JP2005089585A - Manufacturing method for biodegradable high molecular-weight aliphatic polyester - Google Patents
Manufacturing method for biodegradable high molecular-weight aliphatic polyester Download PDFInfo
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- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 27
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 21
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 14
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000005690 diesters Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 229920000728 polyester Polymers 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 25
- 229920000642 polymer Polymers 0.000 description 19
- 229960005261 aspartic acid Drugs 0.000 description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- -1 polybutylene succinate Polymers 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 239000001384 succinic acid Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 4
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229940024606 amino acid Drugs 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 229960002989 glutamic acid Drugs 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、脂肪族ジカルボン酸と脂肪族ジオールから得られる生分解性高分子量脂肪族ポリエステルの迅速な製造方法に関するものである。 The present invention relates to a rapid method for producing a biodegradable high molecular weight aliphatic polyester obtained from an aliphatic dicarboxylic acid and an aliphatic diol.
ポリオレフィンや芳香族ポリエステル等の合成高分子は、日常生活に欠かせない原材料として大量に使われているが、これらの合成高分子は、自然環境で分解されないことから、消費量の増加に伴って環境問題が顕在化している。このため、生分解性プラスチックの開発が進められており、生分解性を有する高分子として、脂肪族ポリエステルが注目されている。なかでもコハク酸またはその誘導体とブタンジオールとから製造されるポリブチレンサクシネートは融点や機械的強度に優れており注目されている。 Synthetic polymers such as polyolefins and aromatic polyesters are used in large quantities as raw materials indispensable for daily life, but these synthetic polymers are not decomposed in the natural environment. Environmental problems are becoming apparent. For this reason, development of biodegradable plastics is underway, and aliphatic polyesters are attracting attention as biodegradable polymers. Among them, polybutylene succinate produced from succinic acid or a derivative thereof and butanediol is attracting attention because of its excellent melting point and mechanical strength.
また、ポリブチレンサクシネートのみでは必ずしも実用上十分な機械的強度及び加工性が得られないため、種々の多価アルコール、ヒドロキシ酸などとの共重合による物性の改良が検討され、本発明者らも、先に3-アルコキシ-1,2-プロパンジオールを脂肪族ジカルボン酸ジエステルと脂肪族ジオールに共重合させることによりホモポリマーよりも高い伸度を示す新規な構造を有する高分子量脂肪族ポリエステルを提案した（特許文献１〜３）。 In addition, since polybutylene succinate alone does not always provide practically sufficient mechanical strength and processability, improvement of physical properties by copolymerization with various polyhydric alcohols, hydroxy acids, etc. has been studied. However, a high molecular weight aliphatic polyester having a novel structure exhibiting higher elongation than a homopolymer by copolymerizing 3-alkoxy-1,2-propanediol with an aliphatic dicarboxylic acid diester and an aliphatic diol first. Proposed (Patent Documents 1 to 3).
しかし、上記の脂肪族ジカルボン酸と脂肪族ジオールからの生分解性高分子量脂肪族ポリエステル及びその共重合体の製造には高分子量化するまで減圧下での長時間の反応時間が必要である、という難点があった。 However, the production of the biodegradable high molecular weight aliphatic polyester and the copolymer thereof from the aliphatic dicarboxylic acid and the aliphatic diol requires a long reaction time under reduced pressure until the molecular weight is increased. There was a difficulty.
一方、生分解性ポリエステルの物性等を向上させるため、ポリエステル中にアミド基を導入することが検討されている（特許文献４〜５）。しかし、天然のアミノ酸を基剤とする生分解性ポリエステルアミドの合成では満足な物性を有するものが得られていない（特許文献６）。また、脂肪族ジカルボン酸−脂肪族ジオール−２官能オキシカルボン酸−天然アミノ酸の重合によるアミド結合を有する高分子量脂肪族ポリエステルを合成する方法も知られているが（特許文献７）、脂肪族オキシカルボン酸が存在しないと十分な分子量を持つポリエステルアミドが生成しないとされ、更には、アスパラギン酸が特異的に重合時間を短縮することは何ら示唆されていない。 On the other hand, in order to improve the physical properties of biodegradable polyester, introduction of an amide group into the polyester has been studied (Patent Documents 4 to 5). However, in the synthesis of biodegradable polyesteramides based on natural amino acids, those having satisfactory physical properties have not been obtained (Patent Document 6). A method for synthesizing a high molecular weight aliphatic polyester having an amide bond by polymerization of aliphatic dicarboxylic acid-aliphatic diol-2 functional oxycarboxylic acid-natural amino acid is also known (Patent Document 7). In the absence of carboxylic acid, it is considered that a polyesteramide having a sufficient molecular weight is not formed, and further, it is not suggested that aspartic acid specifically shortens the polymerization time.
本発明は、高分子量化するまでの反応時間を短縮できると共に生分解性に優れた高分子量脂肪族ポリエステルの工業的に有利な製造方法を提供することを目的とする。 An object of the present invention is to provide an industrially advantageous production method of a high molecular weight aliphatic polyester that can shorten the reaction time until the molecular weight is increased and is excellent in biodegradability.
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、以下の発明が提供される。
下記 一般式（１）で表される脂肪族ジカルボン酸もしくはそのジエステル、
または下記一般式（２）で表される脂肪族ジカルボン酸無水物、
(式中、Ｒ１は前記と同じ)
あるいは両者の混合物と、
下記一般式（３）で表される脂肪族ジオールとの重縮合反応を、
アスパラギン酸の存在下で行うことを特徴とする、
下記一般式（４）で示されるポリエステル部と下記一般式（５）で示されるアスパラギン酸部とを含有する、生分解性高分子量脂肪族ポリエステルの製造方法。
（式中、Ｒ１及びＲ３は前記と同じ。）
That is, according to the present invention, the following inventions are provided.
An aliphatic dicarboxylic acid represented by the following general formula (1) or a diester thereof,
Or an aliphatic dicarboxylic acid anhydride represented by the following general formula (2):
(Wherein R1 is the same as above)
Or a mixture of both,
A polycondensation reaction with an aliphatic diol represented by the following general formula (3):
Characterized in that it is carried out in the presence of aspartic acid,
The manufacturing method of biodegradable high molecular weight aliphatic polyester containing the polyester part shown by following General formula (4), and the aspartic acid part shown by following General formula (5).
(In the formula, R1 and R3 are the same as above.)
そして、本発明の高分子量脂肪族ポリエステルの製造方法は、縮合反応をアスパラギン酸の存在下で行うことから、従来のポリエステルの製造方法に比較して短い反応時間で高分子量ポリエステルを製造することができる。しかも、この高分子量脂肪族ポリエステルは、その脂肪族エステル結合に基づく生分解性を有する。 And since the manufacturing method of the high molecular weight aliphatic polyester of the present invention performs the condensation reaction in the presence of aspartic acid, the high molecular weight polyester can be manufactured in a shorter reaction time than the conventional polyester manufacturing method. it can. Moreover, the high molecular weight aliphatic polyester has biodegradability based on the aliphatic ester bond.
本発明の高分子量脂肪側ポリエステルの製造方法は、一般式（１）で表される脂肪族ジカルボン酸およびそのジエステル、または一般式（２）で表される脂肪族ジカルボン酸無水物、あるいは両者の混合物と、前記一般式（３）で表される脂肪族ジオールと、アスパラギン酸の存在下で縮合反応させることを特徴とする。 The method for producing the high molecular weight fatty polyester of the present invention comprises the aliphatic dicarboxylic acid represented by the general formula (1) and its diester, the aliphatic dicarboxylic acid anhydride represented by the general formula (2), or both of them. A condensation reaction is performed in the presence of the mixture, the aliphatic diol represented by the general formula (3), and aspartic acid.
本発明で用いるアスパラギン酸は、後記比較例にみられるように、ポリエステルの生分解性を向上させる作用の他に上記縮合反応時間をたとえば、1/2〜1/10程度まで短縮する機能を有する。この場合、アスラギン酸以外のアミノ酸たとえはグルタミン酸では、このような作用効果を奏しない。この理由は、現時点では定かではないが、アスパラギン酸分子内のカルボキシル基間の距離が反応性に大きな影響を与えているものと推定される。 Aspartic acid used in the present invention has a function of shortening the condensation reaction time to, for example, about 1/2 to 1/10 in addition to the effect of improving the biodegradability of polyester as seen in Comparative Examples described later. . In this case, amino acids other than asragic acid, such as glutamic acid, do not have such effects. The reason for this is not clear at present, but it is presumed that the distance between the carboxyl groups in the aspartic acid molecule has a great influence on the reactivity.
アスパラギン酸の使用量は、目的とするポリマーの分子量2万以上になるような範囲であればよく、通常、脂肪族ジカルボン酸ユニット1モルあたり、0.0005〜0.30モル、好ましくは0.001〜0.10モルの割合である。アスパラギン酸の使用割合が前記範囲より多くなると、得られるポリマー（重縮合体）の三次元化が進行しゲル化が起こるので好ましくない。 The amount of aspartic acid used may be within a range such that the target polymer has a molecular weight of 20,000 or more, and is usually 0.0005 to 0.30 mol, preferably 0.001 to 0.10 mol, per mol of the aliphatic dicarboxylic acid unit. It is. If the aspartic acid usage rate exceeds the above range, the resulting polymer (polycondensate) will become three-dimensional and gelation will occur, which is not preferable.
前記一般式（１）で示される脂肪族ジカルボン酸及びそのジエステル、ならびに一般式（２）で示される脂肪族ジカルボン酸無水物としては、コハク酸、アジピン酸、スベリン酸、セバシン酸、ドデカン二酸等の脂肪族ジカルボン酸、そのジエステル、及びそれらの酸無水物が挙げられる。 Examples of the aliphatic dicarboxylic acid and its diester represented by the general formula (1) and the aliphatic dicarboxylic acid anhydride represented by the general formula (2) include succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Aliphatic dicarboxylic acids such as diesters thereof, and acid anhydrides thereof.
また、一般式（１）で示される脂肪族ジカルボン酸と縮合させる、前記一般式（３）で表される脂肪族ジオールとしては、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、1,6−ヘキサンジオール、1,4−シクロヘキサンジメタノール等が挙げられる。 Examples of the aliphatic diol represented by the general formula (3) to be condensed with the aliphatic dicarboxylic acid represented by the general formula (1) include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 -Hexanediol, 1,4-cyclohexanedimethanol and the like.
本発明に係る前記縮合反応は、従来公知のエステル交換反応用触媒の存在下で好ましく行われる。これらの系にカプロラクトンのようなラクトン類、乳酸のようなオキシカルボン酸を加えてもよい。前記反応において、その反応温度は、100〜300℃、好ましくは120〜270℃である。反応圧力は、減圧、常圧またはやや加圧（0.5kg/cm２G以下）であることができるが、好ましくは、常圧ないし減圧である。 The condensation reaction according to the present invention is preferably carried out in the presence of a conventionally known transesterification catalyst. Lactones such as caprolactone and oxycarboxylic acids such as lactic acid may be added to these systems. In the reaction, the reaction temperature is 100 to 300 ° C, preferably 120 to 270 ° C. The reaction pressure can be reduced pressure, normal pressure or slightly increased pressure (0.5 kg / cm 2 G or less), preferably normal pressure or reduced pressure.
前記縮合反応を行う場合、反応は予備縮合工程(第１工程)と、高分子量化工程(第２工程)との二つの工程で行うのが好ましい。
前記予備縮合工程においては、末端に脂肪族ジオールの結合した低分子量の縮合物を生成させる。この縮合物の数平均分子量は、5000〜10000にするのがよく、その分子量は反応条件及び反応時間により適当に調節することができる。
When the condensation reaction is performed, the reaction is preferably performed in two steps, a precondensation step (first step) and a high molecular weight step (second step).
In the precondensation step, a low molecular weight condensate having an aliphatic diol bonded to the terminal is formed. The number average molecular weight of the condensate is preferably 5000 to 10,000, and the molecular weight can be appropriately adjusted depending on the reaction conditions and reaction time.
前記高分子量工程においては、低分子量の縮合物の末端に結合する脂肪族ジオールを脱離させながら縮合させて高分子量の縮合物を生成させる工程であり、この工程により、数平均分子量が2万以上の縮合物を生成させることができる。この場合の反応条件は、副生する脂肪族ジオールが気体として存在しうる条件であればよい。この分子量化工程は、前記予備縮合工程を実施する反応装置と同じ装置又は攪拌効率のよい重合装置で実施することができる。同じ装置を用いる場合は、予備縮合反応の終了後に、反応条件を変えて、例えば、反応温度を高くしかつ反応圧力を低くして、予備縮合体の縮合反応を行えばよい。 The high molecular weight step is a step of producing a high molecular weight condensate by condensing an aliphatic diol bonded to the terminal of the low molecular weight condensate while eliminating it, and this step has a number average molecular weight of 20,000. The above condensate can be produced. The reaction conditions in this case may be any conditions that allow the by-produced aliphatic diol to exist as a gas. This molecular weighting step can be carried out in the same apparatus as the reactor for carrying out the precondensation step or a polymerization apparatus having good stirring efficiency. When the same apparatus is used, after completion of the precondensation reaction, the reaction conditions may be changed, for example, the reaction temperature may be increased and the reaction pressure may be decreased to perform the condensation reaction of the precondensate.
本発明方法で得られる生分解性高分子量脂肪族ポリエステルは、前記一般式（４）のポリエステル部と前記一般式（５）のアスパラギン酸部とからなる。
この場合、ポリエステル部を示す一般式（４）において、Ｒ１は鎖状または環状の二価脂肪族基を示すが、その炭素数は１〜１２、好ましくは２〜６である。このような二価脂肪族基としては、アルキレン基、例えば、メチレン、エチレン、プロピレン、ブチレン、ヘキシレン、オクチレン、ドデシレン、シクロヘキシレン、シクロヘキサンジメチレン等が挙げられる。Ｒ３は鎖状または環状の二価脂肪族基を示すが、その炭素数は１〜１２、好ましくは２〜６である。このような二価脂肪族基としては、アルキレン基、例えば、メチレン、エチレン、プロピレン、ブチレン、ヘキシレン、オクチレン、ドデシレン、シクロヘキシレン、シクロヘキサンジメチレン等が挙げられる。
The biodegradable high molecular weight aliphatic polyester obtained by the method of the present invention comprises the polyester part of the general formula (4) and the aspartic acid part of the general formula (5).
In this case, in General formula (4) which shows a polyester part, R1 shows a linear or cyclic divalent aliphatic group, The carbon number is 1-12, Preferably it is 2-6. Examples of such divalent aliphatic groups include alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, octylene, dodecylene, cyclohexylene, and cyclohexanedimethylene. R3 represents a chain or cyclic divalent aliphatic group, and the carbon number thereof is 1 to 12, preferably 2 to 6. Examples of such divalent aliphatic groups include alkylene groups such as methylene, ethylene, propylene, butylene, hexylene, octylene, dodecylene, cyclohexylene, and cyclohexanedimethylene.
本発明の高分子量ポリエステルは、2万以上、好ましくは3万以上の数平均分子量を有するものである。この場合、その数平均分子量の上限は100万程度である。 The high molecular weight polyester of the present invention has a number average molecular weight of 20,000 or more, preferably 30,000 or more. In this case, the upper limit of the number average molecular weight is about 1 million.
次に本発明を実施例によって具体的に説明する。脂肪族ポリエステルの種々の物性値は下記の方法によって測定した。 Next, the present invention will be specifically described with reference to examples. Various physical properties of the aliphatic polyester were measured by the following methods.
（分子量及び分子量分布）ゲルパーミエーションクロマトグラフ（ＧＰＣ）法を用いて標準ポリスチレンから校正曲線を作成し、数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。なお、溶離液はクロロホルムを用いた。 (Molecular weight and molecular weight distribution) Using a gel permeation chromatograph (GPC) method, a calibration curve is prepared from standard polystyrene, and the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are obtained. It was. Note that chloroform was used as the eluent.
（熱的性質）示差走査熱量分析装置（ＤＳＣ）により融解温度及びガラス転移点を求めた。また熱重量分析装置（ＴＧ）により熱分解温度を求めた。 (Thermal properties) Melting temperature and glass transition point were determined by a differential scanning calorimeter (DSC). Moreover, the thermal decomposition temperature was calculated | required with the thermogravimetric analyzer (TG).
実施例１
撹拌羽つき内容量100ミリリットルのガラス製反応器にコハク酸20.8g(0.177モル)、1,4-ブタンジオール16.8g(0.187モル）、L-アスパラギン酸0.526g(3.58 ミリモル)、チタンテトライソプロポキシド20ml（0.1ミリモル）を仕込み、窒素雰囲気下、160℃で1時間反応した。昇温して180℃で1時間反応したのち、30分後200℃に昇温した。さらに30分後反応温度を230℃にして、徐々に減圧し、10分で真空度0.1mmHgに到達した。その後さらに30分反応を続けたところ、反応物は粘性が高くなり撹拌羽に絡みついた。得られたポリマーは白色で、Mn 43,300、Mw 249,400を有し、そのMw/Mnは5.76であった。またその融解温度は111.7℃であり、その2%重量減温度は299.1℃であった。このポリマー中に含まれるアスパラギン酸の割合は、ポリマー中に含まれる脂肪族ジカルボン酸成分100モル当り、2.0モルの割合である。
Example 1
In a glass reactor with a stirring volume of 100 ml, succinic acid 20.8 g (0.177 mol), 1,4-butanediol 16.8 g (0.187 mol), L-aspartic acid 0.526 g (3.58 mmol), titanium tetraisopropoxy 20 ml (0.1 mmol) was charged and reacted at 160 ° C. for 1 hour in a nitrogen atmosphere. After raising the temperature and reacting at 180 ° C. for 1 hour, the temperature was raised to 200 ° C. after 30 minutes. After another 30 minutes, the reaction temperature was raised to 230 ° C., the pressure was gradually reduced, and the degree of vacuum reached 0.1 mmHg in 10 minutes. Thereafter, the reaction was further continued for 30 minutes. As a result, the reaction product became viscous and entangled with the stirring blades. The resulting polymer was white and had Mn 43,300, Mw 249,400, and its Mw / Mn was 5.76. The melting temperature was 111.7 ° C., and the 2% weight loss temperature was 299.1 ° C. The proportion of aspartic acid contained in the polymer is 2.0 moles per 100 moles of the aliphatic dicarboxylic acid component contained in the polymer.
比較例１
撹拌羽つき内容量100ミリリットルのガラス製反応器にコハク酸20.8g(0.177モル)、1,4-ブタンジオール16.8g(0.187モル）、チタンテトライソプロポキシド20μl（0.1ミリモル）を仕込み、窒素雰囲気下、160℃で1時間反応した。昇温して180℃で1時間反応したのち、30分後200℃に昇温した。さらに30分後反応温度を230℃にして、徐々に減圧し、10分で真空度0.1mmHgに到達した。その後さらに３時間反応を続けたところ、反応物は粘性が高くなり撹拌羽に絡みついた。得られたポリマーは白色で、Mn 76,500、Mw 142,000を有し、そのMw/Mnは1.86であった。またその融解温度は114.9℃であり、その2%重量減温度は308.1℃であった。
Comparative Example 1
A glass reactor with a stirring volume of 100 ml is charged with 20.8 g (0.177 mol) of succinic acid, 16.8 g (0.187 mol) of 1,4-butanediol, and 20 μl (0.1 mmol) of titanium tetraisopropoxide in a nitrogen atmosphere. The reaction was carried out at 160 ° C. for 1 hour. After raising the temperature and reacting at 180 ° C. for 1 hour, the temperature was raised to 200 ° C. after 30 minutes. After another 30 minutes, the reaction temperature was raised to 230 ° C., the pressure was gradually reduced, and the degree of vacuum reached 0.1 mmHg in 10 minutes. Thereafter, the reaction was further continued for 3 hours. As a result, the reaction product became viscous and entangled with the stirring blades. The resulting polymer was white and had Mn 76,500, Mw 142,000 and its Mw / Mn was 1.86. The melting temperature was 114.9 ° C., and the 2% weight loss temperature was 308.1 ° C.
実施例２
撹拌羽つき内容量100ミリリットルのガラス製反応器にコハク酸21.2g(0.180モル)、1,4-ブタンジオール17.0g(0.189モル）、L-アスパラギン酸0.237g(1.78 ミリモル)、チタンテトライソプロポキシド20μl（0.1ミリモル）を仕込み、窒素雰囲気下、160℃で1時間反応した。昇温して180℃で1時間反応したのち、30分後200℃に昇温した。さらに30分後反応温度を230℃にして、徐々に減圧し、10分で真空度0.1mmHgに到達した。その後さらに1時間40分反応を続けたところ、反応物は粘性が高くなり撹拌羽に絡みついた。得られたポリマーは白色で、Mn 46,500、Mw 138,000を有し、そのMw/Mnは2.97であった。またその融解温度は109.5℃であり、その2%重量減温度は311.6℃であった。このポリマー中に含まれるアスパラギン酸の割合は、ポリマー中に含まれる脂肪族ジカルボン酸成分100モル当り、1.0モルの割合である。
Example 2
In a glass reactor with a stirring volume of 100 ml, 21.2 g (0.180 mol) of succinic acid, 17.0 g (0.189 mol) of 1,4-butanediol, 0.237 g (1.78 mmol) of L-aspartic acid, titanium tetraisopropoxy 20 μl (0.1 mmol) was charged and reacted at 160 ° C. for 1 hour in a nitrogen atmosphere. After raising the temperature and reacting at 180 ° C. for 1 hour, the temperature was raised to 200 ° C. after 30 minutes. After another 30 minutes, the reaction temperature was raised to 230 ° C., the pressure was gradually reduced, and the degree of vacuum reached 0.1 mmHg in 10 minutes. Thereafter, the reaction was further continued for 1 hour and 40 minutes. As a result, the reaction product became viscous and entangled with the stirring blades. The resulting polymer was white and had Mn 46,500, Mw 138,000, and its Mw / Mn was 2.97. The melting temperature was 109.5 ° C, and the 2% weight loss temperature was 311.6 ° C. The proportion of aspartic acid contained in the polymer is 1.0 mole per 100 moles of the aliphatic dicarboxylic acid component contained in the polymer.
比較例２
撹拌羽つき内容量100ミリリットルのガラス製反応器にコハク酸21.2g(0.180モル)、1,4-ブタンジオール16.9g(0.188モル）、L-グルタミン酸0.261g(1.77 ミリモル)、チタンテトライソプロポキシド20μl（0.1ミリモル）を仕込み、窒素雰囲気下、160℃で1時間反応した。昇温して180℃で1時間反応したのち、30分後200℃に昇温した。さらに30分後反応温度を230℃にして、徐々に減圧し、10分で真空度0.1mmHgに到達した。その後さらに7時間反応を続けた。得られたポリマーは茶色で、Mn 37,800、Mw 75,400を有し、そのMw/Mnは201であった。またその融解温度は111.4℃であり、その2%重量減温度は339.1℃であった。このポリマー中に含まれるグルタミン酸の割合は、ポリマー中に含まれる脂肪族ジカルボン酸成分100モル当り、1.0モルの割合である。
Comparative Example 2
In a glass reactor with a stirring volume of 100 ml, succinic acid 21.2 g (0.180 mol), 1,4-butanediol 16.9 g (0.188 mol), L-glutamic acid 0.261 g (1.77 mmol), titanium tetraisopropoxide 20 μl (0.1 mmol) was charged and reacted at 160 ° C. for 1 hour in a nitrogen atmosphere. After raising the temperature and reacting at 180 ° C. for 1 hour, the temperature was raised to 200 ° C. after 30 minutes. After another 30 minutes, the reaction temperature was raised to 230 ° C., the pressure was gradually reduced, and the degree of vacuum reached 0.1 mmHg in 10 minutes. Thereafter, the reaction was continued for another 7 hours. The resulting polymer was brown and had Mn 37,800, Mw 75,400, and its Mw / Mn was 201. The melting temperature was 111.4 ° C., and the 2% weight loss temperature was 339.1 ° C. The ratio of glutamic acid contained in this polymer is 1.0 mole per 100 moles of the aliphatic dicarboxylic acid component contained in the polymer.
実施例３
撹拌羽つき内容量100ミリリットルのガラス製反応器にコハク酸20.6g(0.175モル)、1,4-ブタンジオール16.8g(0.187モル）、L-アスパラギン酸0.788g(5.36 ミリモル)、チタンテトライソプロポキシド20μl（0.1ミリモル）を仕込み、窒素雰囲気下、160℃で1時間反応した。昇温して180℃で1時間反応したのち、30分後200℃に昇温した。さらに30分後反応温度を230℃にして、徐々に減圧し、10分で真空度0.1mmHgに到達した。その後さらに15分反応を続けたところ、反応物は粘性が高くなり撹拌羽に絡みついた。得られたポリマーは白色で、Mn 36,800、Mw 247,100を有し、そのMw/Mnは6.71であった。またその融解温度は108.9℃であり、その2%重量減温度は300.3℃であった。このポリマー中に含まれるアスパラギン酸の割合は、ポリマー中に含まれる脂肪族ジカルボン酸成分100モル当り、3.0モルの割合である。
Example 3
In a glass reactor with a stirring volume of 100 ml, succinic acid 20.6 g (0.175 mol), 1,4-butanediol 16.8 g (0.187 mol), L-aspartic acid 0.788 g (5.36 mmol), titanium tetraisopropoxy 20 μl (0.1 mmol) was charged and reacted at 160 ° C. for 1 hour in a nitrogen atmosphere. After raising the temperature and reacting at 180 ° C. for 1 hour, the temperature was raised to 200 ° C. after 30 minutes. After another 30 minutes, the reaction temperature was raised to 230 ° C., the pressure was gradually reduced, and the degree of vacuum reached 0.1 mmHg in 10 minutes. When the reaction was continued for another 15 minutes, the reaction product became highly viscous and entangled with the stirring blades. The resulting polymer was white and had Mn 36,800, Mw 247,100, and its Mw / Mn was 6.71. The melting temperature was 108.9 ° C., and the 2% weight loss temperature was 300.3 ° C. The ratio of aspartic acid contained in the polymer is 3.0 moles per 100 moles of the aliphatic dicarboxylic acid component contained in the polymer.
実施例４
撹拌羽つき内容量100ミリリットルのガラス製反応器にコハク酸21.2g(0.180モル)、1,4-ブタンジオール17.0g(0.189モル）、γ-カプロラクトン2.01g(17.6ミリモル）、L-アスパラギン酸0.718g(5.40ミリモル)、チタンテトライソプロポキシド20μl（0.1ミリモル）を仕込み、窒素雰囲気下、160℃で1時間反応した。昇温して180℃で1時間反応したのち、30分後200℃に昇温した。さらに30分後反応温度を230℃にして、徐々に減圧し、10分で真空度0.1mmHgに到達した。その後さらに20分反応を続けたところ、反応物は粘性が高くなり撹拌羽に絡みついた。得られたポリマーは白色で、Mn 38,800、Mw 259,000を有し、そのMw/Mnは6.68であった。またその融解温度は101.6℃であり、その2%重量減温度は300.7℃であった。このポリマー中に含まれるアスパラギン酸の割合は、ポリマー中に含まれる脂肪族ジカルボン酸成分100モル当り、3.0モルの割合である。
Example 4
In a glass reactor with a stirring volume of 100 ml, succinic acid 21.2 g (0.180 mol), 1,4-butanediol 17.0 g (0.189 mol), γ-caprolactone 2.01 g (17.6 mmol), L-aspartic acid 0.718 g (5.40 mmol) and 20 μl (0.1 mmol) of titanium tetraisopropoxide were charged and reacted at 160 ° C. for 1 hour in a nitrogen atmosphere. After raising the temperature and reacting at 180 ° C. for 1 hour, the temperature was raised to 200 ° C. after 30 minutes. After another 30 minutes, the reaction temperature was raised to 230 ° C., the pressure was gradually reduced, and the degree of vacuum reached 0.1 mmHg in 10 minutes. Thereafter, the reaction was further continued for 20 minutes. As a result, the reaction product became highly viscous and entangled with the stirring blades. The resulting polymer was white and had Mn 38,800, Mw 259,000, and its Mw / Mn was 6.68. The melting temperature was 101.6 ° C., and the 2% weight loss temperature was 300.7 ° C. The ratio of aspartic acid contained in the polymer is 3.0 moles per 100 moles of the aliphatic dicarboxylic acid component contained in the polymer.
比較例３
撹拌羽つき内容量100ミリリットルのガラス製反応器にコハク酸21.2g(0.180モル)、1,4-ブタンジオール17.0g(0.189モル）、γ-カプロラクトン2.06g(18.0ミリモル）、チタンテトライソプロポキシド20μl（0.1ミリモル）を仕込み、窒素雰囲気下、160℃で1時間反応した。昇温して180℃で1時間反応したのち、30分後200℃に昇温した。さらに30分後反応温度を230℃にして、徐々に減圧し、10分で真空度0.1mmHgに到達した。その後さらに4時間反応を続けたところ、反応物は粘性が高くなり撹拌羽に絡みついた。得られたポリマーは白色で、Mn 89,900、Mw 137,000を有し、そのMw/Mnは1.52であった。またその融解温度は105.2℃であり、その2%重量減温度は331.3℃であった。
Comparative Example 3
In a glass reactor with a stirring volume of 100 ml, succinic acid 21.2 g (0.180 mol), 1,4-butanediol 17.0 g (0.189 mol), γ-caprolactone 2.06 g (18.0 mmol), titanium tetraisopropoxide 20 μl (0.1 mmol) was charged and reacted at 160 ° C. for 1 hour in a nitrogen atmosphere. After raising the temperature and reacting at 180 ° C. for 1 hour, the temperature was raised to 200 ° C. after 30 minutes. After another 30 minutes, the reaction temperature was raised to 230 ° C., the pressure was gradually reduced, and the degree of vacuum reached 0.1 mmHg in 10 minutes. When the reaction was continued for another 4 hours, the reaction product became viscous and entangled with the stirring blades. The resulting polymer was white and had Mn 89,900, Mw 137,000, and its Mw / Mn was 1.52. The melting temperature was 105.2 ° C, and the 2% weight loss temperature was 331.3 ° C.
Claims (1)
または下記一般式（２）で表される脂肪族ジカルボン酸無水物、
あるいは両者の混合物と、
下記一般式（３）で表される脂肪族ジオールとの重縮合反応を、
アスパラギン酸の存在下で行うことを特徴とする、
下記一般式（４）で示されるポリエステル部と下記一般式（５）で示されるアスパラギン酸部とを含有する生分解性高分子量脂肪族ポリエステルの製造方法。
Or an aliphatic dicarboxylic acid anhydride represented by the following general formula (2):
Or a mixture of both,
A polycondensation reaction with an aliphatic diol represented by the following general formula (3):
Characterized in that it is carried out in the presence of aspartic acid,
The manufacturing method of biodegradable high molecular weight aliphatic polyester containing the polyester part shown by following General formula (4), and the aspartic acid part shown by following General formula (5).
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