JP2016014105A - Polymer alloy and method for producing the same - Google Patents
Polymer alloy and method for producing the same Download PDFInfo
- Publication number
- JP2016014105A JP2016014105A JP2014137136A JP2014137136A JP2016014105A JP 2016014105 A JP2016014105 A JP 2016014105A JP 2014137136 A JP2014137136 A JP 2014137136A JP 2014137136 A JP2014137136 A JP 2014137136A JP 2016014105 A JP2016014105 A JP 2016014105A
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- Prior art keywords
- monomer
- acid
- pores
- polymer alloy
- polymer
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 103
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 67
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000004793 Polystyrene Substances 0.000 description 23
- 229920002223 polystyrene Polymers 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000011701 zinc Substances 0.000 description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 11
- 239000003446 ligand Substances 0.000 description 11
- 239000004926 polymethyl methacrylate Substances 0.000 description 11
- -1 transition metal cation Chemical class 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
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- 238000005259 measurement Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
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- 239000000126 substance Substances 0.000 description 8
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
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- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 5
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- 239000003999 initiator Substances 0.000 description 4
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N H2dhybdc Natural products OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- LCZUOKDVTBMCMX-UHFFFAOYSA-N 2,5-Dimethylpyrazine Chemical compound CC1=CN=C(C)C=N1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-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 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- MAWKLXRVKVOYLR-UHFFFAOYSA-N 4-(4-pyridin-4-ylphenyl)pyridine Chemical compound C1=NC=CC(C=2C=CC(=CC=2)C=2C=CN=CC=2)=C1 MAWKLXRVKVOYLR-UHFFFAOYSA-N 0.000 description 2
- MGFJDEHFNMWYBD-OWOJBTEDSA-N 4-[(e)-2-pyridin-4-ylethenyl]pyridine Chemical group C=1C=NC=CC=1/C=C/C1=CC=NC=C1 MGFJDEHFNMWYBD-OWOJBTEDSA-N 0.000 description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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Abstract
Description
本発明はポリマーアロイ及びその製造方法に関し、詳しくは分子レベルで相溶化したポリマーアロイ及びその製造方法に関する。 The present invention relates to a polymer alloy and a method for producing the same, and more particularly to a polymer alloy compatibilized at a molecular level and a method for producing the same.
複数のポリマーをアロイ化することで、機能の向上や創発的な物性が期待されるが、ほとんどのポリマーの組み合わせでは分子レベルで相溶化しない。一方、金属イオンと有機配位子からなる多孔性金属錯体の細孔を重合反応場として利用することで、得られるポリマーの一次構造や集積構造の制御ができることが報告されている(特許文献１〜４)。しかしながら、特許文献１〜４は、分子レベルで相溶化したポリマーアロイを得る方法は開示していない。 By alloying multiple polymers, functional improvements and emergent physical properties are expected, but most polymer combinations do not compatibilize at the molecular level. On the other hand, it has been reported that the primary structure and integrated structure of a polymer obtained can be controlled by using the pores of a porous metal complex composed of a metal ion and an organic ligand as a polymerization reaction field (Patent Document 1). ~ 4). However, Patent Documents 1 to 4 do not disclose a method for obtaining a polymer alloy compatibilized at a molecular level.
ポリマーの相溶化を行うためにブロック共重合体などの相溶化剤を用いたり、架橋やグラフト重合を行って相溶化する手法が使われているが、新たな添加剤の混入やポリマー組成の変化が起こるため、適切な手法とは言えない。また、機械的混練による物理的な混和も行われているが、ドメインサイズは小さくなるものの、分子レベルで相溶化することはできていない。 In order to compatibilize the polymer, a compatibilizer such as a block copolymer is used, or a method of compatibilization by cross-linking or graft polymerization is used, but mixing of new additives and changes in polymer composition This is not an appropriate technique. Moreover, although physical mixing by mechanical kneading is also performed, although the domain size is small, it cannot be compatibilized at the molecular level.
本発明は複数のポリマーを分子レベルで相溶化させる技術を提供することを主な目的とする。 The main object of the present invention is to provide a technique for compatibilizing a plurality of polymers at the molecular level.
多孔性金属錯体のナノ空間で複数のポリマーを合成し、錯体構造を壊すことで、空間内にランダム配置されたポリマー鎖の配置をある程度保ったまま、単離することにより上記課題を解決できることを本発明者は見出した。 By synthesizing a plurality of polymers in the nanospace of the porous metal complex and breaking the complex structure, it is possible to solve the above problem by isolating while maintaining the arrangement of polymer chains randomly arranged in the space to some extent. The inventor found.
本発明は、以下のポリマーアロイ及びその製造方法を提供するものである。
項１． 以下の工程を含む、分子レベルで相溶化したポリマーアロイの製造方法：
工程１：多孔性金属錯体の細孔内に最初のモノマーを充填する工程
工程２：一部の細孔内のモノマーを重合する工程
工程３：未反応のモノマーを除去する工程
工程４：未反応のモノマーが除去された細孔内に次のモノマーを充填する工程
工程５：細孔内のモノマーを部分的又は完全に重合する工程、
工程６：工程５の後で未重合のモノマーがある場合、工程３〜工程５を必要な回数だけ繰り返す工程
工程７：多孔性金属錯体の構造を壊してポリマーアロイを回収する工程。
項２． 多孔性金属錯体の細孔内に２種以上のポリマーが収容されてなる、多孔性金属錯体とポリマーの複合体。
項３． 項２に記載の複合体において、多孔性金属錯体の構造を壊してポリマーアロイを回収することを特徴とする、分子レベルで相溶化したポリマーアロイの製造方法。
項４． ２種以上のポリマーが分子レベルで相溶化したポリマーアロイ。
項５． ２種以上のポリマー間の平均距離が3nm以下である、項４に記載のポリマーアロイ。
項６． ２種以上のポリマーの溶解度パラメータが５以上異なることを特徴とする、項４又は５に記載のポリマーアロイ。
The present invention provides the following polymer alloy and method for producing the same.
Item 1. A method for producing a polymer alloy compatibilized at the molecular level, comprising the following steps:
Step 1: Step of filling first monomer into pores of porous metal complex Step 2: Step of polymerizing monomer in some pores Step 3: Step of removing unreacted monomer Step 4: Unreacted Step 5 of filling the next monomer in the pores from which the monomer has been removed Step 5: Step of partially or completely polymerizing the monomer in the pores,
Step 6: When there is an unpolymerized monomer after Step 5, Step 7 is a step of repeating Step 3 to Step 5 as many times as necessary. Step 7: Step of destroying the structure of the porous metal complex and recovering the polymer alloy.
Item 2. A composite of a porous metal complex and a polymer, wherein two or more kinds of polymers are accommodated in the pores of the porous metal complex.
Item 3. Item 3. A method for producing a polymer alloy compatibilized at a molecular level, wherein the polymer alloy is recovered by breaking the structure of the porous metal complex in the composite according to Item 2.
Item 4. A polymer alloy in which two or more polymers are compatibilized at the molecular level.
Item 5. Item 5. The polymer alloy according to Item 4, wherein the average distance between two or more polymers is 3 nm or less.
Item 6. Item 6. The polymer alloy according to Item 4 or 5, wherein the solubility parameter of two or more polymers is different by 5 or more.
本発明によれば、溶解度パラメーターが大きく異なり、単純にブレンドしただけでは相溶化することが不可能な異種ポリマー組み合わせでさえ、分子レベルで相溶化することができる。また、得られたポリマーアロイは通常のブレンド体に比べ、高い熱安定性を示す。 According to the present invention, even the dissimilar polymer combinations that have greatly different solubility parameters and cannot be compatibilized by simple blending can be compatibilized at the molecular level. Moreover, the obtained polymer alloy shows high heat stability compared with a normal blend.
本発明で使用される多孔性金属錯体は、遷移金属イオンとそれを連結する有機架橋配位子によって多孔性３次元構造を有する金属錯体であり、好ましくは、遷移金属カチオンと第１有機架橋配位子から構成される２次元シートが層をなし、２座配位可能な第２有機架橋配位子が各層に存在する遷移金属カチオンに配位することで隣接するシートとシートを連結させ、その間に細孔が形成されている構造を有する配位ポリマー、相互嵌入型の配位ポリマーなどが挙げられる。本発明の多孔性金属錯体は、MOF、PCPなどとして知られている多孔性金属錯体を広く包含する。多孔性金属錯体の細孔は、１次元細孔、２次元細孔、３次元細孔のいずれでもよいが、１次元細孔が好ましい。細孔径は、3nm以下、好ましくは2nm以下、より好ましくは1.5nm以下であり、0.3nm以上、好ましくは0.5nm以上、より好ましくは0.7nm以上である。細孔の測定は、単結晶Ｘ線回折、粉末Ｘ線回折によって行うことができる。また、窒素吸着測定によっても細孔径を測定することができる。細孔径が大きすぎると1つの細孔内に多数のポリマーが形成される可能性があり、細孔径が小さすぎると細孔内でのポリマーの形成が困難になる。 The porous metal complex used in the present invention is a metal complex having a porous three-dimensional structure by a transition metal ion and an organic bridging ligand linking the transition metal ion, preferably a transition metal cation and a first organic cross-linked coordination. A two-dimensional sheet composed of ligands forms a layer, and a second organic bridging ligand capable of bidentate coordination is coordinated to a transition metal cation present in each layer, thereby connecting adjacent sheets and sheets, Examples thereof include a coordination polymer having a structure in which pores are formed therebetween, and an interdigitated coordination polymer. The porous metal complexes of the present invention broadly include porous metal complexes known as MOF, PCP and the like. The pores of the porous metal complex may be one-dimensional pores, two-dimensional pores, or three-dimensional pores, but one-dimensional pores are preferred. The pore diameter is 3 nm or less, preferably 2 nm or less, more preferably 1.5 nm or less, 0.3 nm or more, preferably 0.5 nm or more, more preferably 0.7 nm or more. The pores can be measured by single crystal X-ray diffraction or powder X-ray diffraction. The pore diameter can also be measured by nitrogen adsorption measurement. If the pore size is too large, a large number of polymers may be formed in one pore, and if the pore size is too small, it is difficult to form a polymer in the pores.
多孔性金属錯体は、第１有機架橋配位子とともに単座有機配位子を含んでいてもよい。単座有機配位子を加えることで、錯体結晶のサイズを調節することができる。 The porous metal complex may contain a monodentate organic ligand together with the first organic bridging ligand. The size of the complex crystal can be adjusted by adding a monodentate organic ligand.
遷移金属カチオンとしては、金属イオンとしては、周期表の１〜１２族に属する金属の金属イオン、具体的には、金、白金、銀、銅、ルテニウム、スズ、パラジウム、ロジウム、イリジウム、オスミウム、ニッケル、コバルト、亜鉛、鉄、イットリウム、マグネシウム、マンガン、チタン、ジルコニウム、ハフニウム、カルシウム、カドミウム、バナジウム、クロム、モリブデン、スカンジウムなどのイオンが挙げられ、マグネシウム、カルシウム、マンガン、鉄、ルテニウム、コバルト、ロジウム、ニッケル、パラジウム、銅、亜鉛、カドミウム、チタン、バナジウム、クロム、マンガン、白金、モリブデン、ジルコニウム、スカンジウムなどのイオンが好ましく、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、銀、白金、パラジウム、ルテニウム、ロジウムなどの金属のイオンがより好ましい。 As a transition metal cation, as a metal ion, a metal ion of a metal belonging to Group 1 to 12 of the periodic table, specifically, gold, platinum, silver, copper, ruthenium, tin, palladium, rhodium, iridium, osmium, Examples include ions of nickel, cobalt, zinc, iron, yttrium, magnesium, manganese, titanium, zirconium, hafnium, calcium, cadmium, vanadium, chromium, molybdenum, scandium, magnesium, calcium, manganese, iron, ruthenium, cobalt, Ions such as rhodium, nickel, palladium, copper, zinc, cadmium, titanium, vanadium, chromium, manganese, platinum, molybdenum, zirconium, scandium are preferred, manganese, iron, cobalt, nickel, copper, zinc, silver, platinum, palladium , Ruthenium, more preferably metal ions, such as rhodium.
有機架橋配位子のうち、第１有機架橋配位子としては、ベンゼン、ナフタレン、アントラセン、フェナントレン、フルオレン、インダン、インデン、ピレン、１，４−ジヒドロナフタレン、テトラリン、ビフェニレン、トリフェニレン、アセナフチレン、アセナフテンなどの芳香環に２個、３個又は４個のカルボキシル基が結合した化合物（前記有機配位子は、Ｆ，Ｃｌ、Ｂｒ，Ｉなどのハロゲン原子、ニトロ基、アミノ基、アセチルアミノ基などのアシルアミノ基、シアノ基、水酸基、メチレンジオキシ、エチレンジオキシ、メトキシ、エトキシなどの直鎖又は分岐を有する炭素数１〜４のアルコキシ基、メチル、エチル、プロピル、tert-ブチル、イソブチルなどの直鎖又は分岐を有する炭素数１〜４のアルキル基、ＳＨ、トリフルオロメチル基、スルホン酸基、カルバモイル基、メチルアミノなどのアルキルアミノ基、ジメチルアミノなどのジアルキルアミノ基などの置換基で１，２又は３置換されていてもよい）、炭素数５〜１２個の環状飽和脂肪族多価カルボン酸化合物（例えば、１，２−シス−シクロプロパンジカルボン酸、１，２−トランス−シクロプロパンジカルボン酸、１，３−シス−シクロブタンジカルボン酸、１，３−トランス−シクロブタンジカルボン酸、１，４−シス−シクロヘキサンジカルボン酸、１，４−トランス−シクロヘキサンジカルボン酸及び１，３−アダマンタンジカルボン酸など）、（１α，２α，４α）−１，２，４−シクロヘキサントリカルボン酸、フマル酸、マレイン酸、シトラコン酸、イタコン酸などの不飽和２価カルボン酸などが挙げられ、好ましくは、イソフタル酸、５−メトキシイソフタル酸、５−メチルイソフタル酸、５−フルオロイソフタル酸、５−クロロイソフタル酸、５−ブロモイソフタル酸、５−ヨードイソフタル酸、５−ニトロイソフタル酸及び５−シアノイソフタル酸、テレフタル酸（ｔｐ）、２−メチルテレフタル酸、２−メトキシテレフタル酸、２−ニトロテレフタル酸、ジヒドロシクロブタ［１，２−ｂ］テレフタル酸、４，４’−ジカルボキシジフェニルスルホン、２，６−ナフタレンジカルボン酸、９，１０−アントラセンジカルボン酸、２，３−ピラジンジカルボン酸（ｐｚｄｃ）、テトラフルオロテレフタル酸、４，４’−ビ安息香酸、オクタフルオロ−４，４’−ビ安息香酸、４，４’−ビフェニルジカルボン酸、２，７−フルオレンジカルボン酸、２，７−ピレンジカルボン酸、４，５，９，１０−テトラヒドロピレン−２，７−ジカルボン酸、コハク酸、マレイン酸、フマル酸、アセチレンジガルボン酸等のジカルボン酸類が挙げられる。 Among the organic bridging ligands, the first organic bridging ligand includes benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, pyrene, 1,4-dihydronaphthalene, tetralin, biphenylene, triphenylene, acenaphthylene, acenaphthene. A compound in which 2, 3 or 4 carboxyl groups are bonded to an aromatic ring such as (the organic ligand is a halogen atom such as F, Cl, Br, I, nitro group, amino group, acetylamino group, etc. Such as acylamino group, cyano group, hydroxyl group, methylenedioxy, ethylenedioxy, methoxy, ethoxy, etc., linear or branched C1-C4 alkoxy group, methyl, ethyl, propyl, tert-butyl, isobutyl, etc. Linear or branched alkyl group having 1 to 4 carbon atoms, SH, trifluorome Group, a sulfonic acid group, a carbamoyl group, an alkylamino group such as methylamino, or a dialkylamino group such as dimethylamino, which may be substituted by 1, 2 or 3 substituents), having 5 to 12 carbon atoms Cyclic saturated aliphatic polyvalent carboxylic acid compounds (for example, 1,2-cis-cyclopropanedicarboxylic acid, 1,2-trans-cyclopropanedicarboxylic acid, 1,3-cis-cyclobutanedicarboxylic acid, 1,3-trans- Cyclobutanedicarboxylic acid, 1,4-cis-cyclohexanedicarboxylic acid, 1,4-trans-cyclohexanedicarboxylic acid and 1,3-adamantanedicarboxylic acid), (1α, 2α, 4α) -1,2,4-cyclohexanetricarboxylic acid Examples include unsaturated divalent carboxylic acids such as acid, fumaric acid, maleic acid, citraconic acid, and itaconic acid. Preferably, isophthalic acid, 5-methoxyisophthalic acid, 5-methylisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 5-bromoisophthalic acid, 5-iodoisophthalic acid, 5-nitroisophthalic acid And 5-cyanoisophthalic acid, terephthalic acid (tp), 2-methylterephthalic acid, 2-methoxyterephthalic acid, 2-nitroterephthalic acid, dihydrocyclobuta [1,2-b] terephthalic acid, 4,4′-di Carboxydiphenyl sulfone, 2,6-naphthalenedicarboxylic acid, 9,10-anthracene dicarboxylic acid, 2,3-pyrazine dicarboxylic acid (pzdc), tetrafluoroterephthalic acid, 4,4′-bibenzoic acid, octafluoro-4, 4'-bibenzoic acid, 4,4'-biphenyldicarboxylic acid, 2,7-fluorene Carboxylic acid, 2,7-pin dicarboxylic acid, 4,5,9,10- tetrahydropyrene-2,7-dicarboxylic acid, succinic acid, maleic acid, fumaric acid, and dicarboxylic acids such as acetylene Dziga carboxylic acid.
本発明の錯体には、第１有機架橋配位子と組み合わせて単座有機配位子、好ましくはモノカルボン酸をさらに有していてもよい。モノカルボン酸としては、ギ酸、酢酸、トリフルオロ酢酸、プロピオン酸、乳酸、ピルビン酸、ブタン酸、ペンタン酸、ヘキサン酸、シクロヘキサンカルボン酸などが挙げられる。単座配位子を使用することで多孔性金属錯体のサイズを小さくし、細孔の長さを短くすることができる。 The complex of the present invention may further have a monodentate organic ligand, preferably a monocarboxylic acid, in combination with the first organic bridging ligand. Examples of the monocarboxylic acid include formic acid, acetic acid, trifluoroacetic acid, propionic acid, lactic acid, pyruvic acid, butanoic acid, pentanoic acid, hexanoic acid, and cyclohexanecarboxylic acid. By using a monodentate ligand, the size of the porous metal complex can be reduced, and the length of the pores can be shortened.
有機架橋配位子のうち、第２有機架橋配位子としては、例えば、ピラジン、トランス−１，２−ビス（４−ピリジル）エチレン、１，４−ジシアノベンゼン、４，４’−ジシアノビフェニル、１，２−ジシアノエチレン、１，４−ビス（４−ピリジル）ベンゼン、トリエチレンジアミン（ｔｅｄ）、４，４’−ビピリジル（ｂｐｙ）、ジアザピレン、２，５−ジメチルピラジン、２，２’−ジメチル−４，４’−ビピリジン、１，２−ビス（４−ピリジル）エチン、１，４−ビス（４−ピリジル）ブタジイン、１，４−ビス（４−ピリジル）ベンゼン、３，６−ジ（４−ピリジル）−１，２，４，５−テトラジン、２，２’−ビ−１，６−ナフチリジン、フェナジン、２，６−ジ（４−ピリジル）−ベンゾ［１，２−ｃ：４，５−ｃ’］ジピロール−１，３，５，７（２Ｈ，６Ｈ）−テトロン、Ｎ，Ｎ’−ジ（４−ピリジル）−１，４，５，８−ナフタレンテトラカルボキシジイミド、トランス−１，２−ビス（４−ピリジル）エテン、４，４’−アゾピリジン、１，２−ビス（４−ピリジル）エタン、４，４’−ジピリジルスルフィド、１，３−ビス（４−ピリジル）プロパン、１，２−ビス（４−ピリジル）−グリコール、Ｎ−（４−ピリジル）イソニコチンアミド等が挙げられる。 Among the organic bridging ligands, examples of the second organic bridging ligand include pyrazine, trans-1,2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, and 4,4′-dicyanobiphenyl. 1,2-dicyanoethylene, 1,4-bis (4-pyridyl) benzene, triethylenediamine (ted), 4,4′-bipyridyl (bpy), diazapyrene, 2,5-dimethylpyrazine, 2,2′- Dimethyl-4,4′-bipyridine, 1,2-bis (4-pyridyl) ethyne, 1,4-bis (4-pyridyl) butadiyne, 1,4-bis (4-pyridyl) benzene, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine, 2,2′-bi-1,6-naphthyridine, phenazine, 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c '] dip -1,3,5,7 (2H, 6H) -tetron, N, N′-di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide, trans-1,2-bis (4-pyridyl) ethene, 4,4′-azopyridine, 1,2-bis (4-pyridyl) ethane, 4,4′-dipyridyl sulfide, 1,3-bis (4-pyridyl) propane, 1,2- Bis (4-pyridyl) -glycol, N- (4-pyridyl) isonicotinamide and the like can be mentioned.
本発明で使用する多孔性金属錯体は、例えば以下の文献、総説（Angew. Chem. Int. Ed. 2004, 43, 2334-2375.；Angew. Chem. Int. Ed. 2008, 47, 2-14.；Chem. Soc. Rev., 2008, 37, 191-214.；PNAS, 2006, 103, 10186-10191.；Chem.Rev.,2011, 111, 688-764.；Nature, 2003, 423, 705-714.）などに記載されているが、これらに限定されず、公知の多孔性金属錯体あるいは今後製造され得る多孔性金属錯体を広く使用することができる。 Examples of the porous metal complex used in the present invention include the following literatures and reviews (Angew. Chem. Int. Ed. 2004, 43, 2334-2375 .; Angew. Chem. Int. Ed. 2008, 47, 2-14). Chem. Soc. Rev., 2008, 37, 191-214 .; PNAS, 2006, 103, 10186-10191 .; Chem. Rev., 2011, 111, 688-764 .; Nature, 2003, 423, 705 -714.), Etc., but is not limited thereto, and known porous metal complexes or porous metal complexes that can be produced in the future can be widely used.
本発明で使用可能な金属錯体の例を以下に示す。
IRMOF-1, Zn4O(BDC)3 (H2BDC= benzenedicarboxylate)
MOF-69C, Zn3(OH2)(BDC)2
MOF-74, M2(DOBDC) (H2DOBDC=2,5-dihydroxyterephthalate, M=Zn, Co, Ni, Mg)
HKUST-1, Cu3(BTC)2 (H3BTC=1,3,5-benzenetricarboxylate)
MOF-177, Zn4O(BTB)2 (BTB=4,4’,4”-benzene-1,3,5-triyl-tribenzoate)
MOF-508, Zn(BDC)(bipy)0.5
Zn-BDC-DABCO,Zn2(BDC)2(DABCO), (DABCO=1,4-diazabicyclo[2.2.2]-octane)
Cr-MIL-101, Cr3F(H2O)2O(BDC)3
Al-MIL-110, Al8(OH)12{(OH)3(H2O)3}[BTC]3,
MIL-103, M(BTB), (M = light rare-earth elements [La-Ho])
Al-MIL-53, Al(OH)[BDC]
ZIF-8, Zn(MeIM)2, (H-MeIM=2-methylimidazole)
MIL-88B, Cr3OF(O2C-C6H4-CO2)3
MIL-88C, Fe3O(O2C-C10H6-CO2)3
MIL-88D, Cr3OF(O2C-C12H8-CO2)3
CID-1 [Zn2(ip)2(bpy)2] (Hip=isophthalic acid, bpy=4,4'-bipyridine)
Examples of metal complexes that can be used in the present invention are shown below.
IRMOF-1, Zn 4 O (BDC) 3 (H 2 BDC = benzenedicarboxylate)
MOF-69C, Zn 3 (OH2) (BDC) 2
MOF-74, M 2 (DOBDC) (H 2 DOBDC = 2,5-dihydroxyterephthalate, M = Zn, Co, Ni, Mg)
HKUST-1, Cu 3 (BTC) 2 (H 3 BTC = 1,3,5-benzenetricarboxylate)
MOF-177, Zn4O (BTB) 2 (BTB = 4,4 ', 4 ”-benzene-1,3,5-triyl-tribenzoate)
MOF-508, Zn (BDC) (bipy) 0.5
Zn-BDC-DABCO, Zn2 (BDC) 2 (DABCO), (DABCO = 1,4-diazabicyclo [2.2.2] -octane)
Cr-MIL-101, Cr 3 F (H 2 O) 2 O (BDC) 3
Al-MIL-110, Al 8 (OH) 12 {(OH) 3 (H 2 O) 3 } [BTC] 3 ,
MIL-103, M (BTB), (M = light rare-earth elements [La-Ho])
Al-MIL-53, Al (OH) [BDC]
ZIF-8, Zn (MeIM) 2 , (H-MeIM = 2-methylimidazole)
MIL-88B, Cr 3 OF (O 2 CC 6 H 4 -CO 2 ) 3
MIL-88C, Fe 3 O (O 2 CC 10 H 6 -CO 2 ) 3
MIL-88D, Cr 3 OF (O 2 CC 12 H 8 -CO 2 ) 3
CID-1 [Zn 2 (ip) 2 (bpy) 2 ] (Hip = isophthalic acid, bpy = 4,4'-bipyridine)
本発明において、多孔性金属錯体の細孔内に充填されるモノマーは、重合可能なものであればよいが、特に炭素数２〜１０の不飽和モノマーが好ましい。 In the present invention, the monomer filled in the pores of the porous metal complex may be any monomer that can be polymerized, but an unsaturated monomer having 2 to 10 carbon atoms is particularly preferable.
不飽和モノマーの例としては、例えば、エチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、ブタジエン、イソプレン、シクロペンテン、シクロヘキセン、ノルボルネン、ノルボルナジエン、塩化ビニル、酢酸ビニル、メトキシビニル、アクリル酸、アクリル酸メチル、アクリル酸エチルなどのアクリル酸エステル、メタクリル酸、メタクリル酸メチル、メタクリル酸エチルなどのメタクリル酸エステル、アクリロニトリル、スチレン、ビニルナフタレン、ビニルシクロヘキサン、アセチレン、メチルアセチレン、２−エチニルピリジン、トリフルオロエチレン、テトラフルオロエチレン、ビニリデンフルオライド、ヘキサフルオロプロピレン等が挙げられる。 Examples of unsaturated monomers include, for example, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, butadiene, isoprene, cyclopentene, cyclohexene, norbornene, norbornadiene, vinyl chloride, vinyl acetate, methoxyvinyl, acrylic Acrylic acid esters such as acid, methyl acrylate and ethyl acrylate, methacrylic acid esters such as methacrylic acid, methyl methacrylate and ethyl methacrylate, acrylonitrile, styrene, vinyl naphthalene, vinylcyclohexane, acetylene, methylacetylene and 2-ethynylpyridine , Trifluoroethylene, tetrafluoroethylene, vinylidene fluoride, hexafluoropropylene and the like.
本発明の多孔性金属錯体の細孔内にモノマーを収容する方法としては、モノマーがガス又は液体の場合には、例えばAngew. Chem. Int. Ed. 1999, 38, 140記載の方法と同様に、多孔性金属錯体とモノマーを直接接触させる方法が挙げられる。また、モノマーを適当な有機溶媒に溶解させた後、多孔性金属錯体と接触させてもよい。ここで使用される有機溶媒の例としては、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、イソオクタン、シクロペンタン、メチルシクロペンタン、シクロヘキサン、メチルシクロヘキサン、シクロオクタン、デカリン等の脂肪族炭化水素、ベンゼン、トルエン、キシレン、クメン、エチルベンゼン、モノクロロベンゼン、ジクロロベンゼン等の芳香族炭化水素、ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン等のハロゲン化炭化水素等が挙げられる。 As a method for accommodating the monomer in the pores of the porous metal complex of the present invention, when the monomer is a gas or a liquid, for example, the method described in Angew. Chem. Int. Ed. 1999, 38, 140 is the same. And a method in which a porous metal complex and a monomer are brought into direct contact with each other. Alternatively, the monomer may be dissolved in a suitable organic solvent and then contacted with the porous metal complex. Examples of organic solvents used here include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, decalin, benzene, toluene And aromatic hydrocarbons such as xylene, cumene, ethylbenzene, monochlorobenzene and dichlorobenzene, and halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and dichloroethane.
本発明の多孔性配位ポリマーの細孔内に不飽和モノマーを収容し、部分的に重合させる。重合は、ラジカル重合、カチオン重合、アニオン重合などのいずれであってもよい。 An unsaturated monomer is accommodated in the pores of the porous coordination polymer of the present invention and partially polymerized. The polymerization may be any of radical polymerization, cationic polymerization, anionic polymerization and the like.
重合を開始させる方法としては、ラジカル開始剤の存在下／非存在下に加熱あるいは光を照射する方法、酸性物質または塩基性物質を作用させる方法等が挙げられる。 Examples of the method for initiating polymerization include a method of heating or irradiating light in the presence / absence of a radical initiator, a method of causing an acidic substance or a basic substance to act, and the like.
重合の反応温度は、好ましくは０〜２５０℃程度、より好ましくは５０〜２００℃程度であり、反応時間は１〜４８時間程度、好ましくは２〜２４時間程度、より好ましくは３〜１２時間程度である。反応温度と反応時間は、細孔における重合の程度を調節するための因子である。 The polymerization reaction temperature is preferably about 0 to 250 ° C, more preferably about 50 to 200 ° C, and the reaction time is about 1 to 48 hours, preferably about 2 to 24 hours, more preferably about 3 to 12 hours. It is. The reaction temperature and reaction time are factors for adjusting the degree of polymerization in the pores.
使用するラジカル開始剤としては、ラジカル重合の開始剤として通常使用される化合物が挙げられ、例えば、アゾビスイソブチロニトリル（ＡＩＢＮ）、過酸化ベンゾイル等が挙げられる。 Examples of the radical initiator to be used include compounds usually used as an initiator for radical polymerization, and examples thereof include azobisisobutyronitrile (AIBN) and benzoyl peroxide.
使用する酸性物質としては、カチオン重合の開始剤として通常使用される化合物が用いられ、例えば、塩化アルミニウム、硫酸、塩酸等が挙げられる。 As the acidic substance to be used, compounds usually used as an initiator for cationic polymerization are used, and examples thereof include aluminum chloride, sulfuric acid, hydrochloric acid and the like.
使用する塩基性物質としては、ブチルリチウムなどのアルキルリチウムが挙げられる。 Examples of the basic substance to be used include alkyl lithium such as butyl lithium.
本発明では、最初のモノマーを多孔性金属錯体の細孔に充填後、部分的に重合を行う。 In the present invention, after the first monomer is filled in the pores of the porous metal complex, the polymerization is partially performed.
例えば、図１(A)の例ではスチレンを部分的に重合し、細孔の一部においてポリスチレンを形成させる。重合反応は連鎖反応であるので、一部の細孔内で連鎖反応が生じれば、その細孔では重合反応が進行するためポリマー鎖が形成される。一方、重合反応が進行しない細孔ではモノマーがそのまま残るため部分的に重合を行った後、細孔内に残存するモノマーを溶媒などにより除去する。次のモノマーを細孔内に充填し、部分的又は完全に重合を行う。図１(A)では、次のモノマーがMMA(メタクリル酸メチル)であり、ポリスチレン(PSt)とポリメタクリル酸メチル(PMMA)が細孔内に充填された多孔性金属錯体が得られる。なお、図１(A)では全ての細孔にポリマーが充填されているが、２種以上のポリマーが細孔内に存在していれば、一部の細孔においてポリマーが形成されていなくてもよい。また、1つの細孔内では1つのポリマー鎖が形成されることが好ましいが、２つ又は３つのポリマー鎖が１つの細孔内で形成されてもよい。また、１つの細孔内では連鎖的な重合反応が進行するため細孔全体にわたる長さのポリマー鎖が形成され得るが、重合反応が途中で停止して短いポリマー鎖が形成された場合、１つの細孔内で異種のポリマーが形成されることがあってもよい。 For example, in the example of FIG. 1A, styrene is partially polymerized to form polystyrene in a part of the pores. Since the polymerization reaction is a chain reaction, if a chain reaction occurs in some of the pores, the polymerization reaction proceeds in the pores, so that a polymer chain is formed. On the other hand, since the monomer remains as it is in the pores where the polymerization reaction does not proceed, after partial polymerization, the monomer remaining in the pores is removed with a solvent or the like. The next monomer is filled into the pores and the polymerization is carried out partially or completely. In FIG. 1A, a porous metal complex in which the next monomer is MMA (methyl methacrylate) and polystyrene (PSt) and polymethyl methacrylate (PMMA) are filled in the pores is obtained. In FIG. 1 (A), all the pores are filled with the polymer, but if two or more kinds of polymers are present in the pores, the polymer is not formed in some of the pores. Also good. Further, it is preferable that one polymer chain is formed in one pore, but two or three polymer chains may be formed in one pore. In addition, since a chain polymerization reaction proceeds in one pore, a polymer chain having a length over the entire pore can be formed. However, when the polymerization reaction is stopped halfway and a short polymer chain is formed, 1 Different polymers may form within one pore.
次のモノマーを部分的に重合させた場合には、さらに細孔内に残存する次のモノマーの除去とさらにその次のモノマーの充填を行うことができ、以下、必要な回数だけ前のモノマーの細孔からの除去と次のモノマーの細孔への充填と重合を繰り返すことで、３種以上(例えば３種、４種又は５種、好ましくは３種)のポリマーを多孔性金属錯体の細孔内に充填することができる。 When the next monomer is partially polymerized, the next monomer remaining in the pores can be further removed and the next monomer can be further filled. By repeating removal from the pores, filling of the next monomer into the pores and polymerization, three or more (for example, three, four or five, preferably three) polymers can be made fine with the porous metal complex. The holes can be filled.
細孔内におけるモノマーの重合反応を途中で止めるためには、反応温度、反応時間、重合開始剤(ラジカル重合)、酸性物質(カチオン重合)、塩基性物質(アニオン重合)の配合量などをモノマーの種類に応じて調節すればよい。ラジカル重合の停止は、例えばメタノールなどの低級アルコールを用いて行うことができる。メタノールなどの低級アルコールは残ったモノマーを溶解除去し、残存する低級アルコールは蒸発により除去することができる。 In order to stop the monomer polymerization reaction in the pores, the reaction temperature, reaction time, polymerization initiator (radical polymerization), acidic substance (cationic polymerization), basic substance (anionic polymerization), etc. It may be adjusted according to the type. The radical polymerization can be stopped using, for example, a lower alcohol such as methanol. A lower alcohol such as methanol can dissolve and remove the remaining monomer, and the remaining lower alcohol can be removed by evaporation.
図２(A)にはポリスチレン(PSt)とポリメタクリル酸メチル(PMMA)が細孔内に充填された多孔性金属錯体を得るために、PStの重合時間を５時間、７時間、９時間と延ばしていくと、PStの割合が０．２６、０．５５，０．７１に増加することを示す。温度、時間、配合量などの適切な反応条件は、多孔性金属錯体、モノマー、重合開始剤／酸性物質／塩基性物質などの試薬の種類と配合量、溶媒、濃度などにより異なるので、各ポリマーが適切な割合で多孔性金属錯体中で形成されるための適切な反応条件は、反応条件を変えた複数の実験により決定できる。 Fig. 2 (A) shows that the polymerization time of PSt is 5 hours, 7 hours, and 9 hours in order to obtain a porous metal complex filled with polystyrene (PSt) and polymethyl methacrylate (PMMA). As it is extended, the PSt ratio increases to 0.26, 0.55, and 0.71. Appropriate reaction conditions such as temperature, time, and blending amount depend on the type and blending amount of the porous metal complex, monomer, polymerization initiator / acidic substance / basic substance, solvent, concentration, etc. Appropriate reaction conditions for forming an appropriate proportion in the porous metal complex can be determined by multiple experiments with varying reaction conditions.
２種以上のポリマーを細孔内で順次反応させる場合、特に限定されるわけではないが、重合反応の遅いポリマーを先に形成させ、次いで重合反応の速いポリマーを順次形成するのが、ポリマー形成を途中で止めるために好ましい。 When two or more kinds of polymers are sequentially reacted in the pores, the polymer formation is not particularly limited, but the polymer having a slow polymerization reaction is formed first, and then the polymer having a fast polymerization reaction is sequentially formed. Is preferable for stopping the process on the way.
多孔性金属錯体の細孔径は、モノマーが細孔内部に入り込み、細孔内である程度回転などの運動ができる程度の自由度が必要であるので、モノマーが大きくなるに従って細孔径の大きな多孔性金属錯体を選択することが望ましい。 The pore size of the porous metal complex requires a degree of freedom that allows the monomer to enter the inside of the pore and to move to some extent within the pore, so that the porous metal has a larger pore size as the monomer increases. It is desirable to select a complex.
本発明において、細孔内にポリマーを含む多孔性金属錯体の複合体は、金属錯体の構造を保持している。これは、X線回折パターンにより確認することができる。 In the present invention, the porous metal complex composite containing the polymer in the pores retains the structure of the metal complex. This can be confirmed by an X-ray diffraction pattern.
次にポリマーを細孔内に含む多孔性金属錯体の構造を壊すことにより、細孔内でのポリマーの配置を部分的又は完全に反映したポリマーアロイを得ることができる。金属錯体の構造の破壊は、例えばキレート剤を作用させることにより金属イオンを錯体から引き抜くことで達成できる。使用されるキレート剤としては、ＥＤＴＡ（エチレンジアミン四酢酸）、ＥＧＴＡ（エチレングリコール−ビス−（ｂ−アミノエチルエーテル）−Ｎ，Ｎ−四酢酸）、ＮＴＡ（ニトリロ三酢酸）、ＤＴＰＡ（ジエチレントリアミン五酢酸）、ＨＥＩＤＡ（Ｎ−（２−ヒドロキシエチル）イミノ二酢酸二ナトリウム塩）、ＩＤＳ（イミノ二コハク酸ナトリウム塩）、ＭＧＤＡ（二酢酸メチルグリシン）、グルコン酸、２，２’−ビピリジル、イミノ二酢酸（ＩＤＡ）、ニトリロトリスメチルリン酸（ＮＴＰＯ）、トリエタノールアミン、エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（２−ピリジルメチル）エチレンジアミン（ＴＰＥＮ）、ジエチレントリアミン、ジエチレントリアミン−Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−五酢酸（ＤＴＰＡ）、トリエチレンテトラアミン、トリエチレンテトラミン−Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”’，Ｎ”’−六酢酸（ＴＴＨＡ）、１，１０−フェナントロリン、Ｏ，Ｏ’−ビス（２−アミノフェニル）エチレングリコール−Ｎ，Ｎ，Ｎ’，Ｎ’−四酢酸（ＢＡＰＴＡ）、Ｎ，Ｎ−ビス（２−ハイドロキシエチル）グリシン（Ｂｉｃｉｎｅ）、トランス−１，２−ジアミノシクロヘキサン−Ｎ，Ｎ，Ｎ’，Ｎ’−四酢酸（ＣｙＤＴＡ）などが挙げられる。金属錯体を構成する配位子は、ポリマーを溶解しない水又は有機溶媒で洗浄除去できる。 Next, by breaking the structure of the porous metal complex containing the polymer in the pores, a polymer alloy that partially or completely reflects the arrangement of the polymer in the pores can be obtained. The destruction of the structure of the metal complex can be achieved, for example, by extracting a metal ion from the complex by acting a chelating agent. As the chelating agent used, EDTA (ethylenediaminetetraacetic acid), EGTA (ethyleneglycol-bis- (b-aminoethylether) -N, N-tetraacetic acid), NTA (nitrilotriacetic acid), DTPA (diethylenetriaminepentaacetic acid) ), HEIDA (N- (2-hydroxyethyl) iminodiacetic acid disodium salt), IDS (iminodisuccinic acid sodium salt), MGDA (methylglycine diacetate), gluconic acid, 2,2'-bipyridyl, iminodi Acetic acid (IDA), nitrilotrismethyl phosphoric acid (NTPO), triethanolamine, ethylenediamine, N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine (TPEN), diethylenetriamine, diethylenetriamine-N, N, N ′, N ″, N ″ -pentaacetic acid (DTPA , Triethylenetetraamine, triethylenetetramine-N, N, N ′, N ″, N ″ ′, N ″ ′-hexaacetic acid (TTHA), 1,10-phenanthroline, O, O′-bis (2-amino) Phenyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid (BAPTA), N, N-bis (2-hydroxyethyl) glycine (Bicine), trans-1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid (CyDTA), etc. The ligand constituting the metal complex can be removed by washing with water or an organic solvent that does not dissolve the polymer.
本明細書において、有機溶媒としては、メタノール、エタノール、イソプロパノールなどのアルコール、アセトン、メチルエチルケトンなどのケトン類、ジエチルエーテル、ジイソプロピルエーテルなどのエーテル類、アセトニトリル、酢酸エチルなどのエステル類、塩化メチレン、クロロホルム、ジクロルエタンなどの塩素化炭化水素、ベンゼン、トルエンなどの芳香族炭化水素類、ヘキサン、シクロヘキサンなどの脂肪族又は脂環式炭化水素類、ＴＨＦ，ＤＭＦ，ＤＭＳＯ，ジメチルアセトアミド、Ｎ−メチルピロリドンなどが挙げられる。 In this specification, examples of the organic solvent include alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and diisopropyl ether, esters such as acetonitrile and ethyl acetate, methylene chloride, and chloroform. , Chlorinated hydrocarbons such as dichloroethane, aromatic hydrocarbons such as benzene and toluene, aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane, THF, DMF, DMSO, dimethylacetamide, N-methylpyrrolidone, etc. Can be mentioned.
多孔性金属錯体とポリマーを含む複合体（図１(B)）、多孔性金属錯体部分を除去したポリマーアロイ（図２(B)）は、いずれも粒子の形状を有し、多孔性構造を保持している。各ポリマーは複合体の各細孔内にランダムに配置されており、この配置をポリマーアロイで維持するために、ポリマーが単分子鎖レベルで分散された、分子レベルの相溶化が実現できる。 A composite containing a porous metal complex and a polymer (FIG. 1 (B)) and a polymer alloy from which the porous metal complex part has been removed (FIG. 2 (B)) both have a particle shape and have a porous structure. keeping. Each polymer is randomly arranged in each pore of the composite, and in order to maintain this arrangement by a polymer alloy, compatibilization at a molecular level in which the polymer is dispersed at a single molecular chain level can be realized.
２種以上のポリマーを含む溶液をキャストしてフィルムを作成する場合、２種以上のポリマーが相分離した海島構造を通常形成するが(図３A)、本発明のポリマーアロイは多孔性構造を保持しており(図3B)、分子レベルで2種以上のポリマーが相溶した構造を有する。これは、多孔性金属錯体の細孔に２種以上のポリマーを含む複合体と、この複合体から多孔性金属錯体を除いたポリマーアロイがいずれも粒子の形状を保持していることから、分子レベルで相溶化した構造が維持されていることが示される。 When a film is made by casting a solution containing two or more kinds of polymers, a sea-island structure in which two or more kinds of polymers are phase-separated usually forms (FIG. 3A), but the polymer alloy of the present invention retains a porous structure. (FIG. 3B), and has a structure in which two or more kinds of polymers are compatible at the molecular level. This is because both the composite containing two or more polymers in the pores of the porous metal complex and the polymer alloy obtained by removing the porous metal complex from the composite retain the shape of the particles. It is shown that the structure compatibilized at the level is maintained.
本発明のポリマーアロイにおいて、2種以上のポリマーが3nm以下、例えば2〜3nmの距離で存在していることは、固体NMR測定により回転系スピン格子緩和時間（T1ρ）を求め、相溶性を評価することで確認できる(図４)。異種ポリマーが2〜3nm以内に存在すれば回転系スピン格子緩和時間（T1ρ）は近い値を取ることが知られている（J.Wang, M.K.Cheung, Y.Mi, Polymer, 2002, 43, 1357）。回転系スピン格子緩和時間（T1ρ）が約2ms以下であれば、2〜3nm以内に異種ポリマーが存在すると考えられる。 In the polymer alloy of the present invention, the presence of two or more kinds of polymers at a distance of 3 nm or less, for example, 2 to 3 nm is determined by determining the rotational spin lattice relaxation time (T 1ρ ) by solid-state NMR measurement, This can be confirmed by evaluation (FIG. 4). It is known that the rotational spin-lattice relaxation time (T 1ρ ) takes a close value when a heterogeneous polymer exists within 2 to 3 nm (J. Wang, MKCheung, Y. Mi, Polymer, 2002, 43, 1357 ). If the rotational spin lattice relaxation time (T 1ρ ) is about 2 ms or less, it is considered that a different polymer exists within 2 to 3 nm.
また、本発明のポリマーアロイは、相溶化により熱安定性が大幅に向上する。これは、熱重量（TG）測定により高温側にシフトすることにより確認できる（例えば図４、図５）。重量減少が始まる温度は、２種以上のポリマーをブレンドしたものと比較して２０〜２００℃、好ましくは５０〜１８０℃、より好ましくは８０〜１６０℃程度高くなる。 In addition, the polymer alloy of the present invention is greatly improved in thermal stability due to compatibilization. This can be confirmed by shifting to a higher temperature side by thermogravimetric (TG) measurement (for example, FIGS. 4 and 5). The temperature at which weight reduction starts is 20 to 200 ° C., preferably 50 to 180 ° C., more preferably about 80 to 160 ° C., compared to a blend of two or more polymers.
本発明のポリマーアロイが２種のポリマーＡ、Ｂから構成される場合、ポリマーＡ：ポリマーＢ（重量比）＝１：９９〜９９：１、好ましくは１：９〜９：１、より好ましくは２：８〜８：２。さらに好ましくは３：７から７：３、特に好ましくは４：６〜６：４である。 When the polymer alloy of the present invention is composed of two types of polymers A and B, polymer A: polymer B (weight ratio) = 1: 99 to 99: 1, preferably 1: 9 to 9: 1, more preferably 2: 8-8: 2. More preferably, it is 3: 7 to 7: 3, and particularly preferably 4: 6 to 6: 4.
本発明のポリマーアロイを構成するポリマーの溶解度パラメータを以下に例示する。 The solubility parameter of the polymer constituting the polymer alloy of the present invention is exemplified below.
ポリマーは細孔内で合成してもよく、ポリマーを細孔内に導入してもよい。 The polymer may be synthesized within the pores, or the polymer may be introduced into the pores.
２種以上のポリマーにおいて、溶解度パラメータの最大の差の絶対値は０．１〜８程度、好ましくは０．２〜７．５程度、より好ましくは０．３〜７程度である。溶解度パラメータが近いほど２つのポリマーは相溶しやすい。本発明の製造方法によれば、溶解度パラメータの差が５以上のポリマーであっても分子レベルで相溶化させることができ、溶解度パラメータの差が６．４であるポリスチレンとポリアクリロニトリルであっても分子レベルで相溶させることができる。 In two or more kinds of polymers, the absolute value of the maximum difference in solubility parameter is about 0.1 to 8, preferably about 0.2 to 7.5, and more preferably about 0.3 to 7. The closer the solubility parameter, the easier the two polymers are compatible. According to the production method of the present invention, even a polymer having a solubility parameter difference of 5 or more can be compatibilized at the molecular level, and even a polystyrene and polyacrylonitrile having a solubility parameter difference of 6.4. Can be compatible at the molecular level.
以下に、本発明を実施例により更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
参考例１
多孔性金属錯体［Ｚｎ２（ｔｐ）２ｔｅｄ］ｎを、J. Phys. Chem. B 2002, 106, 1380記載の方法に準じて、硫酸亜鉛のメタノール溶液をｔｐのギ酸／メタノール（１／１００）溶液中に加え、数日間室温で攪拌した後、ｔｅｄのトルエン溶液を加え、オートクレーブ中４３３Ｋで数時間加熱し、得られた結晶を濾別することにより合成した。得られた錯体の１次元細孔サイズは０．７５nmであった。
Reference example 1
In accordance with the method described in J. Phys. Chem. B 2002, 106, 1380, the porous metal complex [Zn 2 (tp) 2 ted] n was converted to a methanol solution of zinc sulfate with tp formic acid / methanol (1/100 ) After being added to the solution and stirred for several days at room temperature, a toluene solution of ted was added, heated at 433 K in an autoclave for several hours, and the resulting crystals were synthesized by filtration. The obtained complex had a one-dimensional pore size of 0.75 nm.
実施例１
パイレックス（登録商標）製の反応管に参考例１で合成した［Ｚｎ２（ｔｐ）２ｔｅｄ］ｎを２００ｍｇ仕込み、８０Ｐａの減圧下、１３０℃で３時間乾燥させた。引き続きスチレン１ｍＬとＡＩＢＮ４ｍｇを室温で投入し、過剰のスチレンを室温で８０Ｐａの減圧下２時間かけて完全に留去した。その後、反応管を７０℃に加熱し、６時間反応させた。反応液にメタノールを加えて重合反応を停止し、未反応のスチレンを溶解除去し、さらにメタノールを減圧下に蒸発させた。次にメタクリル酸メチル１ｍＬとＡＩＢＮ ４ｍｇを室温で投入し、過剰のメタクリル酸メチルを室温で８０Ｐａの減圧下２時間かけて完全に留去した。その後、反応管を７０℃に加熱し、２４時間反応させた。
Example 1
200 mg of [Zn 2 (tp) 2 ted] n synthesized in Reference Example 1 was placed in a Pyrex (registered trademark) reaction tube, and dried at 130 ° C. for 3 hours under reduced pressure of 80 Pa. Subsequently, 1 mL of styrene and 4 mg of AIBN were added at room temperature, and excess styrene was completely distilled off at room temperature under a reduced pressure of 80 Pa over 2 hours. Thereafter, the reaction tube was heated to 70 ° C. and reacted for 6 hours. Methanol was added to the reaction solution to terminate the polymerization reaction, unreacted styrene was dissolved and removed, and methanol was evaporated under reduced pressure. Next, 1 mL of methyl methacrylate and 4 mg of AIBN were added at room temperature, and excess methyl methacrylate was completely distilled off at room temperature under reduced pressure of 80 Pa for 2 hours. Thereafter, the reaction tube was heated to 70 ° C. and reacted for 24 hours.
反応終了後、得られた粉末をメタノールで洗浄し、室温で乾燥させることにより、ポリスチレンとポリメタクリル酸メチルを収容した多孔性金属錯体［Ｚｎ２（ｔｐ）２ｔｅｄ］ｎの複合体を得た。 After completion of the reaction, the obtained powder was washed with methanol and dried at room temperature to obtain a composite of porous metal complex [Zn 2 (tp) 2 ted] n containing polystyrene and polymethyl methacrylate. .
得られた複合体をＥＤＴＡ・２Ｎａ水溶液と反応させて多孔性金属錯体を除去し、本発明のポリマーアロイを得た。ポリマーアロイにおいて、モル比でＰＳｔ：ＰＭＭＡ＝１．０：０．８であった。 The obtained composite was reacted with an EDTA · 2Na aqueous solution to remove the porous metal complex, and the polymer alloy of the present invention was obtained. In the polymer alloy, the molar ratio was PSt: PMMA = 1.0: 0.8.
得られた複合体とポリマーアロイについてＸ線回折測定とＳＥＭ画像を得た（図１，２）。 X-ray diffraction measurement and SEM images were obtained for the resulting composite and polymer alloy (FIGS. 1 and 2).
ＰＳｔとＰＭＭＡのキャストされたバルク（コントロール）と本発明のポリマーアロイについてのＨＡＡＤＦ−ＳＴＥＭの測定結果を図３に示す。 The HAADF-STEM measurement results for the cast bulk (control) of PSt and PMMA and the polymer alloy of the present invention are shown in FIG.
ＰＳｔとＰＭＭＡのポリマーアロイについて固体１３Ｃ−ＮＭＲを測定し、緩和時間（Ｔ１ρ）を測定した。結果を図４，図５に示す。 Solid state 13 C-NMR was measured for the polymer alloy of PSt and PMMA, and the relaxation time (T 1ρ ) was measured. The results are shown in FIGS.
さらに、ＰＳｔ、ＰＭＭＡ、ＰＳｔとＰＭＭＡのキャストされたバルク及びポリマーアロイについて熱重量（ＴＧ）を測定した結果を図６に示す。 Furthermore, the result of having measured the thermogravimetric (TG) about the cast bulk and polymer alloy of PSt, PMMA, PSt, and PMMA is shown in FIG.
実施例２
パイレックス（登録商標）製の反応管に参考例１で合成した［Ｚｎ２（ｔｐ）２ｔｅｄ］ｎを２００ｍｇ仕込み、８０Ｐａの減圧下、１３０℃で３時間乾燥させた。引き続きスチレン１ｍＬとＡＩＢＮ４ｍｇを室温で投入し、過剰のスチレンを室温で８０Ｐａの減圧下２時間かけて完全に留去した。その後、反応管を７０℃に加熱し、６時間反応させた。反応液にメタノールを加えて重合反応を停止し、未反応のスチレンを溶解除去し、さらにメタノールを減圧下に蒸発させた。次にアクリロニトリル１ｍＬとＡＩＢＮ ４ｍｇを室温で投入し、過剰のアクリロニトリルを室温で８ｋＰａの減圧下２時間かけて完全に留去した。その後、反応管を１００℃に加熱し、２４時間反応させた。
Example 2
200 mg of [Zn 2 (tp) 2 ted] n synthesized in Reference Example 1 was placed in a Pyrex (registered trademark) reaction tube, and dried at 130 ° C. for 3 hours under reduced pressure of 80 Pa. Subsequently, 1 mL of styrene and 4 mg of AIBN were added at room temperature, and excess styrene was completely distilled off at room temperature under a reduced pressure of 80 Pa over 2 hours. Thereafter, the reaction tube was heated to 70 ° C. and reacted for 6 hours. Methanol was added to the reaction solution to terminate the polymerization reaction, unreacted styrene was dissolved and removed, and methanol was evaporated under reduced pressure. Next, 1 mL of acrylonitrile and 4 mg of AIBN were added at room temperature, and excess acrylonitrile was completely distilled off at room temperature under a reduced pressure of 8 kPa for 2 hours. Thereafter, the reaction tube was heated to 100 ° C. and reacted for 24 hours.
反応終了後、得られた粉末をメタノールで洗浄し、室温で乾燥させることにより、ポリスチレン（ＰＳｔ、溶解度パラメータ＝９．０）とポリアクリロニトリル（ＰＡＮ、溶解度パラメータ＝１５．４）を収容した多孔性金属錯体［Ｚｎ２（ｔｐ）２ｔｅｄ］ｎの複合体を得た。 After completion of the reaction, the resulting powder was washed with methanol and dried at room temperature, thereby containing a porous material containing polystyrene (PSt, solubility parameter = 9.0) and polyacrylonitrile (PAN, solubility parameter = 15.4). A complex of metal complex [Zn 2 (tp) 2 ted] n was obtained.
得られた複合体について実施例１と同様にしてＥＤＴＡ・２Ｎａを用いて多孔性金属錯体を除去し、本発明のポリマーアロイを得た。ポリマーアロイにおいて、モル比でＰＳｔ：ＰＡＮ＝１．０：１．０であった。 About the obtained composite body, the porous metal complex was removed using EDTA · 2Na in the same manner as in Example 1 to obtain a polymer alloy of the present invention. In the polymer alloy, the molar ratio was PSt: PAN = 1.0: 1.0.
ＰＡＮ，ＰＳｔ、ポリマーアロイについてＸＲＰＤを測定した。結果を図７に示す。 XRPD was measured for PAN, PSt, and polymer alloy. The results are shown in FIG.
さらに、キャストされたバルクＰＳｔ＋ＰＡＮと本発明のＰＳｔ＋ＰＡＮ(ポリマーアロイ)についてＨＡＡＤＦ−ＳＴＥＭ測定と緩和時間（T1ρ）測定の結果を図８に示す。 Further, FIG. 8 shows the results of HAADF-STEM measurement and relaxation time (T 1ρ ) measurement for cast bulk PSt + PAN and PSt + PAN (polymer alloy) of the present invention.
本発明のポリマーアロイは、高機能エンジニアリングプラスチック、自動車用部品、航空機用部品、医療材料などの様々な分野に応用できる。 The polymer alloy of the present invention can be applied to various fields such as high-performance engineering plastics, automotive parts, aircraft parts, and medical materials.
Claims (6)
工程１：多孔性金属錯体の細孔内に最初のモノマーを充填する工程
工程２：一部の細孔内のモノマーを重合する工程
工程３：未反応のモノマーを除去する工程
工程４：未反応のモノマーが除去された細孔内に次のモノマーを充填する工程
工程５：細孔内のモノマーを部分的又は完全に重合する工程、
工程６：工程５の後で未重合のモノマーがある場合、工程３〜工程５を必要な回数だけ繰り返す工程
工程７：多孔性金属錯体の構造を壊してポリマーアロイを回収する工程。 A method for producing a polymer alloy compatibilized at the molecular level, comprising the following steps:
Step 1: Step of filling first monomer into pores of porous metal complex Step 2: Step of polymerizing monomer in some pores Step 3: Step of removing unreacted monomer Step 4: Unreacted Step 5 of filling the next monomer in the pores from which the monomer has been removed Step 5: Step of partially or completely polymerizing the monomer in the pores,
Step 6: When there is an unpolymerized monomer after Step 5, Step 7 is a step of repeating Step 3 to Step 5 as many times as necessary. Step 7: Step of destroying the structure of the porous metal complex and recovering the polymer alloy.
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| JP2002239033A (en) * | 2000-12-12 | 2002-08-27 | Sumitomo Rubber Ind Ltd | Multipiece solid golf ball |
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| JP2002239033A (en) * | 2000-12-12 | 2002-08-27 | Sumitomo Rubber Ind Ltd | Multipiece solid golf ball |
| JP2009519116A (en) * | 2005-11-14 | 2009-05-14 | ビーエーエスエフ ソシエタス・ヨーロピア | Porous metal organic framework material containing another polymer |
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