JPH03265635A - New biodegradable polymer - Google Patents
New biodegradable polymerInfo
- Publication number
- JPH03265635A JPH03265635A JP6388790A JP6388790A JPH03265635A JP H03265635 A JPH03265635 A JP H03265635A JP 6388790 A JP6388790 A JP 6388790A JP 6388790 A JP6388790 A JP 6388790A JP H03265635 A JPH03265635 A JP H03265635A
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- formulas
- chitin
- formula
- chitosan
- 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
- 229920002988 biodegradable polymer Polymers 0.000 title claims abstract description 26
- 239000004621 biodegradable polymer Substances 0.000 title claims abstract description 26
- 229920001661 Chitosan Polymers 0.000 claims abstract description 37
- 229920002101 Chitin Polymers 0.000 claims abstract description 33
- 229920001542 oligosaccharide Polymers 0.000 claims abstract description 18
- 150000002482 oligosaccharides Chemical class 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000002252 acyl group Chemical group 0.000 claims abstract description 10
- QLTSDROPCWIKKY-PMCTYKHCSA-N beta-D-glucosaminyl-(1->4)-beta-D-glucosamine Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O)[C@@H](CO)O1 QLTSDROPCWIKKY-PMCTYKHCSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 5
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 26
- 239000000047 product Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229920005603 alternating copolymer Polymers 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- RQFQJYYMBWVMQG-IXDPLRRUSA-N chitotriose Chemical compound O[C@@H]1[C@@H](N)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](N)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](CO)O1 RQFQJYYMBWVMQG-IXDPLRRUSA-N 0.000 description 3
- 150000002016 disaccharides Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 241000194110 Bacillus sp. (in: Bacteria) Species 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CDOJPCSDOXYJJF-KSKNGZLJSA-N N-acetyl-beta-D-glucosaminyl-(1->4)-N-acetyl-beta-D-glucosamine Chemical compound O[C@@H]1[C@@H](NC(=O)C)[C@H](O)O[C@H](CO)[C@H]1O[C@H]1[C@H](NC(C)=O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CDOJPCSDOXYJJF-KSKNGZLJSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- CDOJPCSDOXYJJF-UHFFFAOYSA-N UNPD21501 Natural products OC1C(NC(=O)C)C(O)OC(CO)C1OC1C(NC(C)=O)C(O)C(O)C(CO)O1 CDOJPCSDOXYJJF-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- BUZMJVBOGDBMGI-UHFFFAOYSA-N 1-phenylpropylbenzene Chemical compound C=1C=CC=CC=1C(CC)C1=CC=CC=C1 BUZMJVBOGDBMGI-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- CDOJPCSDOXYJJF-CBTAGEKQSA-N N,N'-diacetylchitobiose Chemical compound O[C@@H]1[C@@H](NC(=O)C)C(O)O[C@H](CO)[C@H]1O[C@H]1[C@H](NC(C)=O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CDOJPCSDOXYJJF-CBTAGEKQSA-N 0.000 description 1
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- JLCPHMBAVCMARE-UHFFFAOYSA-N [3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[3-[[3-[[3-[[3-[[3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-[[5-(2-amino-6-oxo-1H-purin-9-yl)-3-hydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxyoxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(6-aminopurin-9-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-5-(4-amino-2-oxopyrimidin-1-yl)oxolan-2-yl]methyl [5-(6-aminopurin-9-yl)-2-(hydroxymethyl)oxolan-3-yl] hydrogen phosphate Polymers Cc1cn(C2CC(OP(O)(=O)OCC3OC(CC3OP(O)(=O)OCC3OC(CC3O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c3nc(N)[nH]c4=O)C(COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3COP(O)(=O)OC3CC(OC3CO)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3ccc(N)nc3=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cc(C)c(=O)[nH]c3=O)n3cc(C)c(=O)[nH]c3=O)n3ccc(N)nc3=O)n3cc(C)c(=O)[nH]c3=O)n3cnc4c3nc(N)[nH]c4=O)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)n3cnc4c(N)ncnc34)O2)c(=O)[nH]c1=O JLCPHMBAVCMARE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000012648 alternating copolymerization Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 108010089807 chitosanase Proteins 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- AFLBAXPZSPPPIW-UHFFFAOYSA-N disodium;dioxidoboranylformonitrile Chemical compound [Na+].[Na+].[O-]B([O-])C#N AFLBAXPZSPPPIW-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000019462 natural additive Nutrition 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規生分解性ポリマー、さらに詳しくは、微
生物によって分解可能な新規高分子化合物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel biodegradable polymer, and more particularly to a novel polymer compound degradable by microorganisms.
（従来の技術）
近年、プラスチックの廃棄処理や、プラスチック製品の
処分後の活用が重要な社会問題として注目されており、
この要請に応するため種々の生分解性ポリマーの開発が
なされている。(Conventional technology) In recent years, the disposal of plastics and the utilization of plastic products after disposal have attracted attention as important social issues.
In order to meet this demand, various biodegradable polymers have been developed.
このような生分解性ポリマーの製造としては、生物分解
性を増強させるために、非生分解性ポリマーに生物分解
性を付与する添加剤を配合する方法や、微生物によって
直接破壊され易い分子構造をポリマーの分子鎖中に導入
する方法等がある。In order to increase biodegradability, such biodegradable polymers can be produced by adding additives to non-biodegradable polymers to make them biodegradable, or by modifying molecular structures that are easily destroyed by microorganisms. There are methods of introducing it into the molecular chain of a polymer.
前者の例としては、たとえばでんぷんが、ポリエチレン
、ポリビニルアルコールに生物分解性を付与する添加剤
として用いられ、また多くのポリマーに対してテストが
行われている。As an example of the former, starch, for example, is used as an additive to impart biodegradability to polyethylene, polyvinyl alcohol, and has been tested on many polymers.
一方、後者の例としては、たとえばセルロースにジイソ
シアネートをグラフトし、その後、他のポリマーを反応
させた生分解性ポリマーや、ポリエチレンとでんぷん若
しくはセルロースとの共重合体、ゼラチンとポリエチル
アクリレートとの共重合体等、ポリマー分子鎮中に生物
分解性基を導入した種々のポリマーが開発されている。On the other hand, examples of the latter include biodegradable polymers obtained by grafting diisocyanate onto cellulose and then reacting it with other polymers, copolymers of polyethylene and starch or cellulose, and copolymers of gelatin and polyethyl acrylate. Various polymers, such as polymers, have been developed in which biodegradable groups are introduced into the polymer molecule.
（発明が解決しようとする課題）
しかしながら、上記のような従来の生分解性ポリマー並
びに生物分解性を付与する手段においては、いずれも、
得られたポリマーの物性及び加工性が良好ではないとい
う共通の問題点を有し、さらに前者の例においてはポリ
マーに対する相溶性が悪く、また後者の例においては製
造コストが高くつく等の問題点をそれぞれ有していた。(Problems to be Solved by the Invention) However, in the conventional biodegradable polymers and means for imparting biodegradability as described above,
They have a common problem that the physical properties and processability of the obtained polymer are not good, and furthermore, the former example has poor compatibility with the polymer, and the latter example has problems such as high manufacturing cost. They each had
本発明は、このような問題点を解決するためになされた
もので、優れた生分解性を有するとともに、物性、加工
性、製造コスト等、ポリマーに本来必要な条件を充足す
るような新規生分解性ポリマーを提供することを課題と
する。The present invention was made to solve these problems, and it is a novel product that has excellent biodegradability and satisfies the originally necessary conditions for polymers such as physical properties, processability, and manufacturing cost. The objective is to provide a degradable polymer.
（課題を解決するための手段）
本発明は、このような課題を解決するために、地球上で
豊富なバイオマス資源の１つであるキチン、キトサン、
及びこれらの部分分解物であるオリゴ糖、キトビオース
類を利用する点に着目してなされたものである。(Means for Solving the Problems) In order to solve such problems, the present invention utilizes chitin, chitosan, which is one of the abundant biomass resources on earth,
This invention has been made by focusing on the use of oligosaccharides and chitobiose, which are partially decomposed products of these.
すなわち、本発明の新規生分解性ポリマーは、次の式〔
Ａ〕、式〔Ｂ〕、及び式〔Ｃ〕で示される構成単位を含
むキチン若しくはキトサン若しくはこれらの部分分解物
であるオリゴ糖類、又はキチン若しくはキトサンの誘導
体若しくはこれらの部分分解物であるオリゴ糖類誘導体
が、構成一成分として１〜９７重量％含まれてなること
を特徴とする特
〔式中Ｒ，−Ｒ，はそれぞれ同−又は異なる炭素数１〜
１８のアルキル基、炭素数２〜１８のアシル基、ポリオ
キシアルキレン（炭素数２若しくは３）オキシド基、（
ＣＨ２）、、Ｃ○ＯＨ（ｎ ＝ １〜１８）、又は水素
原子を示し、ｋ、ｍは１〜２００００の整数を示し、ｎ
は０〜２００００の整数を示す。〕また、本発明の他の
新規生分解性ポリマーは、上記式〔Ａ〕、式〔Ｂ〕、及
び式〔Ｃ〕で示される構成単位を含むキチン若しくはキ
トサン若しくはこれらの部分分解物であるオリゴ糖類、
又はキチン若しくはキトサンの誘導体若しくはこれらの
部分分解物であるオリゴ糖類誘導体が、共有結合を介し
て構成一成分として１〜９７モル％含まれてなることを
特徴とする。That is, the novel biodegradable polymer of the present invention has the following formula [
A], an oligosaccharide that is chitin or chitosan, or a partial decomposition product thereof, or a derivative of chitin or chitosan, or an oligosaccharide that is a partial decomposition product thereof, containing the structural units represented by formula [B] and formula [C] A special product characterized in that the derivative is contained in an amount of 1 to 97% by weight as a constituent component [wherein R, -R, each have the same or different carbon number 1 to
18 alkyl group, acyl group having 2 to 18 carbon atoms, polyoxyalkylene (2 or 3 carbon atoms) oxide group, (
CH2), C○OH (n = 1 to 18), or a hydrogen atom, k and m are integers from 1 to 20,000, and n
represents an integer from 0 to 20,000. ] In addition, other novel biodegradable polymers of the present invention include chitin or chitosan, or oligonucleotides that are partially decomposed products thereof, including structural units represented by the above formulas [A], [B], and [C]. sugars,
Alternatively, it is characterized in that it contains 1 to 97 mol % of a chitin or chitosan derivative or an oligosaccharide derivative which is a partially decomposed product thereof as one component via a covalent bond.
尚、これらの新規生分解性ポリマーにおいて、前記キチ
ン若しくはキトサン誘導体若しくはこれらの部分分解物
であるオリゴ糖類には、前記Ｒ。In addition, in these new biodegradable polymers, the oligosaccharides which are the chitin or chitosan derivatives or their partial decomposition products include the above-mentioned R.
〜Ｒ６の異なる複数種の構成単位が含まれる場合がある
。A plurality of different types of structural units of ~R6 may be included.
さらに、本発明の他の新規生分解性ポリマーは、次式〔
Ｄ〕
ＨＮ−Ｒ，ＨＮ−Ｒ。Furthermore, the other novel biodegradable polymer of the present invention has the following formula [
D] HN-R, HN-R.
Ｒ，Ｒ。R,R.
〔式中、Ｒｒ〜Ｒ１゜は、それぞれ同−又は異なる炭素
数１〜１８のアルキル基、炭素数２〜１８のアシル基、
ポリオキシアルキレン（炭素数２若しくは３）オキシド
基、（ＣＨ２）−Ｃ○○Ｈ（ｎ＝１〜１８）、又は水素
原子を示す。〕で表されるキトビオース又はキトビオー
ス誘導体が、共有結合を介して構成一成分として１〜９
７モル％含まれてなることにある。[In the formula, Rr to R1° are the same or different alkyl groups having 1 to 18 carbon atoms, acyl groups having 2 to 18 carbon atoms,
Indicates a polyoxyalkylene (carbon number 2 or 3) oxide group, (CH2)-C○○H (n=1 to 18), or a hydrogen atom. ] Chitobiose or chitobiose derivative represented by 1 to 9 as one component through a covalent bond.
It contains 7 mol%.
さらに、本発明の他の新規生分解性ポリマーは、次式［
Ｅ）
〔式中Ｒ、、Ｒ、、Ｒ、、Ｒ，はそれぞれ同−又は異な
る炭素数１〜１８のアルキル基、炭素数２〜１８のアシ
ル基、ポリオキシアルキレン〈炭素数２若しくは３）オ
キシド基、（ＣＨ，）、Ｃ○ＯＨ（ｎ＝１〜１８）、又
は水素原子を示す。〕で表されるキトビオース又はキト
ビオース誘導体が共有結合を介して構成一成分として含
まれてなることにある。Furthermore, other novel biodegradable polymers of the present invention have the following formula [
E) [In the formula, R, , R, , R, , R, are the same or different alkyl groups having 1 to 18 carbon atoms, acyl groups having 2 to 18 carbon atoms, polyoxyalkylene (having 2 or 3 carbon atoms) Indicates an oxide group, (CH,), C○OH (n=1-18), or a hydrogen atom. Chitobiose or a chitobiose derivative represented by ] is contained as one component through a covalent bond.
上記のようなキトビオース又はキトビオース誘導体を含
む新規生分解性ポリマーにおいては、上記Ｒ１−’−Ｒ
Ｉ０が異なる数種の２糖体が含まれる場合がある。In the novel biodegradable polymer containing chitobiose or a chitobiose derivative as described above, the R1-'-R
Several types of disaccharides with different I0 may be included.
（作用並びに導入化合物の調製法）
本発明の上記のような各新規生分解性ポリマーに含まれ
るキチン、キトサン、及びこれらの部分分解物であるオ
リゴ糖、キトビオース類は、次のような特徴を有してい
る。(Action and method for preparing introduced compounds) Chitin, chitosan, and oligosaccharides and chitobiose, which are partially decomposed products thereof, contained in the above-mentioned novel biodegradable polymers of the present invention have the following characteristics. have.
（１）天然物であるため、生分解性に優れている。(1) Being a natural product, it has excellent biodegradability.
（２）製造コストが安い。(2) Manufacturing costs are low.
（３）安全性が高い。(3) High safety.
（４）特に、キトサン類については、分子内に反応性の
アミン基を有しているため、化学修飾が可能である。（
キチンについても一部アミノ基が残存している）。(4) In particular, chitosans can be chemically modified because they have reactive amine groups in their molecules. (
Some amino groups remain in chitin as well).
従って、これらを、生分解性を付与する添加剤としてポ
リマーへ配合した場合、ポリマーの生分解性を著しく促
進するとともに、天然物添加剤であるため、安全性の面
でも問題はなく、また製造コストも低い。Therefore, when these are added to a polymer as an additive that imparts biodegradability, they significantly promote the biodegradability of the polymer, and since they are natural additives, there are no safety issues, and there are no problems with manufacturing. Cost is also low.
また、キトサン類等の分子内のアミノ基に対しては、長
鎖アシル基等の導入が可能であり、これらの誘導体につ
いては、各種ポリマーに対する相溶性が高まり、これら
の誘導体を配合して得られたポリマーの物性及び加工性
が良好となる。In addition, it is possible to introduce long-chain acyl groups into the amino groups in molecules such as chitosans, and these derivatives have increased compatibility with various polymers, making it possible to obtain products by blending these derivatives. The physical properties and processability of the resulting polymer are improved.
これは、セルロース、でんぷんには見られない特徴であ
る。This is a feature not found in cellulose and starch.
また、キトサン類については、分子内に数多くのアミノ
基、水酸基を有するため、これらを架橋剤として用いる
と、共有結合により分子鎮中に組み込ませたポリマーを
合成できる。特に、キチン。Furthermore, since chitosans have many amino groups and hydroxyl groups in their molecules, when these are used as crosslinking agents, it is possible to synthesize polymers that are incorporated into the molecular chain through covalent bonds. Especially chitin.
キトサンの部分分解物の一種であるＮ、 Ｎ’ −ジア
セチルキトビオースやキトビオース等の２糖体について
は、分子内に２個のアミ７基或いは一級水酸基（６位水
酸基）を有するため、架橋剤としてのみならず、２官能
性モノマーとして交互共重合等により、新規な生分解性
ポリマーを合成することができる。Disaccharides such as N,N'-diacetylchitobiose and chitobiose, which are a type of partial decomposition products of chitosan, have two ami7 groups or primary hydroxyl groups (6-position hydroxyl group) in the molecule, so they are not crosslinked. New biodegradable polymers can be synthesized not only as agents but also as bifunctional monomers by alternating copolymerization.
得られたポリマーは、微生物により直接破壊され易い分
子構造を含んでいるため、優れた生分解性を示す。The obtained polymer exhibits excellent biodegradability because it contains a molecular structure that is easily destroyed directly by microorganisms.
次に、上記のようなジアセチルキトビオースのｇｌｉ製
は、たとえば特願昭６３−７３６２９号のバチルスｓｐ
、ＰＩ−７３（微工研菌寄第９８４３号）から生産され
る酵素と、キチン又はキチンの部分分解物とを反応させ
ることによってなされる（特願昭６３−２３０５４０号
）。Next, the above-mentioned diacetylchitobiose produced by gli, for example, Bacillus sp.
, by reacting an enzyme produced from PI-73 (Feikoken Kyoiku No. 9843) with chitin or a partial decomposition product of chitin (Japanese Patent Application No. 63-230540).
また、キトサンオリゴ糖は、たとえば上記バチルスｓｐ
、 ＰＩ−７Ｓ由来のキトサナーゼをキトサンに作用さ
せ、部分分解により酵素的につくられる。このものをう
まく制御すれば、２糖以上のキトサンオリゴ糖が得られ
る（特願平１−２１９５５５号）。Furthermore, chitosan oligosaccharides can be used, for example, in the above-mentioned Bacillus sp.
, is enzymatically produced through partial decomposition of chitosan by the action of chitosanase derived from PI-7S. If this is well controlled, chitosan oligosaccharides having two or more saccharides can be obtained (Japanese Patent Application No. 1-219555).
また、キチンオリゴ糖は、キトサンオリゴ糖をアセチル
化して調製できる。アセチル化法は、たとえば［Ｈｉｒ
ａｎｏ、 Ｓ、 、 ｅｔ ａｌ、 Ｃａｒｂｏｈｙｄ
ｒｏ、 Ｒｅｓ、 、 ４７．３１５（１９７６）、
］の文献記載の方法によって可能である。Furthermore, chitin oligosaccharides can be prepared by acetylating chitosan oligosaccharides. The acetylation method is, for example, [Hir
ano, S., et al., Carbohyd
ro, Res, 47.315 (1976),
] This is possible by the method described in the literature.
以上の化合物類をポリエチレン、ポリビニルアルコール
等に配合（添加）して得られたポリマーは、優れた生分
解性を有するとともに高い安全性を示した。Polymers obtained by blending (adding) the above compounds to polyethylene, polyvinyl alcohol, etc. had excellent biodegradability and exhibited high safety.
（実施例） 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
実施例１
本実施例は、ポリマーへの導入化合物として、長鎖アル
キル導入化合物を用いる実施例である。Example 1 This example uses a long-chain alkyl-introducing compound as the compound to be introduced into the polymer.
導入化合物の一例として、−ａ式；
％式％（）
で示されるキチン若しくはキトサン誘導体が用いられる
。この式において、（Ｘ 、）、 （Ｘ ２）、 （ｘ
、）はそれぞれ次式ＣＦ）、［Ｇ：１．［Ｈ］で表さ
れるキチン、キトサン誘導体の構成単位である。また、
ｋは１〜２００００の整数、ｍ、ｎは０〜２００００の
整数をそれぞれ示す。As an example of the introduced compound, a chitin or chitosan derivative represented by the formula -a; % formula %() is used. In this formula, (X , ), (X 2), (x
, ) are respectively expressed by the following formulas CF) and [G:1. It is a structural unit of chitin and chitosan derivatives represented by [H]. Also,
k represents an integer from 1 to 20,000, and m and n represent integers from 0 to 20,000, respectively.
（上記式［Ｆ］において、Ｒｏは炭素数２〜１８のアル
キル基を示す。(In the above formula [F], Ro represents an alkyl group having 2 to 18 carbon atoms.
Ｊ、 Ｍｅｍｂｒａｎｅ Ｓｃｉ、、 １６．２９５
（１９８３） 〕に従い、キチン。J. Membrane Sci., 16.295
(1983) ], chitin.
キトサン誘導体中のアミン基とアルデヒドとの反応で生
成するシッフ塩基をシアノホウ素ナトリウム等で還元し
て、Ｎ一部分的アルキル化キチン。N-partially alkylated chitin is obtained by reducing the Schiff base produced by the reaction of the amine group in the chitosan derivative with an aldehyde using sodium cyanoboronate or the like.
キトサン誘導体を合成した。A chitosan derivative was synthesized.
その反応式を次に示す。ただし、下記反応式において、
（Ｘ ａ）、 （Ｘ ３）は上記［Ｇ］、 ［Ｈ］で
表されるキチン、キトサンの構成体であり、（Ｘ、）。The reaction formula is shown below. However, in the reaction formula below,
(X a) and (X 3) are constituents of chitin and chitosan represented by the above [G] and [H], and (X,).
（Ｘ、）は、それぞれ次式（Ｉ〕、 ＣＪ”Ｊで表さ
れるキチン、キトサン誘導体の構成単位である。(X,) are structural units of chitin and chitosan derivatives represented by the following formulas (I) and CJ''J, respectively.
Ｒ１２ＣＨ○ （Ｌ）ｋ、、（Ｌ）、。R12CH○ (L)k,,(L),.
（Ｘ、）ｋ（Ｌ）、（ＸＳ）、。(X,)k(L), (XS),.
Ｎａ ＢＨｓＣＮ
（ＸＳ）ｋ（Ｘ２）、（ＸＳ）、
Ｍｕｚａｒｅｌｌｉらの方法
［Ｍｕｚａｒｅｌｌｉ、 Ｒ，＾、＾、、ｅｔ１１
（上記式ＣＩ）、 ＣＪ’Ｊにおいて、Ｒ１２は炭素
数１〜１７のアルキル基を示す。）
実施例２
本実施例は、ポリマーへの導入化合物として、長鎖アシ
ル導入化合物を用いる実施例である。Na BHsCN (XS)k(X2), (XS), Muzarelli et al.'s method [Muzarelli, R, ^, ^,, et11 (formula CI above), In CJ'J, R12 is an alkyl group having 1 to 17 carbon atoms shows. ) Example 2 This example is an example in which a long-chain acyl-introducing compound is used as the compound to be introduced into the polymer.
導入化合物の他の例として、−形式；
％式％）
で示されるキチン若しくはキトサン誘導体が用いられる
。コの式におイテ、（Ｘ ｌ）、 （Ｘ ２）、 （Ｘ
３） ハ上記式［Ｆ）、 ［Ｇ］、［Ｈ］で表され
るキチン。As another example of the compound to be introduced, a chitin or chitosan derivative represented by -form; % formula %) is used. (X l), (X 2), (X
3) Chitin represented by the above formulas [F], [G], and [H].
キトサン誘導体の構成単位である。ただし本実施例では
、これらの式において、Ｒ１，はＣ２〜ＣＩ８のアシル
基を示す。It is a structural unit of chitosan derivatives. However, in this example, in these formulas, R1 represents a C2 to CI8 acyl group.
Ｈｉｒａｎｏらの方法〔旧ｒａｎｏ、 Ｓ、ｅｔ ａｔ
、 、 Ｃａｒｂｏｈｙｄｒｏ。Hirano et al.'s method [formerly Hirano, S, et at
, , Carbohydro.
Ｒｅｓ、、４７，３１５（１９７６） ：］に従い、希
塩酸−メタノール混合液中にて、キチン、キトサン誘導
体を酸無水物と反応させてＮ一部分的アシル化キチン、
キトサン誘導体を台底した。Res., 47, 315 (1976): ], chitin and chitosan derivatives were reacted with an acid anhydride in a dilute hydrochloric acid-methanol mixture to produce N-partially acylated chitin,
Chitosan derivatives have reached the bottom.
その反応式を次に示す。ただし、下記反応式において、
（Ｘ２）、（ＸＳ）は上記［Ｇ］、 ［Ｈ：］で表わ
されるキチン、キトサンの構成単位であり、また（Ｘ６
）は、次式〔Ｋ〕で表されるキチン、キトサン誘導体の
構成単位である。The reaction formula is shown below. However, in the reaction formula below,
(X2) and (XS) are the structural units of chitin and chitosan represented by [G] and [H:] above, and (X6
) is a structural unit of a chitin or chitosan derivative represented by the following formula [K].
（Ｒ，２ＣＯ）、○ （Ｘ２）ｋ、、（Ｘ、）ｆｉ （Ｘ６）ｋ（Ｘ２）、（Ｘ、）、。(R,2CO),○ (X2)k,, (X,)fi (X6)k(X2), (X, ),.
むエポキシ硬化樹脂についての実施例である。This is an example of an epoxy cured resin.
エポキシ樹脂の架橋剤（硬化剤）として、たとえばキト
サンオリゴ糖を使用すると、末端エポキシ基とオリゴ糠
中のアミノ基との開環付加反応により架橋が生じ、硬化
した。When chitosan oligosaccharide, for example, is used as a crosslinking agent (curing agent) for an epoxy resin, crosslinking occurs due to a ring-opening addition reaction between the terminal epoxy group and the amino group in the oligo bran, resulting in curing.
得られたエポキシ硬化樹脂は、生物分解により分子鎖の
切断が生じ、結果として分子量の低下が認められた。In the obtained epoxy cured resin, molecular chain scission occurred due to biodegradation, and as a result, a decrease in molecular weight was observed.
キトサンオリゴ糖としてキトビオースを使用する場合に
ついて、その反応式を次に示す。反応式中において、Ｒ
１３は次式〔Ｍ〕で示すジフェニルプロパンである。The reaction formula when chitobiose is used as the chitosan oligosaccharide is shown below. In the reaction formula, R
13 is diphenylpropane represented by the following formula [M].
上記実施例１．２の化合物類は、ポリエチレン、ポリビ
ニルアルコール等に対して良好な相溶性を示し、配合し
て得られたポリマーは優れた生分解性を示した。The compounds of Example 1.2 showed good compatibility with polyethylene, polyvinyl alcohol, etc., and the resulting polymer showed excellent biodegradability.
実施例３
本実施例は、キトサンオリゴ糖を分子鎮中に含←
実施例４
本実施例は、キトビオース類とジカルボン酸との交互共
重合体についての実施例である。Example 3 This example contains a chitosan oligosaccharide in the molecular weight Example 4 This example is an example of an alternating copolymer of chitobiose and dicarboxylic acid.
ジシクロへキシルカルボジイミド（ＤＣＣ）等を使用し
たＮＨ２とジカルボン酸との選択的な縮合反応によりキ
トビオースを交互共重合体１戊分としてなるポリマーを
得た。A polymer consisting of chitobiose as an alternating copolymer was obtained by selective condensation reaction of NH2 and dicarboxylic acid using dicyclohexylcarbodiimide (DCC) or the like.
ジカルボン酸としては、マロン酸、コハク酸。Dicarboxylic acids include malonic acid and succinic acid.
グルタル酸、アジピン酸、ピメリン酸、スペリン酸、ア
ゼライン酸、セバシン酸等の脂肪族飽和ジカルボン酸、
フマル酸等の不飽和ジカルボン酸、テレフタル酸等の芳
香族ジカルボン酸、リンゴ酸等のヒドロキシカルボン酸
等が利用できる。aliphatic saturated dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid,
Unsaturated dicarboxylic acids such as fumaric acid, aromatic dicarboxylic acids such as terephthalic acid, and hydroxycarboxylic acids such as malic acid can be used.
特に、コハク酸、リンゴ酸等の天然に存在するジカルボ
ン酸を共重合用モノマーとして使用した場合、当然のこ
とながら生成したポリマーの生分解産物も天然物となる
ので安全性が高く医療用高分子としての用途もある。In particular, when naturally occurring dicarboxylic acids such as succinic acid and malic acid are used as monomers for copolymerization, the biodegradation products of the resulting polymers are also natural products, making them highly safe medical polymers. There is also a use as.
ポリマー生成の反応式を次に示す。The reaction formula for polymer production is shown below.
上記反応式によって生成される化合物〔Ｎ〕が本実施例
の生分解性ポリマーである。The compound [N] produced by the above reaction formula is the biodegradable polymer of this example.
尚、上記反応式中におけるＲ １４は、飽和、不飽和炭
化水素、又は芳香族炭化水素等、ジカルボン酸の主鎖や
基本骨格となりうる任意の構造体を示す。Note that R 14 in the above reaction formula represents any structure that can be the main chain or basic skeleton of a dicarboxylic acid, such as a saturated hydrocarbon, an unsaturated hydrocarbon, or an aromatic hydrocarbon.
実施例５
本実施例は、上記ジカルボン酸の一例としての、アジピ
ン酸とキトビオースとの交互共重合体の実施例である。Example 5 This example is an example of an alternating copolymer of adipic acid and chitobiose as an example of the above dicarboxylic acid.
その製造方法について説明すると、先ずキトビオース３
．４ｇ （１０ｍｍｏｌ）を水４０−に溶解した。これ
にアジピン酸１．４６ｇ （１０ｍｍｏｌ）とＮ、 Ｎ
’ −ジシクロへキシルカルボジイミド２．２８ｇ （
ｌｌｍｍｏｌ）を６０−のジメチルホルムアミドに溶解
したものを加えた。To explain the manufacturing method, first, chitobiose 3
．． 4 g (10 mmol) was dissolved in 40 mm of water. To this, 1.46 g (10 mmol) of adipic acid and N, N
'-Dicyclohexylcarbodiimide 2.28g (
11 mmol) dissolved in 60-dimethylformamide was added.
この混合物を室温下で１２０時間攪拌した後、過剰量の
木炭酸水素ナトリウム水溶液に加え攪拌した。生じた沈
澱物を濾過により採取し、水及びメタノールにて洗浄し
て、目的とする化合物ＣＯ〕を得た。This mixture was stirred at room temperature for 120 hours, and then added to an excess amount of an aqueous sodium bicarbonate solution and stirred. The resulting precipitate was collected by filtration and washed with water and methanol to obtain the target compound CO].
この化合物〔○〕の構造と、製造するための反応式は上
記のとおりである。The structure of this compound [○] and the reaction formula for producing it are as described above.
その他の実施例
さらに、上記実施例３のようなエポキシ樹脂のみならず
、ポリアクリル酸等のカルボキシル基を有するポリマー
に対しても、キトビオース類は架橋剤として用いること
ができ、この場合は生分解性、安全性の高い高吸水性樹
脂としての利用が可能である。Other Examples Furthermore, chitobiose can be used as a crosslinking agent not only for epoxy resins as in Example 3, but also for polymers with carboxyl groups such as polyacrylic acid, and in this case, chitobiose can be used as a crosslinking agent for polymers having carboxyl groups such as polyacrylic acid. It can be used as a highly water-absorbent resin with high properties and safety.
（発明の効果）
（イ）叙上のように、本発明によって、キチン若しくは
キトサン誘導体、又はこれらの部分分解物であるキトサ
ンオリゴ糖を、その構造中に含んだ全く新規な生分解性
ポリマーを得るに至った。(Effects of the Invention) (a) As described above, the present invention provides a completely novel biodegradable polymer containing chitin or chitosan derivatives, or chitosan oligosaccharides, which are partially decomposed products thereof, in its structure. I ended up getting it.
（ロ）特に、キトビオースやＮ、 Ｎ’ −ジアセチル
キトビオース等の２糖体については、生分解性ポリマー
を構成するに際し、２官能性モノマーとしての利用が可
能となる利点がある。(b) In particular, disaccharides such as chitobiose and N,N'-diacetylchitobiose have the advantage that they can be used as bifunctional monomers when constructing biodegradable polymers.
（ハ）そして、このような生分解性ポリマーは、天然物
であるキチン、キトサンの誘導体等を含むものであるた
め、優れた生分解性を示し、しかも安全性が高い。(c) Since such biodegradable polymers contain natural products such as chitin and chitosan derivatives, they exhibit excellent biodegradability and are highly safe.
（ハ）さらには、従来の生分解性ポリマーに比べても、
物性、加工性、相溶性、及び製造コスト等が著しく優れ
ているという効果がある。(c) Furthermore, compared to conventional biodegradable polymers,
It has the effect of being significantly superior in physical properties, processability, compatibility, manufacturing cost, etc.
Claims (1)
構成単位を含むキチン若しくはキトサン若しくはこれら
の部分分解物であるオリゴ糖類、又はキチン若しくはキ
トサンの誘導体若しくはこれらの部分分解物であるオリ
ゴ糖類誘導体が、構成一成分として１〜９７重量％含ま
れてなることを特徴とする新規生分解性ポリマー。 ▲数式、化学式、表等があります▼・・・〔Ａ〕 ▲数式、化学式、表等があります▼・・・〔Ｂ〕 ▲数式、化学式、表等があります▼・・・〔Ｃ〕 〔式中Ｒ＿１〜Ｒ＿６はそれぞれ同一又は異なる炭素数
１〜１８のアルキル基、炭素数２〜１８のアシル基、ポ
リオキシアルキレン（炭素数２若しくは３）オキシド基
、（ＣＨ＿２）＿ｎＣＯＯＨ（ｎ＝１〜１８）、又は水
素原子を示し、ｋ，ｍは１〜２００００の整数を示し、
ｎは０〜２００００の整数を示す。〕 ２、次の式〔Ａ〕、式〔Ｂ］、及び式〔Ｃ〕で示される
構成単位を含むキチン若しくはキトサン若しくはこれら
の部分分解物であるオリゴ糖類、又はキチン若しくはキ
トサンの誘導体若しくはこれらの部分分解物であるオリ
ゴ糖類誘導体が、共有結合を介して構成一成分として１
〜９７モル％含まれてなることを特徴とする新規生分解
性ポリマー。 ▲数式、化学式、表等があります▼・・・〔Ａ〕 ▲数式、化学式、表等があります▼・・・〔Ｂ〕 ▲数式、化学式、表等があります▼・・・〔Ｃ〕 〔式中Ｒ＿１〜Ｒ＿６はそれぞれ同一又は異なる炭素数
１〜１８のアルキル基、炭素数２〜１８のアシル基、ポ
リオキシアルキレン（炭素数２若しくは３）オキシド基
、（ＣＨ＿２）＿ｎＣＯＯＨ（ｎ＝１〜１８）、又は水
素原子を示し、ｋ，ｍは１〜２００００の整数を示し、
ｎは０〜２００００の整数を示す。〕 ３、次式〔Ｄ〕 ▲数式、化学式、表等があります▼・・・〔Ｄ〕 式中Ｒ＿１〜Ｒ＿１＿０は、それぞれ同一又は異なる炭
素数１〜１８のアルキル基、炭素数２〜１８のアシル基
、ポリオキシアルキレン（炭素数２若しくは３）オキシ
ド基、（ＣＨ＿２）＿ｎＣＯＯＨ（ｎ＝１〜１８）、又
は水素原子を示す。〕で示されるキトビオース又はキト
ビオース誘導体が、共有結合を介して構成一成分として
１〜９７モル％含まれてなることを特徴とする新規生分
解性ポリマー。 ４、次式〔Ｅ〕 ▲数式、化学式、表等があります▼・・・〔Ｅ〕 〔式中Ｒ＿１，Ｒ＿２，Ｒ＿５，Ｒ＿６はそれぞれ同一
又は異なる炭素数１〜１８のアルキル基、炭素数２〜１
８のアシル基、ポリオキシアルキレン（炭素数２若しく
は３）オキシド基、（ＣＨ＿２）＿ｎＣＯＯＨ（ｎ＝１
〜１８）、又は水素原子を示す。 〕で示されるキトビオース又はキトビオース誘導体が、
共有結合を介して構成一成分として１〜９７モル％含ま
れてなることを特徴とする新規生分解性ポリマー。[Scope of Claims] 1. Chitin or chitosan, or an oligosaccharide that is a partially decomposed product thereof, or chitin or chitosan containing the structural units represented by the following formulas [A], [B], and [C] A novel biodegradable polymer characterized in that it contains 1 to 97% by weight of an oligosaccharide derivative which is a derivative of or a partially decomposed product thereof as a constituent component. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[C] [Formula R_1 to R_6 are the same or different alkyl groups having 1 to 18 carbon atoms, acyl groups having 2 to 18 carbon atoms, polyoxyalkylene (2 or 3 carbon atoms) oxide groups, (CH_2)_nCOOH (n=1 to 18 ), or a hydrogen atom, k and m are integers of 1 to 20,000,
n represents an integer from 0 to 20,000. ] 2. Chitin or chitosan, or oligosaccharides which are partial decomposition products thereof, or derivatives of chitin or chitosan, or derivatives thereof, including structural units represented by the following formulas [A], formula [B], and formula [C] Oligosaccharide derivatives, which are partial decomposition products, are combined as one component through covalent bonds.
A novel biodegradable polymer characterized by containing ~97 mol%. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[C] [Formula R_1 to R_6 are the same or different alkyl groups having 1 to 18 carbon atoms, acyl groups having 2 to 18 carbon atoms, polyoxyalkylene (2 or 3 carbon atoms) oxide groups, (CH_2)_nCOOH (n=1 to 18 ), or a hydrogen atom, k and m are integers of 1 to 20,000,
n represents an integer from 0 to 20,000. ] 3. The following formula [D] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ... [D] In the formula, R_1 to R_1_0 are the same or different alkyl groups having 1 to 18 carbon atoms, and C 2 to 18 alkyl groups, respectively. Indicates an acyl group, a polyoxyalkylene (carbon number 2 or 3) oxide group, (CH_2)_nCOOH (n=1-18), or a hydrogen atom. ] A novel biodegradable polymer characterized in that it contains 1 to 97 mol% of chitobiose or a chitobiose derivative as a constituent via a covalent bond. 4. The following formula [E] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... [E] [In the formula, R_1, R_2, R_5, R_6 are the same or different alkyl groups with 1 to 18 carbon atoms, and 2 carbon atoms. ~1
8 acyl group, polyoxyalkylene (2 or 3 carbon atoms) oxide group, (CH_2)_nCOOH (n=1
~18), or a hydrogen atom. ] The chitobiose or chitobiose derivative represented by
A novel biodegradable polymer characterized by containing 1 to 97 mol% as a constituent via covalent bonds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6388790A JPH03265635A (en) | 1990-03-14 | 1990-03-14 | New biodegradable polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6388790A JPH03265635A (en) | 1990-03-14 | 1990-03-14 | New biodegradable polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03265635A true JPH03265635A (en) | 1991-11-26 |
Family
ID=13242251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6388790A Pending JPH03265635A (en) | 1990-03-14 | 1990-03-14 | New biodegradable polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03265635A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999001479A1 (en) * | 1997-07-03 | 1999-01-14 | National Starch And Chemical Investment Holding Corporation | Chitosan derivatives and methods of manufacturing the same |
-
1990
- 1990-03-14 JP JP6388790A patent/JPH03265635A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999001479A1 (en) * | 1997-07-03 | 1999-01-14 | National Starch And Chemical Investment Holding Corporation | Chitosan derivatives and methods of manufacturing the same |
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