JPH11240941A - Method for producing hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin - Google Patents
Method for producing hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resinInfo
- Publication number
- JPH11240941A JPH11240941A JP4560498A JP4560498A JPH11240941A JP H11240941 A JPH11240941 A JP H11240941A JP 4560498 A JP4560498 A JP 4560498A JP 4560498 A JP4560498 A JP 4560498A JP H11240941 A JPH11240941 A JP H11240941A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- copolymer resin
- hydrolyzable
- acid copolymer
- monofunctional
- 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.)
- Pending
Links
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 229920006026 co-polymeric resin Polymers 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000004310 lactic acid Substances 0.000 claims abstract description 10
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 10
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000011975 tartaric acid Substances 0.000 claims abstract description 5
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000015165 citric acid Nutrition 0.000 claims abstract description 3
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 239000001630 malic acid Substances 0.000 claims abstract description 3
- 235000011090 malic acid Nutrition 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 229920001519 homopolymer Polymers 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- MWFOVBOCPFXQMF-UHFFFAOYSA-L dibutyl-chloro-[dibutyl(chloro)stannyl]oxystannane Chemical compound CCCC[Sn](Cl)(CCCC)O[Sn](Cl)(CCCC)CCCC MWFOVBOCPFXQMF-UHFFFAOYSA-L 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000012567 medical material Substances 0.000 abstract description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 6
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005031 thiocyano group Chemical group S(C#N)* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WVZPYZMQQDNINJ-UHFFFAOYSA-N tributyl(butylstannyloxy)stannane Chemical compound CCCC[SnH](CCCC)O[SnH](CCCC)CCCC WVZPYZMQQDNINJ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
(57)【要約】
【課題】回収困難な農業・園芸用資材及び漁業用資材
や、医療用具および医薬用素材として使用することがで
き、廃棄されても時間の経過とともに加水分解ないし土
中の微生物により二酸化炭素と水に分解され環境汚染源
にならない加水分解性及び／又は生分解性ポリヒドロキ
シカルボン酸共重合樹脂を容易に製造する方法を提供す
ること。
【解決手段】単官能ヒドロキシカルボン酸（乳酸、グリ
コール酸など）１００重量部と多官能ヒドロキシカルボ
ン酸（酒石酸、クエン酸、リンゴ酸など）０．００１〜
２０重量部との混合物中に重合触媒（１，３−ジクロロ
ー１、１、３、３ーテトラブチルジスタノキサンなど）
を添加し、減圧下に加熱攪拌して脱水共重合を行うこと
により、加水分解性及び生分解性のポリヒドロキシカル
ボン酸共重合樹脂を製造する。
【効果】得られるポリヒドロキシカルボン酸共重合樹脂
は、単官能ヒドロキシカルボン酸の単独重合樹脂と比べ
て、重量平均分子量が大で、かつ溶融粘度が大であるな
どの特性を有する。(57) [Abstract] [Problem] It can be used as agricultural and horticultural materials and fishery materials that are difficult to recover, and as medical and medical materials. Provided is a method for easily producing a hydrolyzable and / or biodegradable polyhydroxycarboxylic acid copolymer resin which is decomposed by a microorganism into carbon dioxide and water and does not become an environmental pollution source. SOLUTION: 100 parts by weight of monofunctional hydroxycarboxylic acid (lactic acid, glycolic acid, etc.) and 0.001 to polyfunctional hydroxycarboxylic acid (tartaric acid, citric acid, malic acid, etc.)
Polymerization catalyst (1,3-dichloro-1,1,3,3-tetrabutyldistannoxane, etc.) in a mixture with 20 parts by weight
Is added, and the mixture is heated and stirred under reduced pressure to perform dehydration copolymerization, thereby producing a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin. The resulting polyhydroxycarboxylic acid copolymer resin has properties such as a higher weight average molecular weight and a higher melt viscosity than the homopolymer resin of monofunctional hydroxycarboxylic acid.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は加水分解性及び生分
解性のポリヒドロキシカルボン酸共重合樹脂の製造方法
に関するものである。The present invention relates to a method for producing a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
種々の樹脂成形物が農業・園芸用資材（例えばポリ塩化
ビニルフィルム）及び漁業用資材（例えばポリエチレン
繊維の漁網）として用いられているが、これらの資材は
いずれは廃棄されるものである。したがって、廃棄され
ても公害源とならず、時間の経過とともに加水分解され
るか又は土中の微生物により生分解される樹脂が要望さ
れている。本発明は、このような農業・園芸用資材、漁
業用資材、粘結剤などに利用でき、使用後に廃棄されて
も土中の微生物などにより二酸化炭素と水に分解される
加水分解性及び／又は生分解性ポリヒドロキシカルボン
酸共重合樹脂を容易に製造する方法を提供することを目
的とするものである。2. Description of the Related Art
Various resin moldings are used as agricultural and horticultural materials (for example, polyvinyl chloride film) and fishing materials (for example, fishing nets made of polyethylene fiber), and any of these materials is discarded. Therefore, there is a demand for a resin that does not become a source of pollution even when discarded, and is hydrolyzed over time or biodegraded by microorganisms in the soil. The present invention can be used for such agricultural and horticultural materials, fishery materials, binders, and the like. Another object is to provide a method for easily producing a biodegradable polyhydroxycarboxylic acid copolymer resin.
【０００３】[0003]
【課題を解決するための手段】本発明者らは上記の目的
を達成するために鋭意検討の結果、単官能ヒドロキシカ
ルボン酸と多官能ヒドロキシカルボン酸とから加水分解
性及び生分解性のポリヒドロキシカルボン酸共重合樹脂
を製造することができることを見出し、本発明を完成す
るに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a monofunctional hydroxycarboxylic acid and a polyfunctional hydroxycarboxylic acid can be used to form a hydrolyzable and biodegradable polyhydroxycarboxylic acid. They have found that a carboxylic acid copolymer resin can be produced, and have completed the present invention.
【０００４】すなわち本発明は、単官能ヒドロキシカル
ボン酸の少なくとも１種以上と多官能ヒドロキシカルボ
ン酸の少なくとも１種以上との混合物中に重合触媒を添
加し、減圧下に加熱攪拌して脱水共重合を行うことによ
り、加水分解性及び生分解性のポリヒドロキシカルボン
酸共重合樹脂を製造することを特徴とするものである。That is, according to the present invention, a polymerization catalyst is added to a mixture of at least one or more monofunctional hydroxycarboxylic acids and at least one or more polyfunctional hydroxycarboxylic acids, and the mixture is heated and stirred under reduced pressure to carry out dehydration copolymerization. By performing the above, a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin is produced.
【０００５】[0005]
【発明の実施の形態】本発明で使用する単官能ヒドロキ
シカルボン酸としては、乳酸、グリコール酸などいずれ
を使用してもよいが、入手のし易さなどの点で特に乳酸
を使用することが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION As the monofunctional hydroxycarboxylic acid used in the present invention, any of lactic acid, glycolic acid and the like may be used, but lactic acid is particularly preferably used in terms of availability. preferable.
【０００６】本発明で使用する多官能ヒドロキシカルボ
ン酸としては、安価な点で特に酒石酸、クエン酸、リン
ゴ酸などを使用することが好ましい。As the polyfunctional hydroxycarboxylic acid used in the present invention, tartaric acid, citric acid, malic acid and the like are particularly preferably used from the viewpoint of inexpensiveness.
【０００７】多官能ヒドロキシカルボン酸の配合量は、
単官能ヒドロキシカルボン酸１００重量部に対して０．
００１〜２０重量部が好ましい。配合量が０．００１重
量部未満の場合には顕著な分子量増大効果が得られず、
一方配合量が２０重量部を超える場合には、得られるポ
リヒドロキシカルボン酸共重合樹脂は重量平均分子量が
減少し、黒色に着色する。The amount of the polyfunctional hydroxycarboxylic acid is as follows:
0.1 parts by weight per 100 parts by weight of monofunctional hydroxycarboxylic acid.
001 to 20 parts by weight are preferred. When the amount is less than 0.001 part by weight, a remarkable molecular weight increasing effect cannot be obtained,
On the other hand, when the compounding amount exceeds 20 parts by weight, the obtained polyhydroxycarboxylic acid copolymer resin has a reduced weight average molecular weight and is colored black.
【０００８】本発明において単官能ヒドロキシカルボン
酸と多官能ヒドロキシカルボン酸との共重合反応に用い
られる重合触媒としては、１，３−置換−１，１，３，
３−テトラオルガノジスタノキサンを挙げることができ
る。ここで、スズ原子に結合するオルガノ基はメチル
基、エチル基、プロピル基、ブチル基、オクチル基、ア
リル基、ベンジル基、フェニル基のいずれでもよいが、
溶解度やコストなどを考え合わせるとブチル基が好まし
い。また、１，３位の置換基はハロゲン、チオシアノ
基、水酸基、アルコキシ基、カルボキシル基のいずれで
もよい。特に好ましい重合触媒として、１，３−ジクロ
ロー１、１、３、３ーテトラブチルジスタノキサンを挙
げることができる。In the present invention, the polymerization catalyst used for the copolymerization reaction between the monofunctional hydroxycarboxylic acid and the polyfunctional hydroxycarboxylic acid includes 1,3-substituted-1,1,3,3.
3-Tetraorganodistanoxane can be mentioned. Here, the organo group bonded to the tin atom may be any of a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an allyl group, a benzyl group, and a phenyl group.
Considering the solubility and cost, a butyl group is preferred. The substituent at the 1,3-position may be any of a halogen, a thiocyano group, a hydroxyl group, an alkoxy group, and a carboxyl group. Particularly preferred polymerization catalysts include 1,3-dichloro-1,1,3,3-tetrabutyldistannoxane.
【０００９】[0009]
【作用】上述した手段によって加水分解性及び生分解性
のポリヒドロキシカルボン酸共重合樹脂をワンポットで
容易かつ効率よく製造することができ、得られたポリヒ
ドロキシカルボン酸共重合樹脂は、単官能ヒドロキシカ
ルボン酸の単独重合樹脂と比べて、重量平均分子量が大
で、かつ溶融粘度が大であるなどの特性を有する。そし
てこれらの樹脂は廃棄されても時間の経過とともに加水
分解及び／又は土中の微生物などにより二酸化炭素と水
に分解される。According to the above-mentioned means, a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin can be easily and efficiently produced in one pot. Compared to a carboxylic acid homopolymer resin, it has properties such as a large weight average molecular weight and a large melt viscosity. And even if these resins are discarded, they are hydrolyzed and / or decomposed into carbon dioxide and water by microorganisms in the soil with the passage of time.
【００１０】[0010]
【実施例】実施例１（乳酸と酒石酸との共重合樹脂） ９０％Ｌ−乳酸１ｍｏｌ（１００ｇ）と酒石酸１ｍｍｏ
ｌ（０．１５ｇ）と１，３−ジクロロー１、１、３、３
ーテトラブチルジスタノキサン０．１ｍｍｏｌ（５０ｍ
ｇ）とを５００ｍｌの反応器に入れ、１８０℃で２４時
間減圧下に加熱撹伴した。得られたポリ乳酸共重合体の
重量平均分子量（Ｍｗ）は４２，０００であった。ま
た、１６０℃における溶融粘度は９．５×１０4ポイズ
であった。EXAMPLES Example 1 (Copolymer resin of lactic acid and tartaric acid) 1 mol (100 g) of 90% L-lactic acid and 1 mmol of tartaric acid
l (0.15 g) and 1,3-dichloro-1,1,3,3
-0.1 mmol of tetrabutyldistannoxane (50 m
g) was placed in a 500 ml reactor and heated and stirred at 180 ° C. under reduced pressure for 24 hours. The weight average molecular weight (Mw) of the obtained polylactic acid copolymer was 42,000. The melt viscosity at 160 ° C. was 9.5 × 10 4 poise.
【００１１】なお、得られたポリヒドロキシカルボン酸
樹脂の分子量はゲル濾過クロマトグラフ（ＧＰＣ）を用
いて測定した。溶媒はクロロホルムを使用し、温度４０
℃で流量は１．０ｍｌ／ｍｉｎである。ＧＰＣ装置は日
本ミリポアリミテッド（株）製高圧ポンプ（高速液体ク
ロマトグラフ用５１０型）と、昭和電工（株）製示差屈
折率検出器（ＳｈｏｄｅｘＲＩ−７１）およびカラムＧ
ＰＣＫ８０６Ｍである。また分子量はポリスチレンを標
準試料とし、換算した値である。また、溶融粘度の測定
は(株)島津製作所製、島津フローテスタＣＦＴ−５００
Ｃによる。The molecular weight of the obtained polyhydroxycarboxylic acid resin was measured by using a gel filtration chromatograph (GPC). The solvent used was chloroform and the temperature was 40
At 100C, the flow rate is 1.0 ml / min. The GPC apparatus is a high pressure pump (Model 510 for high performance liquid chromatography) manufactured by Nippon Millipore Limited, a differential refractive index detector (Showex RI-71) manufactured by Showa Denko KK, and a column G.
PCK806M. The molecular weight is a value obtained by converting polystyrene as a standard sample. The melt viscosity was measured by Shimadzu Flow Tester CFT-500 manufactured by Shimadzu Corporation.
According to C.
【００１２】実施例２（乳酸とクエン酸との共重合樹
脂） ９０％Ｌ−乳酸１ｍｏｌ（１００ｇ）とクエン酸１ｍｍ
ｏｌ（０．１９ｇ）と１，３−ジクロロー１、１、３、
３ーテトラブチルジスタノキサン０．１ｍｍｏｌ（５０
ｍｇ）とを５００ｍｌの反応器に入れ、１８０℃で２４
時間減圧下に加熱撹伴を行った。得られたポリ乳酸共重
合体の重量平均分子量（Ｍｗ）は３８，０００であっ
た。また、１６０℃における溶融粘度は９．３×１０4
ポイズであった。Example 2 (Copolymer resin of lactic acid and citric acid) 1 mol (100 g) of 90% L-lactic acid and 1 mm of citric acid
ol (0.19 g) and 1,3-dichloro-1,1,3,
0.1 mmol of 3-tetrabutyldistannoxane (50
mg)) in a 500 ml reactor and
Heating and stirring were performed under reduced pressure for a time. The weight average molecular weight (Mw) of the obtained polylactic acid copolymer was 38,000. The melt viscosity at 160 ° C. is 9.3 × 10 4
Poise.
【００１３】比較例（乳酸の単独重合樹脂） ９０％Ｌ−乳酸１ｍｏｌ（１００ｇ）と１，３−ジクロ
ロー１、１、３、３ーテトラブチルジスタノキサン０．
１ｍｍｏｌ（５０ｍｇ）とを５００ｍｌの反応器に入
れ、１８０℃で２４時間減圧下に加熱撹伴を行った。得
られたポリ乳酸（乳酸ホモポリマー）の重量平均分子量
（Ｍｗ）は２０，０００であった。また、１６０℃にお
ける溶融粘度は１．５×１０4ポイズであった。Comparative Example (Homopolymerized Resin of Lactic Acid) 1 mol (100 g) of 90% L-lactic acid and 1,3-dichloro-1,1,3,3-tetrabutyldistanoxane 0.1 mol.
1 mmol (50 mg) was placed in a 500 ml reactor, and heated and stirred at 180 ° C. for 24 hours under reduced pressure. The weight average molecular weight (Mw) of the obtained polylactic acid (lactic acid homopolymer) was 20,000. The melt viscosity at 160 ° C. was 1.5 × 10 4 poise.
【００１４】（加水分解促進試験による生分解性の評
価）一般に生分解性樹脂の微生物による分解は、まず加
水分解が起こり、樹脂の分子量の低下が起こったのち、
微生物による分解が起こることが知られている。したが
って生分解性樹脂については、易加水分解性の評価をそ
のまま生分解性の評価方法の一つとして採用することが
できる。そこで、ポリヒドロキシカルボン酸樹脂の易加
水分解性を評価するため、０．１Ｎ ＮａＯＨ水溶液中
に実施例１、２で得られたポリ乳酸共重合体と比較例で
得られた乳酸ホモポリマーの２ｍｍシートを浸漬して４
日後の重量の減少を測定した。最初の重量を１００とし
た場合、乳酸ホモポリマーは９６に減少したのに対し、
ポリ乳酸共重合体は９２に減少した。このことから、本
発明により得られるポリヒドロキシカルボン酸共重合樹
脂はポリヒドロキシカルボン酸ホモポリマーと比べて生
分解速度が大であることが判明した。(Evaluation of Biodegradability by Hydrolysis Acceleration Test) In general, biodegradation of a biodegradable resin by microorganisms first occurs after hydrolysis and a reduction in the molecular weight of the resin occurs.
It is known that degradation by microorganisms occurs. Therefore, as for the biodegradable resin, the evaluation of the easily hydrolyzable property can be directly employed as one of the methods for evaluating the biodegradability. Then, in order to evaluate the hydrolyzability of the polyhydroxycarboxylic acid resin, 2 mm of the polylactic acid copolymer obtained in Examples 1 and 2 and the lactic acid homopolymer obtained in Comparative Example in a 0.1 N NaOH aqueous solution were used. Soak the sheet 4
The weight loss after days was measured. Lactic acid homopolymer was reduced to 96 when the initial weight was 100, whereas
The polylactic acid copolymer was reduced to 92. From this, it has been found that the polyhydroxycarboxylic acid copolymer resin obtained according to the present invention has a higher biodegradation rate than the polyhydroxycarboxylic acid homopolymer.
【００１５】[0015]
【発明の効果】以上説明したように本発明によれば、加
水分解性及び生分解性のポリヒドロキシカルボン酸共重
合樹脂をワンポットで容易かつ効率よく製造することが
でき、得られたポリヒドロキシカルボン酸共重合樹脂
は、単官能ヒドロキシカルボン酸の単独重合樹脂と比べ
て、重量平均分子量が大で、かつ溶融粘度が大であるな
どの特性を有する。そしてこれらの樹脂は粘結剤とし
て、またその成形物は回収困難な農業・園芸用資材及び
漁業用資材や、医療用具および医薬用素材として使用す
ることができ、廃棄されても時間の経過とともに加水分
解ないし土中の微生物により二酸化炭素と水に分解され
るので、環境汚染源にならない。As described above, according to the present invention, a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin can be easily and efficiently produced in one pot, and the resulting polyhydroxycarboxylic acid can be produced. The acid copolymer resin has properties such as a higher weight average molecular weight and a higher melt viscosity than a homopolymer resin of a monofunctional hydroxycarboxylic acid. These resins can be used as binders, and their molded products can be used as agricultural and horticultural materials and fishery materials that are difficult to recover, as medical tools and medical materials, and even if they are discarded over time. It does not become a source of environmental pollution because it is hydrolyzed or decomposed into carbon dioxide and water by soil microorganisms.
Claims (5)
１種以上と多官能ヒドロキシカルボン酸の少なくとも１
種以上との混合物中に重合触媒を添加し、減圧下に加熱
攪拌して脱水共重合を行うことを特徴とする加水分解性
及び生分解性のポリヒドロキシカルボン酸共重合樹脂の
製造方法。(1) at least one kind of monofunctional hydroxycarboxylic acid and at least one kind of polyfunctional hydroxycarboxylic acid;
A method for producing a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin, comprising adding a polymerization catalyst to a mixture of at least one species and heating and stirring under reduced pressure to carry out dehydration copolymerization.
ロキシカルボン酸との混合割合が、単官能ヒドロキシカ
ルボン酸１００重量部に対して多官能ヒドロキシカルボ
ン酸０．００１〜２０重量部であることを特徴とする請
求項１記載の加水分解性及び生分解性のポリヒドロキシ
カルボン酸共重合樹脂の製造方法。2. The mixing ratio of the monofunctional hydroxycarboxylic acid and the polyfunctional hydroxycarboxylic acid is 0.001 to 20 parts by weight of the polyfunctional hydroxycarboxylic acid per 100 parts by weight of the monofunctional hydroxycarboxylic acid. The method for producing a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin according to claim 1.
グリコール酸であることを特徴とする請求項１または２
記載の加水分解性及び生分解性のポリヒドロキシカルボ
ン酸共重合樹脂の製造方法。3. The method according to claim 1, wherein the monofunctional hydroxycarboxylic acid is lactic acid or glycolic acid.
A method for producing the hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin described in the above.
エン酸またはリンゴ酸であることを特徴とする請求項１
または２記載の加水分解性及び生分解性のポリヒドロキ
シカルボン酸共重合樹脂の製造方法。4. The method according to claim 1, wherein the polyfunctional hydroxycarboxylic acid is tartaric acid, citric acid or malic acid.
Or the method for producing a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin according to 2 or 3.
−テトラオルガノジスタノキサンであることを特徴とす
る請求項１または２記載の加水分解性及び生分解性のポ
リヒドロキシカルボン酸共重合樹脂の製造方法。5. A polymerization catalyst comprising 1,3-substituted-1,1,3,3
3. The method for producing a hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin according to claim 1, wherein the resin is a tetraorganodistanoxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4560498A JPH11240941A (en) | 1998-02-26 | 1998-02-26 | Method for producing hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4560498A JPH11240941A (en) | 1998-02-26 | 1998-02-26 | Method for producing hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11240941A true JPH11240941A (en) | 1999-09-07 |
Family
ID=12723967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4560498A Pending JPH11240941A (en) | 1998-02-26 | 1998-02-26 | Method for producing hydrolyzable and biodegradable polyhydroxycarboxylic acid copolymer resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11240941A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009082924A1 (en) * | 2007-12-24 | 2009-07-09 | Anhui Zhongren Science & Technology Co., Ltd. | A process for preparing high molecular weight poly (l-lactic acid) |
| WO2009087910A1 (en) * | 2008-01-09 | 2009-07-16 | National University Corporation Kyoto Institute Of Technology | Process for production of biodegradable polymer |
| WO2011132537A1 (en) * | 2010-04-20 | 2011-10-27 | 株式会社クレハ | Underwater antifouling material, melt-moulded article and coating material |
| WO2014038608A1 (en) * | 2012-09-07 | 2014-03-13 | 三井化学株式会社 | Aqueous dispersion, and additive for fracturing work |
| JP2016210981A (en) * | 2015-05-08 | 2016-12-15 | 学校法人立教学院 | Biodegradable resin porous body |
-
1998
- 1998-02-26 JP JP4560498A patent/JPH11240941A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009082924A1 (en) * | 2007-12-24 | 2009-07-09 | Anhui Zhongren Science & Technology Co., Ltd. | A process for preparing high molecular weight poly (l-lactic acid) |
| WO2009087910A1 (en) * | 2008-01-09 | 2009-07-16 | National University Corporation Kyoto Institute Of Technology | Process for production of biodegradable polymer |
| WO2011132537A1 (en) * | 2010-04-20 | 2011-10-27 | 株式会社クレハ | Underwater antifouling material, melt-moulded article and coating material |
| WO2014038608A1 (en) * | 2012-09-07 | 2014-03-13 | 三井化学株式会社 | Aqueous dispersion, and additive for fracturing work |
| JPWO2014038608A1 (en) * | 2012-09-07 | 2016-08-12 | 三井化学株式会社 | Aqueous dispersions and additives for fracturing work |
| JP2016210981A (en) * | 2015-05-08 | 2016-12-15 | 学校法人立教学院 | Biodegradable resin porous body |
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