JPH0713129B2 - Biodegradable aliphatic polyester polymer and method for producing the same - Google Patents
Biodegradable aliphatic polyester polymer and method for producing the sameInfo
- Publication number
- JPH0713129B2 JPH0713129B2 JP12476492A JP12476492A JPH0713129B2 JP H0713129 B2 JPH0713129 B2 JP H0713129B2 JP 12476492 A JP12476492 A JP 12476492A JP 12476492 A JP12476492 A JP 12476492A JP H0713129 B2 JPH0713129 B2 JP H0713129B2
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- aliphatic polyester
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- polyester polymer
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Description
【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。FIELD OF THE INVENTION The present invention relates to a biodegradable aliphatic polyester polymer and a method for producing the same.
【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。2. Description of the Related Art In recent years, synthetic polymers having a new function of biodegradability from the viewpoint of ease of waste disposal for use in the fields of medicine, agriculture, forestry and fisheries, and disposable daily necessities such as packaging materials. Research and development is being conducted.
【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。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。It is already known that aliphatic polyesters are biodegradable. Further, by introducing a hydroxyl group into the side chain of the polyester to improve hydrophilicity, or by covalently bonding an organic low molecule or polymer compound having a functional group to the polyester, a polymer derivative having a new function 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。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。However, the aliphatic polyesters having a functional group such as a hydroxyl group or a carboxyl group in the side chain, which have been developed to date, do not have a sufficiently large molecular weight, and the number of functional groups in the side chain is increased. If so, the biodegradability is improved, but the mechanical properties of the polyester are inevitably deteriorated. Thus, a high molecular weight aliphatic polyester having excellent mechanical properties and biodegradability has not yet been developed.
【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。SUMMARY OF THE INVENTION An object of the present invention is to provide a high molecular weight aliphatic polyester having excellent mechanical properties and biodegradability.
【０００６】即ち、本発明は、下記一般式That is, the present invention has the following general formula
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】［式中Ｒ1 及びＲ2 は、同一又は異なっ
て、水素原子又は水酸基を示す。ｍ及びｎは、同一又は
異なって、０又は１〜５０の整数を示す。］で表わされ
る繰返し単位を有し、数平均分子量が３０００〜１００
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。[In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydroxyl group. m and n are the same or different and each represents 0 or an integer of 1 to 50. ] And has a number average molecular weight of 3,000 to 100.
000, which is a substantially 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The biodegradable aliphatic polyester polymer of the present invention has, for example, the general formula
【００１０】[0010]
【化５】 [Chemical 5]
【００１１】［式中Ｒ1 、Ｒ2 及びｎは前記に同じ。］
で表わされるジカルボン酸と一般式[Wherein R 1 , R 2 and n are the same as defined above. ]
Dicarboxylic acid represented by the general formula
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】［式中ｍは前記に同じ。］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。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
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。[In the formula, m is the same as above. ] It manufactures by making it react with the diglycidyl ester represented by this. In this reaction, liquid or solid dicarboxylic acid (2) and diglycidyl ester (3) are mixed and melted at an appropriate ratio, and then 90 to 1 in an inert gas, for example, an argon stream.
It proceeds by heating to about 30 ° C., and thus the desired biodegradable aliphatic polyester polymer is easily produced.
【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。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、
リパーゼ含有物等によっても分解され得る。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。The polymer of the present invention is completely biodegradable in natural environments such as soil and seawater. Further, the polymer of the present invention can be rapidly biodegraded even in rapid compost treatment under aerobic conditions known as a method for treating municipal solid waste and surplus sludge in sewage treatment plants, etc., as well as lipase-producing bacteria. ,
It can also be decomposed by a lipase-containing substance and the like. Therefore, when the polymer of the present invention is buried in the soil, it is completely decomposed without producing any residue, and even if it is discharged into the sea, it is decomposed similarly, as seen in non-degradable plastics. It does not cause pollution problems.
【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 polymer of the present invention having such characteristics can be processed into a fiber or a film at a molding temperature of 150 ° C. or lower by itself or by blending with other biodegradable polymer, and in the field of agriculture and forestry. For example, in pots and mulch films for planting trees, in the pharmaceutical field it is used as a support for sustained-release pharmaceuticals by utilizing its biodegradability, and in the fields of daily necessities and industrial products, the polymer of the present invention alone or as a polyester, polyethylene film It can be used by being mixed in an appropriate amount and used as an additive or the like of a disintegrating film material.
【００１６】[0016]
【発明の効果】本発明の重合体は、機械的性質に優れ、
しかも生分解性を有するものである。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。更に本発明の方法に
よれば、Ｒ1 、Ｒ2 、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。The polymer of the present invention has excellent mechanical properties,
Moreover, it has biodegradability. Moreover, according to the method of the present invention, the polymer of the present invention can be easily produced at a temperature of about 100 ° C. without a solvent and without a catalyst. Further, according to the method of the present invention, R 1 , R 2 , m and n are changed to appropriately adjust the number of hydroxyl groups and the ester content in the unit unit of the polymer of the present invention represented by the general formula (1). You 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 The present invention will be described in more detail with reference to the following examples, but the present invention is not 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、
岡村製油（株）製、エポキシ当量２９６．１）１２．０
ｇ（０．０２モル）及びアジピン酸（分子量１４６）
２．９２ｇ（０．０２モル）を四つ口フラスコに同時に
入れる。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。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。Example 1 Bis [2,3-epoxypropyl] -1,18-octadecanedicarboxylate (trade name: SL-20G, m = 18 diglycidyl ester in the general formula (3),
Okamura Oil Co., Ltd., epoxy equivalent 296.1) 12.0
g (0.02 mol) and adipic acid (molecular weight 146)
2.92 g (0.02 mol) are placed simultaneously in a four neck flask. After purging air from the system through nitrogen gas, the contents are melted and heated and stirred at 100 to 105 ° C. for 10 hours. After dissolving the generated viscous substance in chloroform,
Reprecipitation with methanol gives the desired polymer of the present invention.
【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。Yield of methanol precipitation part: 12.70 g (85.1%) Melting point: 59 to 76 ° C. Intrinsic viscosity (chloroform 30 ° C.): 0.07 Number average molecular weight (VPO method): 4280 The IR spectrum is shown 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
Ｒ1 ＝Ｒ2 ＝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。Example 2 SL-20G (12.0 g, 0.02 mol) and eicosanedioic acid (trade name: SL-20, dicarboxylic acid represented by the general formula (2) in which R 1 = R 2 = H, n = 16) Okamura Oil Co., Ltd.) (6.84 g, 0.02 mol) was used in the same manner as in Example 1 to obtain the polymer of the present invention.
【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
ＭＲスペクトル図を図３に、13Ｃ−ＮＭＲスペクトル図
を図４にそれぞれ示す。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
FIG. 3 shows the MR spectrum and FIG. 4 shows the 13 C-NMR spectrum.
【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。Example 3 A polymer of the present invention was obtained in the same manner as in Example 1 above using 100 g (0.17 mol) of SL-20G and 51.6 g (0.15 mol) of eicosanedioic acid.
【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
ＭＲスペクトル図を図６に、13Ｃ−ＮＭＲスペクトル図
を図７にそれぞれ示す。Yield of methanol precipitate: 128.9 g (85.0%) Melting point: 82-87 ° C. Intrinsic viscosity (chloroform 30 ° C.): 0.51 Number average molecular weight (VPO method): 37500 Obtained polymer Figure 5 the IR spectrum diagram, 1 H-N
FIG. 6 shows the MR spectrum and FIG. 7 shows the 13 C-NMR spectrum.
【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。Example 4 A polymer of the present invention was obtained in the same manner as in Example 1 using 180 g (0.30 mol) of SL-20G and 40.7 g (0.30 mol) of malic acid.
【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。Yield of methanol precipitation part: 181 g (82.0%) Melting point: 70.9 to 81 ° C. 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。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。そ
の後１００〜１０５℃で２０時間加熱攪拌する。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。Example 5 225 g (0.38 mol) of SL-20G and 116.3 g (0.34 mol) of eicosanedioic acid are simultaneously charged into a four-necked flask. After purging air from the system through nitrogen gas, the contents were melted and 1 g (0.011 mol) of purified dimethylacetamide was added thereto. Then, the mixture is heated and stirred at 100 to 105 ° C. for 20 hours. The viscous product thus produced is dissolved in chloroform and then reprecipitated with methanol to obtain the intended polymer of the present invention.
【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。Yield of methanol precipitate: 278.3 g (88.0%) Melting point: 85 to 91 ° C. Intrinsic viscosity (chloroform 30 ° C.): 0.76 Number average molecular weight (VPO method): 87500.
【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。即ち、各重合体２５ｍｇを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
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。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。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。結果を下記表１に
示す。Example 6 The biodegradability of each of the polymers obtained in Examples 1 to 5 was evaluated by an enzymatic decomposition method. That is, 30 mg of each polymer 25 mg
After soaking in 2 ml of distilled water at ℃ for 48 hours to completely remove water-soluble components, 2 ml of phosphate buffer solution (pH 7) was added and suspended, and lipase (Rhizopus alphysus) 25 μ
1 (1250 units) was added, and after standing for a certain period of time, the polymer was taken out, washed with water, dried and weighed. Further, one drop of concentrated hydrochloric acid was added to the phosphoric acid buffer solution filtered with a 0.2 μm filter, and then the water-soluble organic matter was quantified using a TOC measuring device. For comparison, the same operation was performed when the enzyme was not included. The results are shown in Table 1 below.
【００２９】[0029]
【表１】 [Table 1]
【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 diagram of the polymer obtained in Example 1. FIG.
【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。2 is an IR spectrum diagram of the polymer obtained in Example 2. FIG.
【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。FIG. 3 is a 1 H-NMR spectrum diagram of the polymer obtained in Example 2.
【図４】実施例２で得られる重合体の13Ｃ−ＮＭＲスペ
クトル図である。FIG. 4 is a 13 C-NMR spectrum diagram 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。5 is an IR spectrum diagram of the polymer obtained in Example 3. FIG.
【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 diagram of the polymer obtained in Example 3. FIG.
【図７】実施例３で得られる重合体の13Ｃ−ＮＭＲスペ
クトル図である。FIG. 7 is a 13 C-NMR spectrum diagram of the polymer obtained in Example 3.
───────────────────────────────────────────────────── フロントページの続き (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 審査官 杉原 進 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhisa Takii No. 4-5 Kawaramachi, Kashiwabara-shi, Osaka Okamura Refinery Stock Company (72) Inventor Yoshishige Kida No. 4-5 Kawaramachi, Kashiwara-shi, Osaka Okamura Refinery In-house (72) Inventor Michio Ishioka 4-5 Kawaramachi, Kashiwara-shi, Osaka Okamura Oil Co., Ltd. (72) Inventor Tokuyoshi Miyoshi 4-5 Kawahara-cho, Kashiwara-shi, Osaka Okamura Oil Co., Ltd. Inspector Susumu Sugihara
Claims (2)
は水酸基を示す。ｍ及びｎは、同一又は異なって、０又
は１〜５０の整数を示す。］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、
実質的に線状な生分解性脂肪族ポリエステル重合体。1. The following general formula: [In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydroxyl group. m and n are the same or different and each represents 0 or an integer of 1 to 50. ] And the number average molecular weight is 3,000 to 100,000.
A substantially linear biodegradable aliphatic polyester polymer.
ジカルボン酸と一般式 【化３】 ［式中ｍは前記に同じ。］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。2. A general formula: [Wherein R 1 , R 2 and n are the same as defined above. ] And a dicarboxylic acid represented by the general formula: [In the formula, m is the same as above. ] The diglycidyl ester represented by these is reacted, The manufacturing method of the biodegradable aliphatic polyester polymer of Claim 1 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12476492A JPH0713129B2 (en) | 1992-05-18 | 1992-05-18 | Biodegradable aliphatic polyester polymer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12476492A JPH0713129B2 (en) | 1992-05-18 | 1992-05-18 | Biodegradable aliphatic polyester polymer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05320326A JPH05320326A (en) | 1993-12-03 |
| JPH0713129B2 true JPH0713129B2 (en) | 1995-02-15 |
Family
ID=14893537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12476492A Expired - Lifetime JPH0713129B2 (en) | 1992-05-18 | 1992-05-18 | Biodegradable aliphatic polyester polymer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713129B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022210364A1 (en) | 2021-03-30 | 2022-10-06 | 東洋紡株式会社 | Polyester and production method therefor |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496910A (en) * | 1994-07-21 | 1996-03-05 | The Dow Chemical Company | Hydroxyfunctional thermoplastic polyesters |
| 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 |
| US5665786A (en) * | 1996-05-24 | 1997-09-09 | Bradley University | Biodegradable polyester and natural polymer compositions and expanded articles 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 |
| AU2064597A (en) * | 1996-02-28 | 1997-09-16 | Biotechnology Research And Development Corporation | Biodegradable polyester compositions with natural polymers and articles thereo |
| US5861216A (en) * | 1996-06-28 | 1999-01-19 | 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 |
| US5780582A (en) * | 1996-12-31 | 1998-07-14 | The Dow Chemical Company | Hydroxy-functionalized polyester and poly(ester ether) oligomers |
| US5962624A (en) * | 1998-03-10 | 1999-10-05 | Hendel Kommanditgesellschaft Auf Aktien | Enzymatic synthesis of polyesters |
| KR100734171B1 (en) * | 2006-05-23 | 2007-07-02 | 재단법인서울대학교산학협력재단 | Water soluble and biodegradable high molecular weight functional polyester and synthesis method thereof |
-
1992
- 1992-05-18 JP JP12476492A patent/JPH0713129B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022210364A1 (en) | 2021-03-30 | 2022-10-06 | 東洋紡株式会社 | Polyester and production method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05320326A (en) | 1993-12-03 |
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