時間加熱攪拌する。 After the air was expelled from the system through the nitrogen gas, to melt the contents, for 10 hours heated with stirring at 100-105 ° C.. 生成した粘稠物をクロロホルムに溶解後、 After dissolving the resulting viscous chloroform,
メタノールで再沈殿し、目的とする本発明の重合体を得る。 Reprecipitated in methanol to obtain a polymer of the present invention of interest.

【0019】 メタノール沈殿部の収量:12.70g(85.1%) 溶融点:59〜76℃ 極限粘度(クロロホルム30℃):0.07 数平均分子量(VPO法):4280 得られる重合体のIRスペクトル図を図1に示す。 The methanol precipitation of Yield: 12.70 g (85.1%) melting point: 59 to 76 ° C. The intrinsic viscosity (chloroform 30 ° C.): 0.07 number-average molecular weight (VPO method): the 4280 resulting polymer the IR spectrum diagram in FIG.

【0020】実施例2 SL−20G 12.0g(0.02モル)及びエイコサン二酸(商品名:SL−20、一般式(2)においてR 1 =R 2 =H,n=16のジカルボン酸、岡村製油(株)製)6.84g(0.02モル)を用い、上記実施例1と同様にして本発明の重合体を得る。 [0020] Example 2 SL-20G 12.0g (0.02 mol) and eicosanoic acid (trade name: SL-20, in the general formula (2) R 1 = R 2 = H, dicarboxylic acids n = 16 , oil and Co.) 6.84 g (0.02 mol) using Okamura, obtaining a polymer of the present invention in the same manner as in example 1.

【0021】 メタノール沈殿部の収量:16.50g(87.6%) 溶融点:79〜83℃ 極限粘度(クロロホルム30℃):0.31 得られる重合体のIRスペクトル図を図2に、 1 H−N The methanol precipitation of Yield: 16.50 g (87.6%) melting point: 79 to 83 ° C. The intrinsic viscosity (chloroform 30 ° C.): The IR spectrum of 0.31 obtained polymer 2, 1 H-N
MRスペクトル図を図3に、 13 C−NMRスペクトル図を図4にそれぞれ示す。 The MR spectrum diagram in FIG. 3, respectively the 13 C-NMR spectrum diagram in FIG.

【0022】実施例3 SL−20G 100g(0.17モル)及びエイコサン二酸51.6g(0.15モル)を用い、上記実施例1と同様にして本発明の重合体を得る。 [0022] Using Example 3 SL-20G 100g (0.17 mol) and eicosadioate 51.6 g (0.15 mol), obtaining a polymer of the present invention in the same manner as in Example 1.

【0023】 メタノール沈殿部の収量:128.9g(85.0%) 溶融点:82〜87℃ 極限粘度(クロロホルム30℃):0.51 数平均分子量(VPO法):37500 得られる重合体のIRスペクトル図を図5に、 1 H−N The methanol precipitation of Yield: 128.9 g (85.0%) melting point: 82-87 ° C. The intrinsic viscosity (chloroform 30 ° C.): 0.51 number-average molecular weight (VPO method): the 37500 resulting polymer Figure 5 the IR spectrum diagram, 1 H-N
MRスペクトル図を図6に、 13 C−NMRスペクトル図を図7にそれぞれ示す。 The MR spectrum diagram in FIG. 6, respectively the 13 C-NMR spectrum diagram in FIG.

【0024】実施例4 SL−20G 180g(0.30モル)及びりんご酸40.7g(0.30モル)を用い、上記実施例1と同様にして本発明の重合体を得る。 [0024] Using Example 4 SL-20G 180g (0.30 mol) and malic acid 40.7 g (0.30 mol), obtaining a polymer of the present invention in the same manner as in Example 1.

【0025】 メタノール沈殿部の収量:181g(82.0%) 溶融点:70.9〜81℃ 極限粘度(クロロホルム30℃):0.30 数平均分子量(VPO法):9800。 The methanol precipitation of Yield: 181 g (82.0%) melting point: 70.9-81 ° C. The intrinsic viscosity (chloroform 30 ° C.): 0.30 number-average molecular weight (VPO method): 9800.

【0026】実施例5 SL−20G 225g(0.38モル)及びエイコサン二酸116.3g(0.34モル)を四つ口フラスコに同時に仕込む。 The charged Example 5 SL-20G 225g (0.38 mol) and eicosanoic simultaneously diacid 116.3g of (0.34 mol) in a four-necked flask. 窒素ガスを通じて空気を系内より追い出した後、内容物を融解させ、その中に精製したジメチルアセトアミド1g(0.011モル)を添加する。 After the air was expelled from the system through the nitrogen gas, to melt the contents, adding dimethylacetamide 1 g (0.011 mol) of purified therein. その後100〜105℃で20時間加熱攪拌する。 Thereafter 20 hours stirring at 100-105 ° C.. 生成した粘稠物をクロロホルムに溶解後、メタノールで再沈殿し、目的とする本発明の重合体を得る。 After dissolving the resulting viscous in chloroform, reprecipitated with methanol, to obtain a polymer of the present invention of interest.

【0027】 メタノール沈殿部の収量:278.3g(88.0%) 溶融点:85〜91℃ 極限粘度(クロロホルム30℃):0.76 数平均分子量(VPO法):87500。 The methanol precipitation of Yield: 278.3g (88.0%) melting point: from 85 to 91 ° C. The intrinsic viscosity (chloroform 30 ° C.): 0.76 number-average molecular weight (VPO method): 87,500.

【0028】実施例6 上記実施例1〜5で得られた各重合体の生分解性を酵素分解法により評価した。 [0028] The biodegradability of each polymer obtained in Example 6 above Example 1-5 was evaluated by enzymatic hydrolysis. 即ち、各重合体25mgを30 That is, each polymer 25 mg 30
℃の蒸留水2ml中に48時間浸漬して水可溶分を完全に除去した後、リン酸緩衝液(pH7)2mlを加えて懸濁し、リパーゼ(リゾープス・アルフィズス)25μ Of distilled water in 2ml of ° C. 48 hours immersed in After complete removal of the water-soluble component, phosphate buffer solution (pH7) was added to 2ml suspended, lipase (Rhizopus Arufizusu) 25.mu.
l(1250ユニット)を加え、一定時間放置後、重合体を取出し、水洗、乾燥後、秤量した。 l a (1250 units) added and left for a predetermined time, taken out of the polymer, washed with water, dried and weighed. また、リン酸緩衝液を0.2μmフィルターで濾過したものについて濃塩酸1滴を加えた後、水に可溶の有機物をTOC測定装置を用いて定量した。 Further, after adding one drop of concentrated hydrochloric acid for those filtered phosphate buffer at 0.2μm filter and quantified soluble organic matter with TOC measurement device in water. 比較のために、酵素を含まない場合についても同様の操作を行なった。 For comparison, also performed the same operation for the case without enzyme. 結果を下記表1に示す。 The results are shown in Table 1 below.

【0029】 [0029]

【表1】 [Table 1]

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】実施例1で得られる重合体のIRスペクトル図である。 1 is an IR spectrum of the polymer obtained in Example 1.

【図2】実施例2で得られる重合体のIRスペクトル図である。 Figure 2 is an IR spectrum of the polymer obtained in Example 2.

【図3】実施例2で得られる重合体の1 H−NMRスペクトル図である。 Figure 3 is a 1 H-NMR spectrum of the polymer obtained in Example 2.

【図4】実施例2で得られる重合体の13 C−NMRスペクトル図である。 4 is a 13 C-NMR spectrum of the polymer obtained in Example 2.

【図5】実施例3で得られる重合体のIRスペクトル図である。 Figure 5 is an IR spectrum of the polymer obtained in Example 3.

【図6】実施例3で得られる重合体の1 H−NMRスペクトル図である。 6 is a 1 H-NMR spectrum of the polymer obtained in Example 3.

【図7】実施例3で得られる重合体の13 C−NMRスペクトル図である。 7 is a 13 C-NMR spectrum of the polymer obtained in Example 3.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 伊与田 惇 大阪府池田市緑丘1−7−10 (72)発明者 瀧井 和久 大阪府柏原市河原町4番5号 岡村製油株 式会社内 (72)発明者 木田 吉重 大阪府柏原市河原町4番5号 岡村製油株 式会社内 (72)発明者 石岡 道男 大阪府柏原市河原町4番5号 岡村製油株 式会社内 (72)発明者 三好 徳享 大阪府柏原市河原町4番5号 岡村製油株 式会社内 ────────────────────────────────────────────────── ─── of the front page continued (72) inventor Atsushi Iyoda Osaka Prefecture Ikeda Midorigaoka 1-7-10 (72) inventor Takii Kazuhisa Osaka Prefecture Kashiwara Kawaramachi No. 4 No. 5 Okamura oil shares in the company (72) invention who Kida YoshiShigeru Osaka Prefecture Kashiwara Kawaramachi No. 4 No. 5 Okamura oil shares in the company (72) inventor Michio Ishioka Osaka Prefecture Kashiwara Kawaramachi No. 4 No. 5 Okamura oil shares in the company (72) inventor Miyoshi IsaoToru Osaka Prefecture Kashiwara Kawaramachi No. 4 No. 5 Okamura oil shares in the company

Claims (2)

    【特許請求の範囲】 [The claims]
  1. 【請求項1】下記一般式 【化1】 1. A following general formula ## STR1 ## [式中R 1及びR 2は、同一又は異なって、水素原子又は水酸基を示す。 [Wherein R 1 and R 2 are the same or different, represent a hydrogen atom or a hydroxyl group. m及びnは、同一又は異なって、0又は1〜50の整数を示す。 m and n are the same or different and are each an integer of 0 or 1 to 50. ]で表わされる繰返し単位を有し、数平均分子量が3000〜100000である、 Has a repeating unit represented by, a number average molecular weight of 3,000 to 100,000,
    実質的に線状な生分解性脂肪族ポリエステル重合体。 Substantially linear biodegradable aliphatic polyester polymer.
  2. 【請求項2】一般式 【化2】 2. A general formula 2] [式中R 1 、R 2及びnは前記に同じ。 [Wherein R 1, R 2 and n are as defined above. ]で表わされるジカルボン酸と一般式 【化3】 Dicarboxylic acids with the general formula ## STR3 ## represented by] [式中mは前記に同じ。 [M in the formula are the same as defined above. ]で表わされるジグリシジルエステルとを反応させることを特徴とする請求項1記載の生分解性脂肪族ポリエステル重合体の製造法。 Preparation of a biodegradable aliphatic polyester polymer of claim 1, wherein the reacting a diglycidyl ester represented by.
JP12476492A 1992-05-18 1992-05-18 Biodegradable aliphatic polyester polymer and its preparation Expired - Lifetime JPH0713129B2 (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996003454A1 (en) * 1994-07-21 1996-02-08 The Dow Chemical Company Hydroxy-functional thermoplastic polyesters
WO1997031979A1 (en) * 1996-02-28 1997-09-04 Biotechnology Research And Development Corporation Biodegradable polyester compositions with natural polymers and articles thereof
WO1997044388A1 (en) * 1996-05-24 1997-11-27 Biotechnology Research And Development Corporation Biodegradable polyester and natural polymer compositions and expanded articles therefrom
US5821286A (en) * 1996-05-24 1998-10-13 The United States Of America As Represented By The Secretary Of The Agriculture Biodegradable polyester and natural polymer compositions and films therefrom
US5852078A (en) * 1996-02-28 1998-12-22 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester compositions with natural polymers and articles thereof
WO1998051728A3 (en) * 1996-12-31 1999-04-01 Dow Chemical Co Hydroxy-functionalized polyester and poly(ester ether) oligomers
WO1999046397A1 (en) * 1998-03-10 1999-09-16 Cognis Deutschland Gmbh Enzymatic synthesis of polyesters
US6040063A (en) * 1996-06-28 2000-03-21 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer laminates
US6893527B1 (en) 1996-06-28 2005-05-17 William M. Doane Biodegradable polyester and natural polymer laminates
KR100734171B1 (en) * 2006-05-23 2007-06-26 재단법인서울대학교산학협력재단 Water soluble and biodegradable high molecular weight functional polyester and synthesis method thereof

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WO1996003454A1 (en) * 1994-07-21 1996-02-08 The Dow Chemical Company Hydroxy-functional thermoplastic polyesters
WO1997031979A1 (en) * 1996-02-28 1997-09-04 Biotechnology Research And Development Corporation Biodegradable polyester compositions with natural polymers and articles thereof
US6054510A (en) * 1996-02-28 2000-04-25 The United States Of America As Represented By The Secretary Of The Agriculture Biodegradable formed article
US5852078A (en) * 1996-02-28 1998-12-22 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester compositions with natural polymers and articles thereof
WO1997044388A1 (en) * 1996-05-24 1997-11-27 Biotechnology Research And Development Corporation Biodegradable polyester and natural polymer compositions and expanded articles therefrom
US5854345A (en) * 1996-05-24 1998-12-29 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer compositions and expanded articles therefrom
US5821286A (en) * 1996-05-24 1998-10-13 The United States Of America As Represented By The Secretary Of The Agriculture Biodegradable polyester and natural polymer compositions and films therefrom
US6040063A (en) * 1996-06-28 2000-03-21 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable polyester and natural polymer laminates
US6893527B1 (en) 1996-06-28 2005-05-17 William M. Doane Biodegradable polyester and natural polymer laminates
WO1998051728A3 (en) * 1996-12-31 1999-04-01 Dow Chemical Co Hydroxy-functionalized polyester and poly(ester ether) oligomers
WO1999046397A1 (en) * 1998-03-10 1999-09-16 Cognis Deutschland Gmbh Enzymatic synthesis of polyesters
KR100734171B1 (en) * 2006-05-23 2007-06-26 재단법인서울대학교산학협력재단 Water soluble and biodegradable high molecular weight functional polyester and synthesis method thereof

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