JP3291523B2 - Biodegradable polymer material and method for producing the same - Google Patents
Biodegradable polymer material and method for producing the sameInfo
- Publication number
- JP3291523B2 JP3291523B2 JP24769597A JP24769597A JP3291523B2 JP 3291523 B2 JP3291523 B2 JP 3291523B2 JP 24769597 A JP24769597 A JP 24769597A JP 24769597 A JP24769597 A JP 24769597A JP 3291523 B2 JP3291523 B2 JP 3291523B2
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- JP
- Japan
- Prior art keywords
- lignin
- parts
- reaction
- general formula
- 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.)
- Expired - Lifetime
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- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、生分解性高分子材
料及びその製造方法、さらに詳しくは、生分解性を有す
る、多糖誘導体、キチン誘導体及びリグニン誘導体と、
それらの製造方法に関するものである。The present invention relates to a biodegradable polymer material and a method for producing the same, and more particularly, to a biodegradable polysaccharide derivative, a chitin derivative and a lignin derivative,
The present invention relates to a method for producing them.
【０００２】[0002]
【従来の技術】生分解性高分子材料を得るために、セル
ロール等の多糖化合物に環状ラクトンを直接反応させ
て、セルロースの水酸基にその環状ラクトンを開環付加
重合させることは知られている（特開平９−１２５８８
号公報）。この従来法の場合、その反応を円滑に進行さ
せるには、有機溶媒の使用が必要とされるが、多糖類自
体は溶解性の低いものであることから、通常の有機溶媒
には溶解せず、特殊の溶解を必要とし、経済性の点で著
しく不利であった。2. Description of the Related Art In order to obtain a biodegradable polymer material, it is known that a cyclic lactone is directly reacted with a polysaccharide compound such as cellulose, and the cyclic lactone is subjected to ring-opening addition polymerization to a hydroxyl group of cellulose. JP-A-9-12588
No.). In the case of this conventional method, the use of an organic solvent is necessary for the reaction to proceed smoothly, but since the polysaccharide itself has low solubility, it does not dissolve in a normal organic solvent. Requires special dissolution, and is extremely disadvantageous in terms of economy.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、製造コスト
が安価な生分解性高分子材料及びその製造方法を提供す
ることをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a biodegradable polymer material which is inexpensive to produce and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち本発明によれば、下記一般式（１）で表
される生分解性リグニン誘導体及びその製造方法が提供
される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, biodegradable lignin derivative and a production method thereof represented by the following general formula (1) is provided.
【化５】 Embedded image
【０００５】[0005]
【発明の実施の形態】本発明による前記一般式（２）の
リグニン誘導体は、下記一般式（２）BEST MODE FOR CARRYING OUT THE INVENTION The lignin derivative of the general formula ( 2 ) according to the present invention has the following general formula ( 2 )
【化６】 で表されるリグニンを、下記一般式（３）Embedded image The lignin represented by the following general formula ( 3 )
【化７】 （式中、Ｒ1は前記と同じ意味を有する）で表される環
状ラクトン中に溶解させ、重合触媒を存在下で反応させ
ることによって製造することができる。前記リグニンと
環状ラクトンとの使用割合は、そのリグニン中に含まれ
る水酸基１モル当り、１〜１００モル、好ましくは４〜
７０モルの割合である。環状ラクトンは、リグニンに対
する溶媒として作用し、これを溶解させる。重合触媒と
しては、環状ラクトンの開還重合に慣用のものが用いら
れ、その重合温度は室温〜１８０℃、好ましくは３０〜
１５０℃である。また、前記重合反応においては、必要
に応じ、有機溶媒を用いることができる。このような有
機溶媒としては、Ｎ−メチルピロリドン、アセトン、ジ
オキサン等が挙げられる。有機溶媒の使用量は、多糖化
合物１００重量部当り、１００〜１０００重量部、好ま
しくは２００〜５００重量部である。Embedded image (Wherein, R 1 has the same meaning as described above), and can be produced by reacting in the presence of a polymerization catalyst. The use ratio of the lignin and the cyclic lactone is 1 to 100 mol, preferably 4 to 100 mol per mol of the hydroxyl group contained in the lignin.
70 moles. The cyclic lactone acts as a solvent for lignin and dissolves it. As the polymerization catalyst, those commonly used for the ring-opening polymerization of cyclic lactone are used, and the polymerization temperature is room temperature to 180 ° C, preferably 30 to 180 ° C.
150 ° C. In the polymerization reaction, an organic solvent can be used as necessary. Examples of such an organic solvent include N-methylpyrrolidone, acetone, dioxane and the like. The amount of the organic solvent used is 100 to 1000 parts by weight, preferably 200 to 500 parts by weight, per 100 parts by weight of the polysaccharide compound.
【０００６】前記重合反応により、前記一般式（１）で
表されるリグニン誘導体を得ることができる。前記一般
式（１）において、ｑは１以上、好ましくは３以上の数
である。その上限値は、１００程度である。ｐは１以上
の数で、ｎより小さい数である。リグニン誘導体中にに
含まれる水酸基の置換率ｐ／ｎは、1/100〜100/100、好
ましくは5/100〜100/100である。また、ｐとｑの積は、
リグニン誘導体の水酸基に付加した環状ラクトンの数を
示す。The lignin derivative represented by the general formula ( 1 ) can be obtained by the polymerization reaction. In the general formula ( 1 ), q is 1 or more, preferably 3 or more. The upper limit is about 100. p is a number greater than or equal to 1 and less than n. The substitution ratio p / n of the hydroxyl group contained in the lignin derivative is from 1/100 to 100/100, preferably from 5/100 to 100/100. The product of p and q is
The number of the cyclic lactone added to the hydroxyl group of the lignin derivative is shown.
【０００７】本発明のリグニン誘導体は、生分解生を有
し、かつ可溶性で水酸基を含有することから、ジイソシ
アネートと反応させることにより、生分解生ポリウレタ
ンとすることができる。The lignin derivative of the present invention has biodegradability, is soluble and contains a hydroxyl group, and can be converted to biodegradable polyurethane by reacting with diisocyanate.
【０００８】前記した本発明の各高分子材料は、その原
料であるリグニンは環状ラクトンに可溶性を有すること
から、特別の有機溶媒の使用は特に必要とされず、工業
的に有利に製造することができる。[0008] Each polymer material of the present invention described above, the raw material der Brighter lignin is because it has a soluble ring-like lactone, the use of special organic solvent is not specifically required, industrially advantageously Can be manufactured.
【０００９】[0009]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。なお、以外において示す部及び％はいずれも重量
基準である。Next, the present invention will be described in more detail with reference to examples. In addition, all the parts and% shown in other than are based on weight.
【００１０】実施例１ 乾燥したクラフトリグニン１０部に蒸留したε−カプロ
テクトンモノマー（ε−ＣＬ）２０部を加えた。さら
に、少量の触媒 ジブチルスズジラウレート（ＤＢＴＤ
Ｌ）を加えた。撹拌しつつフラスコ内容物の温度を１８
０℃まで上げて、ε−ＣＬ２０部を滴下した後、２時間
反応を続けた。この反応によって得られた生成物（ポリ
カプロラクトン誘導体、ＫＬＰＣＬ１）の赤外線吸収ス
ペクトルには、エステル基に帰属される１７２５ｃｍ-1
に吸収ピークが観測された。Embodiment1 Ε-capro distilled into 10 parts of dried kraft lignin
20 parts of Tekton monomer (ε-CL) was added. Further
In addition, a small amount of catalyst dibutyltin dilaurate (DBTD
L) was added. While stirring, raise the temperature of the flask contents to 18
After raising to 0 ° C and dropping 20 parts of ε-CL, 2 hours
The reaction continued. The product obtained by this reaction (poly
Infrared absorption of caprolactone derivative, KLPCL1)
1725 cm attributed to the ester group in the vector-1
, An absorption peak was observed.
【００１１】実施例２ クラフトリグニン１０部に対して、ε−ＣＬ８０部を反
応させる以外には、実施例２と同様にして生成物を得
た。この反応によって得られた生成物（ＫＬＰＣＬ２）
の赤外線吸収スペクトルには、エステル基に帰属される
１７２５ｃｍ-1に吸収ピークが観測された。Embodiment2 10 parts of kraft lignin, 80 parts of ε-CL
The product was obtained in the same manner as in Example 2 except that
Was. Product obtained by this reaction (KLPCL2)
Is attributed to the ester group in the infrared absorption spectrum of
1725cm-1, An absorption peak was observed.
【００１２】実施例３ クラフトリグニン１０部に対して、ε−ＣＬ１２０部を
反応させる以外には、実施例２と同様にして生成物を得
た。この反応によって得られた生成物（ＫＬＰＣＬ３）
の赤外線吸収スペクトルには、エステル基に帰属される
１７２５ｃｍ-1に吸収ピークが観測された。Embodiment3 For 10 parts of craft lignin, 120 parts of ε-CL
A product was obtained in the same manner as in Example 2 except that the reaction was carried out.
Was. Product obtained by this reaction (KLPCL3)
Is attributed to the ester group in the infrared absorption spectrum of
1725cm-1, An absorption peak was observed.
【００１３】実施例４ クラフトリグニン１０部に対して、ε−ＣＬ１６０部を
反応させる以外には、実施例２と同様にして生成物を得
た。この反応によって得られた生成物（ＫＬＰＣＬ４）
の赤外線吸収スペクトルには、エステル基に帰属される
１７２５ｃｍ-1に吸収ピークが観測された。Embodiment4 For 10 parts of craft lignin, 160 parts of ε-CL
A product was obtained in the same manner as in Example 2 except that the reaction was carried out.
Was. Product obtained by this reaction (KLPCL4)
Is attributed to the ester group in the infrared absorption spectrum of
1725cm-1, An absorption peak was observed.
【００１４】実施例５ 実施例１において得られたＰＣＬ１を１，４−ジオキサ
ンに溶解し、この溶液にジフェニルメタンジイソシアネ
ート（ＭＤＩ）を加えて撹拌下に室温で反応させたの
ち、ガラス板下にキャストし、溶媒を除いた。その後、
１５０℃で２時間硬化させてポリウレタンシート（ＫＬ
ＰＵ１）を調製した。同様にしてＫＬＰＣ２，３及び４
とＭＤＩからＫＬＰＵ２、３及び４を調製した。これら
のＰＵの相転移を示差走査熱量測定（ＤＳＣ）によって
調べた。その結果を表１に示す。Embodiment5 Example1The PCL1 obtained in the above was replaced with 1,4-dioxa
Dissolved in diphenylmethane diisocyanate.
The reaction was carried out at room temperature with stirring.
Then, it was cast under a glass plate to remove the solvent. afterwards,
After curing at 150 ° C for 2 hours, polyurethane sheet (KL
PU1) was prepared. Similarly, KLPC2, 3 and 4
And KLPU 2, 3 and 4 from MDI. these
Phase transition of PU by differential scanning calorimetry (DSC)
Examined. Table 1 shows the results.
【００１５】[0015]
【表１】 [Table 1]
【００１６】実施例６ 乾燥したアルコリシスリグニン１０部に蒸留したε−カ
プロテクトンモノマー（ε−ＣＬ）２０部を加えた。さ
らに、少量の触媒、ジブチルスズジラウレート（ＤＢＴ
ＤＬ）を加えた。撹拌しつつフラスコ内容物の温度を１
８０℃まで上げて、ε−ＣＬ２０部を滴下した後、２時
間反応を続けた。この反応によって得られた生成物（ポ
リカプロラクトン誘導体、ＡＬＰＣＬ１）の赤外線吸収
スペクトルには、エステル基に帰属される１７２５ｃｍ
-1に吸収ピークが観測された。Embodiment6 Distilled ε-ca to 10 parts of dried alcoholysis lignin
20 parts of protecton monomer (ε-CL) were added. Sa
In addition, a small amount of catalyst, dibutyltin dilaurate (DBT
DL) was added. While stirring, raise the temperature of the contents of the flask to 1
After raising to 80 ° C and dropping 20 parts of ε-CL, 2 o'clock
The reaction was continued for a while. The product obtained by this reaction (Po
Infrared absorption of licaprolactone derivative, ALPCL1)
The spectrum shows 1725 cm assigned to the ester group.
-1, An absorption peak was observed.
【００１７】実施例７ アルコリシスリグニン１０部に対して、ε−ＣＬ８０部
を反応させる以外には、実施例７と同様にして生成物を
得た。この反応によって得られた生成物（ＡＬＰＣＬ
２）の赤外線吸収スペクトルには、エステル基に帰属さ
れる１７２５ｃｍ-1に吸収ピークが観測された。Embodiment7 Ε-CL 80 parts for 10 parts of alcoholysis lignin
Except that the reaction was carried out in the same manner as in Example 7.
Obtained. The product obtained by this reaction (ALPCL
2) In the infrared absorption spectrum,
1725cm-1, An absorption peak was observed.
【００１８】実施例８ アルコリシスリグニン１０部に対して、ε−ＣＬ１２０
部を反応させる以外には、実施例７と同様にして生成物
を得た。この反応によって得られた生成物（ＡＬＰＣＬ
３）の赤外線吸収スペクトルには、エステル基に帰属さ
れる１７２５ｃｍ-1に吸収ピークが観測された。Embodiment8 For 10 parts of alcoholysis lignin, ε-CL120
The reaction was carried out in the same manner as in Example 7 except that the
I got The product obtained by this reaction (ALPCL
3) The infrared absorption spectrum of
1725cm-1, An absorption peak was observed.
【００１９】実施例９ アルコリシスリグニン１０部に対して、ε−ＣＬ１６０
部を反応させる以外には、実施例７と同様にして生成物
を得た。この反応によって得られた生成物（ＡＬＰＣＬ
４）の赤外線吸収スペクトルには、エステル基に帰属さ
れる１７２５ｃｍ-1に吸収ピークが観測された。Embodiment9 For 10 parts of alcoholysis lignin, ε-CL160
The reaction was carried out in the same manner as in Example 7 except that the
I got The product obtained by this reaction (ALPCL
4) The infrared absorption spectrum of
1725cm-1, An absorption peak was observed.
【００２０】実施例１０ 実施例７において得られたＡＬＰＣＬ１を１，４−ジオ
キサンに溶解し、この溶液にジフェニルメタンジイソシ
アネート（ＭＤＩ）を加えて撹拌下に室温で反応させた
のち、ガラス板下にキャストし、溶媒を除いた。その
後、１５０℃で２時間硬化させてポリウレタンシート
（ＡＬＰＵ１）を調製した。同様にしてＡＬＰＣＬ２，
３及び４とＭＤＩからＡＬＰＵ２、３及び４を調製し
た。これらのＡＬＰＵの相転移を示差走査熱量測定（Ｄ
ＳＣ）によって調べた。その結果を表２に示す。Embodiment10 The ALPCL1 obtained in Example 7 was replaced with 1,4-geo
Dissolve in hexane and add diphenylmethane diisocy
Anate (MDI) was added and reacted at room temperature with stirring.
Then, it was cast under a glass plate to remove the solvent. That
After curing at 150 ° C for 2 hours, polyurethane sheet
(ALPU1) was prepared. Similarly, ALPCL2,
ALPU 2, 3 and 4 were prepared from 3 and 4 and MDI
Was. The phase transition of these ALPUs was determined by differential scanning calorimetry (D
SC). Table 2 shows the results.
【００２１】[0021]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き 審査官 弘實 謙二 (56)参考文献 特開 平７−109339（ＪＰ，Ａ) Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ，Ｖ ｏｌ．22，Ｎｏ．５，ｐ429−ｐ434 （1990) Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，Ｖｏ ｌ．27，Ｎｏ．１，ｐ５−ｐ11, （1994) Ｐｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔ ｓ，Ｖｏｌ．31，Ｎｏ．１，ｐ655−ｐ 656，（1990) (58)調査した分野(Int.Cl.7，ＤＢ名) C08B 3/00 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing from the front page Examiner Kenji Hiromi (56) References JP-A-7-109339 (JP, A) Polymer Journal, Vol. 22, No. 5, p429-p434 (1990) Macromolecules, Vol. 27, No. 1, p5-p11, (1994) Polymer Preprints, Vol. 31, No. 1, p655-p656, (1990) (58) Fields investigated (Int. Cl. 7 , DB name) C08B 3/00 CA (STN)
Claims (2)
グニン誘導体。 【化１】 （式中、Ｚ2はリグニン骨格を示し、Ｒ1はアルキレン基
を示し、ｎはリグニン中の水酸基の総数を示し、ｐは１
以上でｎより小さい数を示し、ｑは１以上の数を示す）1. A biodegradable lignin derivative represented by the following general formula ( 1 ). Embedded image (Wherein, Z 2 represents a lignin skeleton, R 1 represents an alkylene group, n represents the total number of hydroxyl groups in the lignin, and p represents 1
The above shows a number smaller than n, and q shows a number of 1 or more.)
を示し、ｎはリグニン中の水酸基の総数を示し、ｐは１
以上でｎより小さい数を示し、ｑは１以上の数を示す） で表される生分解性リグニン誘導体を製造する方法にお
いて、下記一般式（２） 【化３】 （式中、Ｚ2及びｎは前記と同じ意味を有する） で表されるリグニンを、下記一般式（３） 【化４】 （式中、Ｒ1は前記と同じ意味を有する） で表される環状ラクトン中に溶解させ、重合反応させる
ことを特徴とする前記の方法。2. The following general formula ( 1 ): (Wherein, Z 2 represents a lignin skeleton, R 1 represents an alkylene group, n represents the total number of hydroxyl groups in the lignin, and p represents 1
In the method for producing a biodegradable lignin derivative represented by the following formula ( 2 ), q represents a number smaller than n and q represents a number of 1 or more. (Wherein Z 2 and n have the same meanings as described above) by converting the lignin represented by the following general formula ( 3 ) to (Wherein, R 1 has the same meaning as described above), and a polymerization reaction is carried out.
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| JP24769597A JP3291523B2 (en) | 1997-08-28 | 1997-08-28 | Biodegradable polymer material and method for producing the same |
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|---|---|---|---|
| JP24769597A JP3291523B2 (en) | 1997-08-28 | 1997-08-28 | Biodegradable polymer material and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
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| JP3291523B2 true JP3291523B2 (en) | 2002-06-10 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001181302A (en) * | 1999-12-24 | 2001-07-03 | Daicel Chem Ind Ltd | Manufacturing method for cyclic ester-modified cellulose derivative |
| JP4559783B2 (en) * | 2004-07-02 | 2010-10-13 | 学校法人金井学園 | Biodegradable polyester having amphiphilic properties and method for producing the same |
| JP2007006827A (en) * | 2005-07-01 | 2007-01-18 | Tokyo Univ Of Marine Science & Technology | Method for synthesis of lignin-polyester copolymer using enzyme |
| JP4893158B2 (en) * | 2006-08-23 | 2012-03-07 | 富士ゼロックス株式会社 | RESIN, RESIN MOLDED BODY, CASE, AND METHOD FOR PRODUCING RESIN MOLDED BODY |
| JP5184953B2 (en) * | 2008-04-22 | 2013-04-17 | 学校法人金井学園 | Hot press molding material with excellent biodegradability, method for producing the same, and hot press molding |
| KR101336465B1 (en) * | 2012-09-07 | 2013-12-04 | 김동관 | Thermoplastic lignin polycondensates and processes for preparing same |
-
1997
- 1997-08-28 JP JP24769597A patent/JP3291523B2/en not_active Expired - Lifetime
Non-Patent Citations (3)
| Title |
|---|
| Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，Ｖｏｌ．２７，Ｎｏ．１，ｐ５−ｐ１１，（１９９４） |
| Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ，Ｖｏｌ．２２，Ｎｏ．５，ｐ４２９−ｐ４３４（１９９０） |
| Ｐｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔｓ，Ｖｏｌ．３１，Ｎｏ．１，ｐ６５５−ｐ６５６，（１９９０） |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1171401A (en) | 1999-03-16 |
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