JP5729408B2 - Polyamide 4 copolymer having a branched structure and method for producing the same - Google Patents
Polyamide 4 copolymer having a branched structure and method for producing the same Download PDFInfo
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- 229920001007 Nylon 4 Polymers 0.000 title claims description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 105
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 56
- 239000003999 initiator Substances 0.000 claims description 51
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000002685 polymerization catalyst Substances 0.000 claims description 11
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical group ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 21
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- 239000007787 solid Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- -1 carboxylic acid compound Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 230000007246 mechanism Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QISSLHPKTCLLDL-UHFFFAOYSA-N N-Acetylcaprolactam Chemical compound CC(=O)N1CCCCCC1=O QISSLHPKTCLLDL-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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Landscapes
- Polyamides (AREA)
Description
本発明は高分子鎖構造と高分子鎖組成の制御により物性(機械的性質、熱的性質等)の改質が可能なポリアミド４共重合体に関するものである。本発明により得られるポリアミド４共重合体は高強度、高融点という優れた物性を有しているのでエンジニアリングプラスチックとしての利用が可能である。さらに土壌中や活性汚泥中の微生物により生分解され、原料モノマーである２-ピロリドンは環境適合性も高く広範囲な応用が可能である。 The present invention relates to a polyamide 4 copolymer whose physical properties (mechanical properties, thermal properties, etc.) can be modified by controlling the polymer chain structure and the polymer chain composition. Since the polyamide 4 copolymer obtained by the present invention has excellent physical properties such as high strength and high melting point, it can be used as an engineering plastic. Furthermore, 2-pyrrolidone, a raw material monomer that is biodegraded by microorganisms in soil and activated sludge, has high environmental compatibility and can be used in a wide range of applications.
ポリアミド４は1956年にWilliam O.Neyらにより、金属カリウムを塩基性触媒とし、アシル基を含む化合物を活性化剤として使用することにより、２-ピロリドンが活性化モノマー機構で開環重合することにより初めて合成された（特許文献１）。その手法を基にして、1950年代から1990年代にかけて断続的に高分子量化、多分散性制御、製造工程の簡素化を目的に、新規触媒系、重合方法、ε-カプロラクタムとの共重合化等の技術開発が行われてきた(非特許文献１−５)。総じて、汎用材料として線状ポリアミド４を工業生産し、経済的に有利な溶融成型により、繊維やフィルムにすることを目標にしていた。それらの研究の中には溶融紡糸が可能となった技術開発例もあったが、加工が難しいことやコスト面で課題があり実用化は断念されている。また、ポリアミド４は高融点という優れた熱的性質を有しているが、融点と熱分解温度が接近しているために、溶融成形が困難であるという欠点がある。 Polyamide 4 is a ring-opening polymerization of 2-pyrrolidone by an activated monomer mechanism by William O. Ney et al. In 1956 using potassium metal as a basic catalyst and an acyl group-containing compound as an activator. For the first time (Patent Document 1). Based on this method, new catalyst system, polymerization method, copolymerization with ε-caprolactam, etc. for the purpose of intermittent high molecular weight, polydispersity control, and simplification of production process from 1950s to 1990s Has been developed (Non-Patent Documents 1-5). In general, linear polyamide 4 was industrially produced as a general-purpose material, and the goal was to produce fibers and films by economically advantageous melt molding. Among these studies, there were examples of technological development that enabled melt spinning, but due to difficulties in processing and problems in cost, practical application has been abandoned. Polyamide 4 has excellent thermal properties such as a high melting point, but has a drawback that melt molding is difficult because the melting point and the thermal decomposition temperature are close to each other.
特許文献２には、塩基性重合触媒および特殊構造または特殊官能基を持つカルボン酸系化合物を使用して２-ピロリドンを重合させることにより、高分子鎖中または高分子鎖末端に特殊構造もしくは官能基を有する２-ピロリドン重合体を製造できること、これにより２-ピロリドン重合体の熱安定性、成形加工性等の諸物性を制御、改善できることが記載されている。特許文献２では２-ピロリドンのホモポリマーについてのみ開示されている。 Patent Document 2 discloses that a special structure or a functional group is formed in a polymer chain or at a polymer chain end by polymerizing 2-pyrrolidone using a basic polymerization catalyst and a carboxylic acid compound having a special structure or a special functional group. It is described that a 2-pyrrolidone polymer having a group can be produced, and that various physical properties such as thermal stability and moldability of the 2-pyrrolidone polymer can be controlled and improved. Patent Document 2 discloses only a homopolymer of 2-pyrrolidone.
本発明は２-ピロリドンの開環重合が活性化モノマー機構で進行することにより、開始剤の構造がポリアミド４高分子鎖に導入できることを利用している。つまり、ポリアミド４高分子鎖に開始剤由来の特殊構造(分岐構造)と他のモノマー由来の構成単位(ε-カプロラクタム)とを共存させることで、高分子鎖構造と高分子鎖組成の制御をすることにより、物性(機械的性質、熱的性質)が改質されたポリアミド４共重合体およびその製造方法を提供することを主目的としている。 The present invention utilizes the fact that the structure of the initiator can be introduced into the polyamide 4 polymer chain by the ring-opening polymerization of 2-pyrrolidone proceeding by an activated monomer mechanism. In other words, the special structure (branched structure) derived from the initiator and the structural unit (ε-caprolactam) derived from other monomers coexist in the polyamide 4 polymer chain, thereby controlling the polymer chain structure and the polymer chain composition. Thus, the main object is to provide a polyamide 4 copolymer having improved physical properties (mechanical properties and thermal properties) and a method for producing the same.
本発明者らは、２-ピロリドン(PRN)の重合の際に、塩基性重合触媒、分岐構造(２分岐以上)を有する開始剤を使用して、ε-カプロラクタム(CLM)との共重合を行うことによって、上記目的を達成することができるという知見を得た。本発明は、これら知見に基づき、更に検討を重ねて完成されたものであり、次のポリアミド４共重合体およびその製造方法を提供すものである。
項１．開始剤由来の２分岐以上の分岐構造を有する２-ピロリドンとε-カプロラクタムの共重合体。
項２．前記開始剤由来の分岐構造が2分岐又は３分岐である項１記載の共重合体。
項３．前記開始剤が、テレフタロイルクロライド又は1,3,5-ベンゼントリカルボニルトリクロライドである項２記載の共重合体。
項４．２-ピロリドンの重合の際に、塩基性重合触媒および２分岐以上の分岐構造を有する開始剤を使用してε-カプロラクタムとの共重合を行うことにより得られる、開始剤に由来する構造を含むことを特徴とする特殊構造を有するポリアミド４共重合体。
項５．前記２分岐以上の分岐構造を有する開始剤が、２分岐又は3分岐の分岐構造を有する開始剤である項４記載のポリアミド４共重合体。
項６．前記２分岐又は3分岐の分岐構造を有する開始剤が、テレフタロイルクロライド又は1,3,5-ベンゼントリカルボニルトリクロライドである項５記載のポリアミド４共重合体。
項７．２-ピロリドンの重合の際に、塩基性重合触媒および２分岐以上の分岐構造を有する開始剤を使用してε-カプロラクタムとの共重合を行うことにより、開始剤に由来する構造を含むポリアミド４共重合体を得ることを特徴とする特殊構造を有するポリアミド４共重合体の製造方法。
項８．前記２分岐以上の分岐構造を有する開始剤として、２分岐又は3分岐の分岐構造を有する開始剤を用いる項７記載の特殊構造を有するポリアミド４共重合体の製造方法。
項９．前記２分岐又は3分岐の分岐構造を有する開始剤として、テレフタロイルクロライド又は1,3,5-ベンゼントリカルボニルトリクロライドを用いる項８記載の特殊構造を有するポリアミド４共重合体の製造方法。
In the polymerization of 2-pyrrolidone (PRN), the present inventors used a basic polymerization catalyst and an initiator having a branched structure (two or more branches) to copolymerize with ε-caprolactam (CLM). The knowledge that the said objective can be achieved by doing was acquired. Based on these findings, the present invention has been completed through further studies, and provides the following polyamide 4 copolymer and a method for producing the same.
Item 1. A copolymer of 2-pyrrolidone and ε-caprolactam having a branched structure of two or more branches derived from an initiator.
Item 2. Item 2. The copolymer according to Item 1, wherein the initiator-derived branched structure is bi-branched or tri-branched.
Item 3. Item 3. The copolymer according to Item 2, wherein the initiator is terephthaloyl chloride or 1,3,5-benzenetricarbonyl trichloride.
Item 4.2 Derived from an initiator obtained by copolymerization with ε-caprolactam using a basic polymerization catalyst and an initiator having a branched structure of two or more branches during polymerization of 2-pyrrolidone A polyamide 4 copolymer having a special structure characterized by comprising a structure.
Item 5. Item 5. The polyamide 4 copolymer according to item 4, wherein the initiator having a branched structure of two or more branches is an initiator having a branched structure of two or three branches.
Item 6. Item 6. The polyamide 4 copolymer according to item 5, wherein the initiator having a branched structure of two or three branches is terephthaloyl chloride or 1,3,5-benzenetricarbonyltrichloride.
Item 7. In polymerization of 2-pyrrolidone, a copolymer derived from an initiator is obtained by copolymerizing with ε-caprolactam using a basic polymerization catalyst and an initiator having a branched structure of two or more branches. A process for producing a polyamide 4 copolymer having a special structure, characterized in that a polyamide 4 copolymer is obtained.
Item 8. Item 8. The method for producing a polyamide 4 copolymer having a special structure according to Item 7, wherein an initiator having a branched structure of two or three branches is used as the initiator having a branched structure of two or more branches.
Item 9. Item 9. A method for producing a polyamide 4 copolymer having a special structure according to Item 8, wherein terephthaloyl chloride or 1,3,5-benzenetricarbonyltrichloride is used as the initiator having a branched structure of two or three branches.
本発明によると、ポリアミド４高分子鎖に開始剤由来の特殊構造(分岐構造)と他のモノマー由来の構成単位(ε-カプロラクタム)とを共存させて、高分子鎖構造と高分子鎖組成の制御をすることにより、物性(機械的性質、熱的性質)の改質が可能となる。更に、本発明のポリアミド4共重合体は土壌中や活性汚泥中の微生物により生分解される。 According to the present invention, a special structure (branched structure) derived from an initiator and a structural unit (ε-caprolactam) derived from another monomer coexist in a polyamide 4 polymer chain, By controlling, physical properties (mechanical properties, thermal properties) can be modified. Furthermore, the polyamide 4 copolymer of the present invention is biodegraded by microorganisms in soil or activated sludge.
以下、本発明につき詳述する。 Hereinafter, the present invention will be described in detail.
本発明の特殊構造を有するポリアミド４共重合体は、２-ピロリドンの重合の際に、塩基性重合触媒および２分岐以上の分岐構造を有する開始剤を使用してε-カプロラクタムとの共重合を行うことにより得られる、開始剤に由来する構造を含むものである。 The polyamide 4 copolymer having a special structure of the present invention is copolymerized with ε-caprolactam using a basic polymerization catalyst and an initiator having a branched structure of two or more branches in the polymerization of 2-pyrrolidone. It includes a structure derived from an initiator, obtained by performing.
また、本発明の特殊構造を有するポリアミド４共重合体の製造方法は、２-ピロリドンの重合の際に、塩基性重合触媒および２分岐以上の分岐構造を有する開始剤を使用してε-カプロラクタムとの共重合を行うことにより、開始剤に由来する構造を含むポリアミド４共重合体を得る方法である。 In addition, the method for producing a polyamide 4 copolymer having a special structure according to the present invention uses ε-caprolactam by using a basic polymerization catalyst and an initiator having a branched structure of two or more branches in the polymerization of 2-pyrrolidone. Is a method of obtaining a polyamide 4 copolymer containing a structure derived from an initiator.
前記２-ピロリドンとε-カプロラクタムの配合割合は(２-ピロリドン/ε-カプロラクタム)=(99/1)〜(２-ピロリドン/ε-カプロラクタム)=(1/99)まで任意の割合が可能であり、その割合により得られたポリアミド４共重合体の物性を制御することができる。 The mixing ratio of the 2-pyrrolidone and ε-caprolactam can be any ratio from (2-pyrrolidone / ε-caprolactam) = (99/1) to (2-pyrrolidone / ε-caprolactam) = (1/99). Yes, the properties of the polyamide 4 copolymer obtained can be controlled by the ratio.
前記塩基性重合触媒としては、ラクタム類のアニオン重合法で一般的に用いられるアルカリ金属（リチウム、ナトリウム、カリウム等）、アルカリ金属またはアルカリ土類金属の水素化物（水素化リチウム、水素化ナトリウム、水素化カルシウム等）、塩基性の有機金属化合物（ｎ−ブチルリチウム等）等を使用できる。これらの中ではナトリウムが扱い易さや収率の点で好ましい。 Examples of the basic polymerization catalyst include alkali metal (lithium, sodium, potassium, etc.), alkali metal or alkaline earth metal hydrides (lithium hydride, sodium hydride, Calcium hydride, etc.), basic organometallic compounds (n-butyllithium, etc.) can be used. Among these, sodium is preferable in terms of ease of handling and yield.
塩基性触媒の使用量は２-ピロリドンとε-カプロラクタムの合計量1 molに対して1.0〜18 mol%、好ましくは1.5〜9 mol%、更に好ましくは3〜4.5 mol%である。使用量が上記の下限および上限を超える場合でも重合は可能である。ただし、収率を高めるために工夫が必要と考えられる。 The amount of the basic catalyst used is 1.0 to 18 mol%, preferably 1.5 to 9 mol%, more preferably 3 to 4.5 mol%, based on 1 mol of the total amount of 2-pyrrolidone and ε-caprolactam. Polymerization is possible even when the amount used exceeds the above lower limit and upper limit. However, ingenuity is considered necessary to increase the yield.
使用する開始剤としてはカルボン酸ハロゲン化物、カルボン酸エステル等のカルボン酸誘導体や広義の活性化されたカルボン酸誘導体類が使用可能である。いくつかの具体例として、ベンゾイルクロライド(BzC)、テレフタロイルクロライド(Bz14DCC)、1,3,5-ベンゼントリカルボニルトリクロライド(Bz135TCC)、アセチルクロライド、ステアロイルクロライド、N-アセチル-ε-カプロラクタム(aCLM)等が挙げられる。ポリアミド４共重合体に導入しようとする構造を含む開始剤を用いればよい。 As the initiator to be used, carboxylic acid derivatives such as carboxylic acid halides and carboxylic acid esters and broadly activated carboxylic acid derivatives can be used. Some specific examples include benzoyl chloride (BzC), terephthaloyl chloride (Bz14DCC), 1,3,5-benzenetricarbonyl trichloride (Bz135TCC), acetyl chloride, stearoyl chloride, N-acetyl-ε-caprolactam ( aCLM). An initiator including a structure to be introduced into the polyamide 4 copolymer may be used.
特に２分岐以上の分岐構造を有する開始剤が好ましい。2分岐を有する開始剤としてテレフタロイルクロライドが、３分岐を有する開始剤として1,3,5-ベンゼントリカルボニルトリクロライドが挙げられる。 In particular, an initiator having a branched structure having two or more branches is preferred. Examples of the initiator having two branches include terephthaloyl chloride, and examples of the initiator having three branches include 1,3,5-benzenetricarbonyl trichloride.
前記開始剤の使用量は２-ピロリドンとε-カプロラクタムの合計量1 molに対して0.5〜16.5 mol%、好ましくは0.5〜7.5 mol%、更に好ましくは0.5〜3 mol%である。 The initiator is used in an amount of 0.5 to 16.5 mol%, preferably 0.5 to 7.5 mol%, more preferably 0.5 to 3 mol%, based on 1 mol of the total amount of 2-pyrrolidone and ε-caprolactam.
反応に際しては、ヘキサンなどの炭化水素系溶媒を使用することもできる。この場合、開始剤を選択することにより(例:ステアロイルクロライド等)、分散重合が可能となり、粉状またはフレーク状のポリアミド４共重合体が得られる。一方、無溶媒でバルク重合を行う場合には、溶媒の除去が不要という利点があるが、塊状のポリアミド４共重合体が得られるので粉砕操作が必要となる。目的により、両手法を使い分ける必要がある。 In the reaction, a hydrocarbon solvent such as hexane can also be used. In this case, by selecting an initiator (eg, stearoyl chloride, etc.), dispersion polymerization is possible, and a powdery or flaky polyamide 4 copolymer is obtained. On the other hand, when bulk polymerization is performed without a solvent, there is an advantage that the removal of the solvent is unnecessary, but a pulverizing operation is required because a bulky polyamide 4 copolymer is obtained. It is necessary to use both methods properly according to the purpose.
また、本発明方法においては、20〜180℃程度の条件で重合を行うことができる。より好ましくは50〜150℃程度、さらにより好ましくは75〜125℃程度の温度である。ただし、仕込みモノマーであるε-カプロラクタムの割合が高い場合はその融点以上にすることが必要である。 In the method of the present invention, the polymerization can be carried out under conditions of about 20 to 180 ° C. The temperature is more preferably about 50 to 150 ° C, and still more preferably about 75 to 125 ° C. However, when the ratio of ε-caprolactam as a charged monomer is high, it is necessary to set the melting point or higher.
また、発生する水素を除去するために、反応は減圧下で行うことが好ましい。 In order to remove generated hydrogen, the reaction is preferably performed under reduced pressure.
このような条件で、２-ピロリドンに塩基性重合触媒を添加し、この塩基性重合触媒が反応して無くなった後、すなわち２〜４時間程度反応させた後、ε−カプロラクタムを加えて均一な反応混合物とする。なお、均一な反応混合物とするのに２-ピロリドン、ε-カプロラクタム、ナトリウムを同時に混合しても良い。さらにカルボン酸系化合物を添加して、12〜168時間程度反応させればよい。 Under such conditions, a basic polymerization catalyst was added to 2-pyrrolidone, and after this basic polymerization catalyst was reacted and disappeared, that is, after reacting for about 2 to 4 hours, ε-caprolactam was added to obtain a uniform mixture. The reaction mixture is taken. In order to obtain a uniform reaction mixture, 2-pyrrolidone, ε-caprolactam, and sodium may be mixed simultaneously. Further, a carboxylic acid compound may be added and reacted for about 12 to 168 hours.
その後、生成した重合体を、常法に従い回収すればよい。 Then, what is necessary is just to collect | recover the produced | generated polymers according to a conventional method.
ポリアミド４共重合体の機械的性質、熱的性質を制御する方法としては、２-ピロリドンとε-カプロラクタムの配合割合、塩基性触媒又は開始剤の種類、反応温度又は反応時間等を変更することが挙げられる。 To control the mechanical and thermal properties of polyamide 4 copolymer, change the blending ratio of 2-pyrrolidone and ε-caprolactam, the type of basic catalyst or initiator, reaction temperature or reaction time, etc. Is mentioned.
高分子鎖中に特殊構造を有するポリアミド４共重合体として以下のものを例示できる。２-ピロリドンの開環重合は活性化モノマー機構により進行し、重合生成物は開始剤の構造が反映されるため、単官能性開始剤では末端線状、二官能性開始剤では二方線状、三官能性開始剤では三方分岐型のポリアミド４共重合体を合成できる。これら二方線状又は三方分岐型のポリアミド４共重合体は、成形加工性や機械的強度に優れる高分子材料としてそのまま用いることができ、さらに他のプラスチックヘの添加剤として用いることにより、成形加工性や機械的強度の改善剤として使用できる。 Examples of the polyamide 4 copolymer having a special structure in the polymer chain include the following. The ring-opening polymerization of 2-pyrrolidone proceeds by an activated monomer mechanism, and the polymerization product reflects the structure of the initiator, so it is terminally linear for monofunctional initiators and bilaterally linear for bifunctional initiators. A trifunctional initiator can synthesize a three-way branched polyamide 4 copolymer. These two-way or three-way branched polyamide 4 copolymer can be used as it is as a polymer material excellent in molding processability and mechanical strength, and further used as an additive to other plastics. It can be used as an improver for workability and mechanical strength.
本発明のポリアミド４共重合体はランダム共重合体又はブロック共重合体のいずれであってもよい。本発明のポリアミド４共重合体は生分解性を有している。 The polyamide 4 copolymer of the present invention may be either a random copolymer or a block copolymer. The polyamide 4 copolymer of the present invention is biodegradable.
以下、本発明を更に詳しく説明するため実施例を挙げる。 Examples are given below to illustrate the present invention in more detail.
以下の各実施例において、数平均分子量及び重量平均分子量は、高速GPCシステム(東ソー社製、(HLC-8220GPCシステム))により、ポリメチルメタクリレートを標準物質として用いて測定した結果から算出した。ポリマー組成比PRN/CLMは1HNMを測定し、CLMユニット由来のメチレンプロトンの強度とPRNユニット由来のメチレンプロトンの比を見積ることにより算出した。 In each of the following Examples, the number average molecular weight and the weight average molecular weight were calculated from the results of measurement using polymethyl methacrylate as a standard substance with a high-speed GPC system (manufactured by Tosoh Corporation, (HLC-8220GPC system)). The polymer composition ratio PRN / CLM was calculated by measuring 1 HNM and estimating the ratio of methylene protons derived from CLM units to methylene protons derived from PRN units.
実施例1
三方分岐型ポリアミド４共重合体は以下のように合成した。減圧装置の付いたフラスコに精製して水分を除去した２-ピロリドン3.40 g(40 mmol)、ナトリウム0.034 g(1.5 mmol)を入れ、減圧下50℃で加熱してナトリウムを反応させた。ナトリウムが完全に反応した後、ε-カプロラクタム1.13 g(10 mmol)を加えて、均一な反応混合物とした(なお、均一な反応混合物とするのに２-ピロリドン、ε-カプロラクタム、ナトリウムを同時に混合しても良い。)。つづいて、1,3,5-ベンゼントリカルボニルトリクロライド0.066 g(0.25 mmol、アシル基として0.75 mmol)を加えて75℃で数時間減圧とし、アルゴン置換を行い、合計24時間程度、重合反応を行った。重合生成物はトリフルオロエタノールに溶解させ、ギ酸を使用してナトリウムによる塩基性を中和した後、ガラスフィルターでろ過して不溶物を除いた。得られた重合生成物の濾液を濃縮し、アセトンで沈澱させ、蒸留水、メタノールで洗浄することにより精製した。これにより淡赤色固体が2.37 g(収率52 %)得られた。ポリマー組成比PRN/CLM=90/10。重量平均分子量272×103。融点266℃。
Example 1
The three-way branched polyamide 4 copolymer was synthesized as follows. 2-Pyrrolidone 3.40 g (40 mmol) and sodium 0.034 g (1.5 mmol), which had been purified to remove water by purification in a flask equipped with a vacuum apparatus, were added and heated at 50 ° C. under reduced pressure to react with sodium. After sodium was completely reacted, 1.13 g (10 mmol) of ε-caprolactam was added to obtain a homogeneous reaction mixture (in addition, 2-pyrrolidone, ε-caprolactam and sodium were mixed at the same time to obtain a homogeneous reaction mixture). You may do it.) Next, 0.066 g (0.25 mmol, 0.75 mmol as an acyl group) of 1,3,5-benzenetricarbonyltrichloride was added, and the pressure was reduced at 75 ° C. for several hours, followed by argon substitution, and the polymerization reaction was performed for a total of about 24 hours. went. The polymerization product was dissolved in trifluoroethanol, and the basicity with sodium was neutralized using formic acid, followed by filtration with a glass filter to remove insoluble matters. The obtained polymerization product filtrate was concentrated, precipitated with acetone, and purified by washing with distilled water and methanol. As a result, 2.37 g (yield 52%) of a pale red solid was obtained. Polymer composition ratio PRN / CLM = 90/10. Weight average molecular weight 272 × 10 3 . Melting point 266 ° C.
実施例2
三方分岐型ポリアミド４共重合体は以下のように合成した。２-ピロリドン2.98 g(35 mmol)とε-カプロラクタム1.70 g(15 mmol)にナトリウム0.034 g(1.5 mmol)を入れ、減圧下50℃で加熱してナトリウムを反応させた。ナトリウムが完全に反応した後、1,3,5-ベンゼントリカルボニルトリクロライド0.066 g(0.25 mmol)を加えて75℃で数時間減圧とし、アルゴン置換を行い、合計24時間程度、重合反応を行った。精製は実施例1と同様の操作を行った。これにより淡赤色固体が2.16 g(収率46 %)得られた。ポリマー組成比PRN/CLM=78/22。重量平均分子量263×103。融点265℃。
Example 2
The three-way branched polyamide 4 copolymer was synthesized as follows. 0.034 g (1.5 mmol) of sodium was added to 2.98 g (35 mmol) of 2-pyrrolidone and 1.70 g (15 mmol) of ε-caprolactam, and sodium was reacted by heating at 50 ° C. under reduced pressure. After the sodium has completely reacted, add 0.03 g (0.25 mmol) of 1,3,5-benzenetricarbonyltrichloride, depressurize at 75 ° C for several hours, and perform argon substitution for a total of 24 hours for the polymerization reaction. It was. Purification was carried out in the same manner as in Example 1. As a result, 2.16 g (yield 46%) of a pale red solid was obtained. Polymer composition ratio PRN / CLM = 78/22. Weight average molecular weight 263 × 10 3 . Melting point 265 ° C.
実施例3
三方分岐型ポリアミド４共重合体は以下のように合成した。２-ピロリドン2.55 g(30 mmol)、ε-カプロラクタム2.26 g(20 mmol)、ナトリウム0.034 g(1.5 mmol)、1,3,5-ベンゼントリカルボニルトリクロライド0.066 g(0.25 mmol)を用いて、実施例2と同様の操作を行った。これにより象牙色固体が0.61 g(収率13 %)得られた。ポリマー組成比PRN/CLM=70/30。重量平均分子量83×103。融点155, 246℃(2つのピーク)。
Example 3
The three-way branched polyamide 4 copolymer was synthesized as follows. Conducted using 2.55 g (30 mmol) of 2-pyrrolidone, 2.26 g (20 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium, 0.066 g (0.25 mmol) of 1,3,5-benzenetricarbonyl trichloride The same operation as in Example 2 was performed. As a result, 0.61 g (yield 13%) of an ivory solid was obtained. Polymer composition ratio PRN / CLM = 70/30. Weight average molecular weight 83 × 10 3 . Melting point 155, 246 ° C. (2 peaks).
実施例4
三方分岐型ポリアミド４共重合体は以下のように合成した。２-ピロリドン2.55 g(30 mmol)、ε-カプロラクタム2.26 g(20 mmol)、ナトリウム0.034 g(1.5 mmol)、1,3,5-ベンゼントリカルボニルトリクロライド0.066 g(0.25 mmol)を用いて、実施例1と同様の操作を行った。これにより淡橙色固体が1.01 g(収率21 %)得られた。ポリマー組成比PRN/CLM=59/41。重量平均分子量196×103。融点154℃。
Example 4
The three-way branched polyamide 4 copolymer was synthesized as follows. Conducted using 2.55 g (30 mmol) of 2-pyrrolidone, 2.26 g (20 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium, 0.066 g (0.25 mmol) of 1,3,5-benzenetricarbonyl trichloride The same operation as in Example 1 was performed. As a result, 1.01 g (yield 21%) of a pale orange solid was obtained. Polymer composition ratio PRN / CLM = 59/41. Weight average molecular weight 196 × 10 3 . Melting point 154 ° C.
実施例5
三方分岐型ポリアミド４共重合体は以下のように合成した。２-ピロリドン2.13 g(25 mmol)、ε-カプロラクタム2.83 g(25 mmol)、ナトリウム0.034 g(1.5 mmol)、1,3,5-ベンゼントリカルボニルトリクロライド0.066 g(0.25 mmol)を用いて、実施例2と同様の操作を行った。これにより象牙色固体が1.06 g(収率21 %)得られた。ポリマー組成比PRN/CLM=51/49。重量平均分子量240×103。融点158℃。
Example 5
The three-way branched polyamide 4 copolymer was synthesized as follows. Conducted with 2.13 g (25 mmol) of 2-pyrrolidone, 2.83 g (25 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium and 0.066 g (0.25 mmol) of 1,3,5-benzenetricarbonyl trichloride The same operation as in Example 2 was performed. As a result, 1.06 g (yield 21%) of an ivory solid was obtained. Polymer composition ratio PRN / CLM = 51/49. Weight average molecular weight 240 × 10 3 . Melting point 158 ° C.
実施例6
三方分岐型ポリアミド４共重合体は以下のように合成した。２-ピロリドン1.70 g(20 mmol)、ε-カプロラクタム3.39 g(30 mmol)、ナトリウム0.034 g(1.5 mmol)、1,3,5-ベンゼントリカルボニルトリクロライド0.066 g(0.25 mmol)を用いて、実施例1と同様の操作を行った。これにより白色固体が1.00 g(収率19 %)得られた。ポリマー組成比PRN/CLM=40/60。重量平均分子量258×103。融点148, 156℃(2つのピーク)。
Example 6
The three-way branched polyamide 4 copolymer was synthesized as follows. Conducted with 2-pyrrolidone 1.70 g (20 mmol), ε-caprolactam 3.39 g (30 mmol), sodium 0.034 g (1.5 mmol), 1,3,5-benzenetricarbonyltrichloride 0.066 g (0.25 mmol) The same operation as in Example 1 was performed. As a result, 1.00 g (yield 19%) of a white solid was obtained. Polymer composition ratio PRN / CLM = 40/60. Weight average molecular weight 258 × 10 3 . Melting point 148, 156 ° C. (2 peaks).
実施例7
三方分岐型ポリアミド４共重合体は以下のように合成した。２-ピロリドン3.83 g(45 mmol)、ε-カプロラクタム0.57 g(5 mmol)、ナトリウム0.034 g(1.5 mmol)、1,3,5-ベンゼントリカルボニルトリクロライド0.066 g(0.25 mmol)を用いて、実施例1と同様の操作を行った。これにより淡赤色固体が2.46 g(収率56 %)得られた。ポリマー組成比PRN/CLM=96/4。重量平均分子量157×103。融点266℃。
Example 7
The three-way branched polyamide 4 copolymer was synthesized as follows. 2-pyrrolidone 3.83 g (45 mmol), ε-caprolactam 0.57 g (5 mmol), sodium 0.034 g (1.5 mmol), 1,3,5-benzenetricarbonyltrichloride 0.066 g (0.25 mmol) The same operation as in Example 1 was performed. As a result, 2.46 g (yield 56%) of a pale red solid was obtained. Polymer composition ratio PRN / CLM = 96/4. Weight average molecular weight 157 × 10 3 . Melting point 266 ° C.
実施例8
二方線状ポリアミド４共重合体は以下のように合成した。２-ピロリドン3.83 g(45 mmol)、ε-カプロラクタム0.57 g(5 mmol)、ナトリウム0.034 g(1.5 mmol)、テレフタロイルクロライド0.076 g(0.375 mmol)を用いて、実施例1と同様の操作を行った。これにより白色固体(粉末)が0.86 g(収率20 %)得られた。ポリマー組成比PRN/CLM=87/13。重量平均分子量47×103。融点253℃。
Example 8
The bilinear polyamide 4 copolymer was synthesized as follows. The same procedure as in Example 1 was performed using 3.83 g (45 mmol) of 2-pyrrolidone, 0.57 g (5 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium, and 0.076 g (0.375 mmol) of terephthaloyl chloride. went. As a result, 0.86 g (yield 20%) of a white solid (powder) was obtained. Polymer composition ratio PRN / CLM = 87/13. Weight average molecular weight 47 × 10 3 . Melting point 253 ° C.
実施例9
二方線状ポリアミド４共重合体は以下のように合成した。２-ピロリドン3.40 g(40 mmol)、ε-カプロラクタム1.13 g(10 mmol)、ナトリウム0.034 g(1.5 mmol)、テレフタロイルクロライド0.076 g(0.375 mmol)を用いて、実施例1と同様の操作を行った。これにより淡赤色固体が0.90 g(収率20 %)得られた。ポリマー組成比PRN/CLM=72/28。重量平均分子量43×103。融点161, 256℃(2つのピーク)。
Example 9
The bilinear polyamide 4 copolymer was synthesized as follows. The same procedure as in Example 1 was performed using 2.40 g (40 mmol) of 2-pyrrolidone, 1.13 g (10 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium, and 0.076 g (0.375 mmol) of terephthaloyl chloride. went. As a result, 0.90 g (yield 20%) of a pale red solid was obtained. Polymer composition ratio PRN / CLM = 72/28. Weight average molecular weight 43 × 10 3 . Melting point 161, 256 ° C. (2 peaks).
実施例10
二方線状ポリアミド４共重合体は以下のように合成した。２-ピロリドン2.55 g(30 mmol)、ε-カプロラクタム2.26 g(20 mmol)、ナトリウム0.034 g(1.5 mmol)、テレフタロイルクロライド0.076g(0.375 mmol)を用いて、実施例1と同様の操作を行った。これにより白色固体(粉末)が1.76 g(収率37 %)得られた。ポリマー組成比PRN/CLM=66/34。重量平均分子量55×103。融点156℃、262℃(2つのピーク)。
Example 10
The bilinear polyamide 4 copolymer was synthesized as follows. The same procedure as in Example 1 was performed using 2.55 g (30 mmol) of 2-pyrrolidone, 2.26 g (20 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium, and 0.076 g (0.375 mmol) of terephthaloyl chloride. went. As a result, 1.76 g (yield 37%) of a white solid (powder) was obtained. Polymer composition ratio PRN / CLM = 66/34. Weight average molecular weight 55 × 10 3 . Melting points 156 ° C., 262 ° C. (2 peaks).
実施例11
対照として末端線状ポリアミド４共重合体を以下のように合成した。２-ピロリドン3.40 g(40 mmol)、ε-カプロラクタム0.57 g(5 mmol)、ナトリウム0.034 g(1.5 mmol)、ベンゾイルクロライド0.105 g(0.75 mmol)を用いて、実施例1と同様の操作を行った。これにより白色固体(粉末)が1.58 g(収率35 %)得られた。ポリマー組成比PRN/CLM=91/9。重量平均分子量28×103。融点265℃。
Example 11
As a control, a terminal linear polyamide 4 copolymer was synthesized as follows. The same operation as in Example 1 was performed using 3.40 g (40 mmol) of 2-pyrrolidone, 0.57 g (5 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium, and 0.105 g (0.75 mmol) of benzoyl chloride. . As a result, 1.58 g (yield 35%) of a white solid (powder) was obtained. Polymer composition ratio PRN / CLM = 91/9. Weight average molecular weight 28 × 10 3 . Melting point 265 ° C.
実施例12
対照として末端線状ポリアミド４共重合体を以下のように合成した。２-ピロリドン3.83 g(45 mmol)、ε-カプロラクタム1.13 g(10 mmol)、ナトリウム0.034 g(1.5 mmol)、N-アセチル-ε-カプロラクタム0.116 g(0.75 mmol)を用いて、実施例1と同様の操作を行った。これにより淡赤色固体が1.28 g(収率29 %)得られた。ポリマー組成比PRN/CLM=90/10。重量平均分子量29×103。融点264℃。
Example 12
As a control, a terminal linear polyamide 4 copolymer was synthesized as follows. Similar to Example 1 using 3.83 g (45 mmol) of 2-pyrrolidone, 1.13 g (10 mmol) of ε-caprolactam, 0.034 g (1.5 mmol) of sodium and 0.116 g (0.75 mmol) of N-acetyl-ε-caprolactam Was performed. As a result, 1.28 g (yield 29%) of a pale red solid was obtained. Polymer composition ratio PRN / CLM = 90/10. Weight average molecular weight 29 × 10 3 . Melting point 264 ° C.
上記実施例１〜12および表の実験結果により、以下のことがわかる。(1)ポリアミド4共重合体の重量平均分子量は、単官能性開始剤を使用して合成した末端線状ポリアミド４共重合体に比べて、二官能性や三官能性開始剤を使用して合成した二方線状ポリアミド４共重合体、三方分岐型ポリアミド４共重合体の方が高くなる。特に、三官能性開始剤を使用した場合は、可溶性ミクロゲルが生成することが原因と考えられる高分子量化が起こる。(2)ポリアミド４共重合体の融点はその組成により熱的性質の調節が可能である。特に、ポリマー組成比でCLM含有率が40%を超える辺りから融点の低下が顕著となる。 The following can be seen from the above Examples 1 to 12 and the experimental results in the table. (1) The weight average molecular weight of the polyamide 4 copolymer is higher than that of a terminal linear polyamide 4 copolymer synthesized using a monofunctional initiator, using a bifunctional or trifunctional initiator. The synthesized two-way linear polyamide 4 copolymer and three-way branched polyamide 4 copolymer are higher. In particular, when a trifunctional initiator is used, a high molecular weight that is considered to be caused by the formation of a soluble microgel occurs. (2) The melting point of the polyamide 4 copolymer can be controlled by its composition. In particular, the decrease in melting point becomes remarkable when the CLM content exceeds 40% in the polymer composition ratio.
実施例13
上記の実施例に基づいて合成したポリアミド４共重合体を使用し、トリフルオロエタノールを溶媒として、溶媒キャスティング法によりフィルムを作成し、引張強度と破断伸度を測定した。対照試料である末端線状ポリアミド４共重合体は測定可能なフィルムが形成されなかった。しかし、二方線状ポリアミド４共重合体、三方分岐型ポリアミド４共重合体は良好なフィルムが形成された。
Example 13
Using the polyamide 4 copolymer synthesized based on the above-mentioned examples, a film was prepared by a solvent casting method using trifluoroethanol as a solvent, and tensile strength and elongation at break were measured. No measurable film was formed with the terminal linear polyamide 4 copolymer as a control sample. However, a good film was formed with the two-way linear polyamide 4 copolymer and the three-way branched polyamide 4 copolymer.
実施例14
溶媒キャスティング法により作成したフィルムを厚さ53μm(平均)、長さ15 mm、幅5 mmの矩形型の試験片に加工した。 万能試験機(Auto com/AC-50、テイ・エス エンジニアリング)を用いて、引張強度、破断伸度を測定し、各試験片について１５個の測定値を平均した(表参照)。
Example 14
A film prepared by the solvent casting method was processed into a rectangular test piece having a thickness of 53 μm (average), a length of 15 mm, and a width of 5 mm. Tensile strength and elongation at break were measured using a universal testing machine (Auto com / AC-50, TS Engineering), and 15 measurements were averaged for each specimen (see table).
単官能性開始剤を使用して合成した末端線状ポリアミド４共重合体に比べて、二官能性や三官能性開始剤を使用して合成した二方線状ポリアミド４共重合体、三方分岐型ポリアミド４共重合体は、力学的性質(引張強度、破断伸び)の改質が可能となることが確認できた。特に、三官能性開始剤を使用した場合は、分岐による絡み合いの効果に加えて、可溶性ミクロゲルが生成することが原因と考えられる高分子量化により、力学的性質が向上したものと考えられる。 Compared to terminal linear polyamide 4 copolymers synthesized using monofunctional initiators, bilinear polyamide 4 copolymers synthesized using bifunctional or trifunctional initiators, three-way branched It was confirmed that the type polyamide 4 copolymer can be modified in mechanical properties (tensile strength, elongation at break). In particular, when a trifunctional initiator is used, in addition to the effect of entanglement due to branching, it is considered that the mechanical properties have been improved by increasing the molecular weight considered to be due to the formation of a soluble microgel.
引張強度、破断伸度については、CLMユニットからなるポリアミド６は70〜83MPa、300%(MARUZEN高分子大辞典、丸善株式会社1994、p980)、PRNユニットからなるポリアミド４は72MPa、51%( Kawasaki, N. et al : Polymer: 46, 9987-9993(2005))というデータがあるが、CLMユニットとPRNユニットを含有する分岐構造を有するポリアミド４共重合体では引張強度は同程度からやや低下するものの、破断伸度は大幅に大きくなった。このことより、ポリアミド４の力学的性質である引張強度、破断伸度を改質する手法として、分岐構造を有して共重合化することは有効であることが分かった。 Regarding tensile strength and elongation at break, polyamide 6 composed of CLM units is 70 to 83 MPa, 300% (MARUZEN Polymer Dictionary, Maruzen Co., Ltd. 1994, p980), and polyamide 4 composed of PRN units is 72 MPa, 51% (Kawasaki , N. et al: Polymer: 46, 9987-9993 (2005)), but the polyamide 4 copolymer with a branched structure containing a CLM unit and a PRN unit has a slightly lower tensile strength from the same level. However, the elongation at break increased significantly. From this, it was found that copolymerization with a branched structure is effective as a method for modifying the tensile properties and elongation at break, which are mechanical properties of polyamide 4.
実施例15
ポリアミド４共重合体の特徴である活性汚泥中における生分解性を以下のように調べた。無機培養液500 mlにポリマー試料200 mgを分散させ、(財)化学物質評価研究機構より提供された標準活性汚泥30 mlを加え、撹拌しながら二酸化炭素を除いた空気で曝気を行い、培養槽の排気をアルカリトラップ(0.025 N 水酸化ナトリウム水溶液)に通し、微生物の代謝により発生した二酸化炭素を捕捉した。発生二酸化炭素は無機炭素量として全有機炭素計(TOC-VCSH、島津製作所)を用いて4週間、1週ごとに測定した。ポリマー試料の生分解性は100 %分解した場合に発生する二酸化炭素量を理論値として以下の式により評価した(表参照)。
生分解(%) = 二酸化炭素(測定値)/二酸化炭素(理論値)×100
Example 15
The biodegradability in activated sludge, which is a characteristic of the polyamide 4 copolymer, was examined as follows. Disperse 200 mg of polymer sample in 500 ml of inorganic culture solution, add 30 ml of standard activated sludge provided by the Chemical Substance Evaluation Research Organization, aerate with carbon dioxide with stirring, and culture tank Was passed through an alkali trap (0.025 N sodium hydroxide aqueous solution) to capture carbon dioxide generated by the metabolism of microorganisms. The generated carbon dioxide was measured every week for 4 weeks using a total organic carbon meter (TOC-V CSH , Shimadzu Corporation) as the amount of inorganic carbon. The biodegradability of the polymer sample was evaluated by the following formula using the amount of carbon dioxide generated when 100% decomposed as a theoretical value (see table).
Biodegradation (%) = carbon dioxide (measured value) / carbon dioxide (theoretical value) x 100
表より、ポリアミド４共重合体の生分解性についての傾向を明らかにするには(分解実験条件が活性汚泥中の時々刻々と変化する微生物相に影響を受け、一定条件を維持するのが困難であるので)測定例を増やすことが必要ではあるが、少なくとも通常の条件では分解しにくいポリアミド６(CLM含有率100%)にPRNユニットを含有させることにより、生分解性の付与をすることが可能であることが分かる。 From the table, to clarify the tendency of polyamide 4 copolymer for biodegradability (degradation experimental conditions are affected by the microbial flora that changes from time to time in activated sludge, it is difficult to maintain constant conditions Although it is necessary to increase the number of measurement examples, biodegradability can be imparted by adding PRN units to polyamide 6 (CLM content 100%) which is difficult to decompose at least under normal conditions. It turns out that it is possible.
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