JP2004315559A - Method for producing metal supporting polymer porous product - Google Patents
Method for producing metal supporting polymer porous product Download PDFInfo
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- JP2004315559A JP2004315559A JP2003107452A JP2003107452A JP2004315559A JP 2004315559 A JP2004315559 A JP 2004315559A JP 2003107452 A JP2003107452 A JP 2003107452A JP 2003107452 A JP2003107452 A JP 2003107452A JP 2004315559 A JP2004315559 A JP 2004315559A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 80
- 239000002184 metal Substances 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000012530 fluid Substances 0.000 claims abstract description 67
- 239000002243 precursor Substances 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 38
- 239000001569 carbon dioxide Substances 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 19
- 238000005187 foaming Methods 0.000 claims description 15
- 230000009477 glass transition Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000002902 organometallic compounds Chemical group 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 37
- 230000008569 process Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- -1 for example Chemical class 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 210000004940 nucleus Anatomy 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
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- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
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- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 210000003855 cell nucleus Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は金属担持ポリマー多孔体を製造する方法に関し、より詳しくは、超臨界流体を金属前駆体の溶剤ならびに発泡剤として用い、気孔表面に金属が分散担持された金属担持ポリマー多孔体を製造する方法、および該方法により得られる微細孔内部まで金属が分散した金属担持ポリマー多孔体に関する。
【０００２】
【従来の技術】
金属担持多孔体は、触媒、電池用電極材料、メンブレンリアクター、導電性または帯電防止プラスチック、電磁気シールド材料等の各種の機能性材料として有用であり、その製造方法の確立が望まれている。触媒はこのような機能性材料の代表例であり、その反応性を上げるためには金属を高分散させて比表面積を増大させることが望ましい。また、高分散であれば、前処理または反応中に金属同士が凝集して粒成長するのを抑制でき、活性の耐久性も向上する。ここで高分散担持するためには担体が比表面積の大きい微多孔体であることが好ましく、従来シリカゲル、活性炭、アルミナ等の無機材料の使用が幅広く検討されてきた。しかし、これら無機材料は基本的にはそれ自身が粉体であるためその成形性・加工性に難がある。このため、フィルムや膜、不織布の形態として用いるためにも、これら無機材料ではなくポリマー微多孔体の担体が注目されてきている。
【０００３】
金属担持ポリマー多孔体の製造工程は、一般的にポリマー多孔体の製造工程とポリマーへの金属担持工程との二段階工程から成る。即ち、別途用意した多孔質ポリマー支持体表面（空孔壁面）に金属微粒子を担持して製造される。
【０００４】
ポリマー多孔体の製造方法としては発泡剤分解法・溶剤気散法等の発泡法、相分離法等があるが、発泡法は発泡剤としてクロロフルオロカーボン類、塩化メチレンなどの低沸点有機化合物を用いるため、コストが高いだけでなく、可燃性や毒性等の危険性を有しており、大気汚染の問題を生じる可能性を持っている。例えばジクロロジフロロメタンをはじめとするフロン系ガス等は、オゾン層破壊の環境問題から全廃の方向へ進んでいる。また微多孔体の製造に多く用いられる相分離法も、有機溶媒等を使用するため環境上好ましくないだけでなく、ポリマー成分を溶媒で溶出除去させて孔を形成するため、その孔を大きくすると「す」の状態となり、金属を高分散担持させるための微多孔体としての機能低下の原因となる。
【０００５】
また、これらのポリマー多孔体に金属を担持する方法としては、金属を溶解した溶液を用いて担持する方法が一般的であり、金属のハロゲン化物、硝酸塩水溶液等の薬液が使用され、それを大気圧下で担体に吸着または含浸させて固定する。しかしながら、上記吸着または含浸法では、比表面積の高い多孔体の表面全体にわたって均一に金属薬液を固定することは極めて困難である。即ち、これらの薬液は微多孔体の細孔の内部まで容易に到達することはできず、細孔の入口近傍により多くの薬液が固定される傾向がある。他の金属超微粒子の担持方法としては、各種金属イオンの無電解メッキ（化学メッキ）により安定に担持する方法が報告されている（特許文献１参照）。しかしこの方法は工程が複雑である上に、含浸法と同様に細孔を覆う形での金属析出が起こりやすいため、メッキ液の濃度を薄くする、予め真空処理を施して細孔内の空気を抜く等の煩雑な条件コントロールが必要となっていた。
【０００６】
上記のように従来の金属担持ポリマー多孔体製造方法は、多孔体製造工程、金属担持工程が各々問題点を有する上に、全体の工程が長く煩雑であり、多大なコストがかかっていた。金属担持多孔体を同時工程で製造する方法としては、金属微粒子とブロックコポリマーとによる金属・有機ポリマー複合体をミクロ相分離により多孔化し、一方の相にのみ金属超微粒子が含有されている金属・有機ポリマー複合体の製造方法が報告されている（特許文献２参照）。しかしこの方法も、クロロホルム、ベンゼン、ヘキサン等の有機溶媒を多量に用いるため、環境に対しては好ましくない技術となっていた。以上のことより、第一に工程が簡便で低コストであり、かつ環境に負荷をかけない金属担持ポリマー多孔体の製法が強く要望されていた。
【０００７】
【特許文献１】
特開平１０−３３０５２８号公報（第１−４頁）
【０００８】
【特許文献２】
特開平１０−３３０４９２号公報（第１−６頁）
【０００９】
【発明が解決しようとする課題】
本発明の目的は、上記従来技術が有していた問題点を解決し、簡便かつ効率的に、環境に負荷をかけることなく、金属担持ポリマー多孔体を製造する方法を提供することにある。また該方法により得られる微細孔表面に金属が分散した金属担持ポリマー多孔体を提供することにある。
【００１０】
【課題を解決するための手段】
本発明者らは、金属担持多孔体を製造する方法について鋭意検討を重ねた結果、金属前駆体が溶解した超臨界流体をポリマー中に浸透、発泡させることで上記目的を達成できることを見出し、本発明を完成するに至った。本発明において最も注目すべき点は、超臨界流体に金属前駆体の溶剤ならびに発泡剤という二つの働きを同時にもたせる点である。これにより、非常に簡便に、同時工程で金属担持ポリマー多孔体を得ることができる。
【００１１】
すなわち、本発明は以下のとおりである。
１．金属が分散担持されたポリマー多孔体を製造する方法であって、超臨界流体若しくは亜臨界流体と金属前駆体とからなる前駆体流体中にポリマーを配置して前駆体流体をポリマーに浸透させた後、発泡させて、気孔表面に金属が分散担持されたポリマー多孔体を得る、金属担持ポリマー多孔体の製造方法。
２．金属前駆体が有機金属化合物である、上記に記載の金属担持ポリマー多孔体の製造方法。
３．有機金属化合物が金属のアセチルアセトナートまたはアルコキシドである、上記に記載の金属担持ポリマー多孔体の製造方法。
４．ポリマーが熱可塑性ポリマーである、上記に記載の金属担持ポリマー多孔体の製造方法。
５．発泡を、ポリマーのガラス転移温度の−１００℃以上、＋１００℃未満の温度条件で行う、上記に記載の金属担持ポリマー多孔体の製造方法。
６．超臨界流体として二酸化炭素の超臨界流体を用いる、上記に記載の金属担持ポリマー多孔体の製造方法。
７．二酸化炭素の超臨界流体を圧力７．５〜２０．０ＭＰａの条件で用いる、上記に記載の金属担持ポリマー多孔体の製造方法。
８．超臨界流体若しくは亜臨界流体に金属前駆体を溶解させた前駆体流体中にポリマーを配置して流体を浸透させた後、発泡させ、気孔表面に金属を分散担持して得られる、金属担持ポリマー多孔体。
９．空隙率が１０％以上７０％未満の範囲内にある上記に記載の金属担持ポリマー多孔体。
１０．担持された金属の粒径が１ｎｍ以上１００ｎｍ未満の範囲内にある上記に記載の金属担持ポリマー多孔体。
１１．上記に記載の金属担持ポリマー多孔体から構成される機能性材料。
【００１２】
【発明の実施の形態】
本発明は上記のとおりの特徴をもつ全く新規な金属担持ポリマー多孔体の製造方法、および金属担持ポリマー多孔体に関するものである。以下にその実施の形態を説明する。
【００１３】
超臨界流体若しくは亜臨界流体と金属前駆体からなる前駆体流体について説明する。該前駆体流体は超臨界流体若しくは亜臨界流体に金属前駆体が溶解したものである。超臨界流体とは臨界温度、臨界圧力を超えた状態の物質を示し液体と気体の両方の特性をもつが、金属溶解能力をもつ超臨界流体としては二酸化炭素、亜酸化窒素、エタン、エチレン、メタノール、エタノール等が挙げられる。超臨界流体の溶解能力は温度、圧力、エントレーナー等により調整でき、また、該溶解能力および金属前駆体の量を調整することにより、多孔体に担持される金属濃度、分散状態、粒径等の制御が可能である。なお、本発明でいう金属前駆体の溶解とは、金属前駆体を含んだ超臨界流体が一つの相として観察されることを意味し、これを前駆体流体と表現する。
【００１４】
本発明において使用される金属前駆体としては、上記の超臨界流体に溶解させることができる任意のものが使用可能であるが、有機金属化合物が好ましく、特に金属のアセチルアセトナートまたはアルコキシドはその超臨界流体への溶解性が高いため、好ましい。例えば、下記式（１）
【００１５】
【化１】
【００１６】
【化２】
（ＣｍＨ２ｍ＋１Ｏ）ｎＭｅ （２）
（ここでＭｅは金属元素、ｍは１〜１０、ｎは１〜８である）
で表されるアルコキシド等が使用可能である。式（２）において好ましくはｍ＝１〜４、ｎ＝１〜５である。Ｍｅとしては、ｓ−ブロック金属元素、ｄ−ブロック金属元素、ｐ−ブロック金属元素、ｆ−ブロック金属元素から広範囲に選択することができ、具体的には、Ｐｔ、Ｐｄ、Ｒｈ、Ｔｉ、Ｓｉ、Ａｕ、Ａｌ、Ｚｒ、Ｃｅ、Ｗ、Ｇａ、Ｍｏ、Ｎｂ、Ｓｎ、Ｈｆ、Ｋ、Ｎａ、Ｍｇ、Ｃａ、Ｂａ、Ｃｏ、Ｎｉ等を挙げることができる。
【００１７】
上記有機金属化合物として、具体的には、白金アセチルアセトナート、パラジウムアセチルアセトナート、ロジウムアセチルアセトナート、ジルコニウムアセチルアセトナート、イリジウムアセチルアセトナートのようなアセチルアセトナート、チタン、イソプロポキシド、タングステンエトキシド、のようなアルコキシドが挙げられ、この他ビスアセテートトリフェニルフォスフェートパラジウム、パラジウムアセテート等も使用可能である。
【００１８】
また、金属前駆体の超臨界流体への溶解度ならびに金属の分散担持状態を制御するためのエントレーナーとしては、メタノール、エタノール、プロパノール等のアルコール、アセトン、エチルメチルケトン等のケトン類、ベンゼン、トルエン、キシレン等の芳香族炭化水素等を用いることができる。
【００１９】
本発明で用いられるポリマーには特に制限がないが、熱可塑性ポリマーが好ましい。本発明では、目的に応じて複数の熱可塑性ポリマーのアロイでもよい。例えば、ポリマーとして、ポリカーボネート、ポリアミド、ポリイミド、ポリアリレート、ポリエチレン、ポリスチレン、ポリプロピレン、ポリメチルペンテン、ポリアセタール、ポリエーテル、ポリエチレンテレフタレート、ポリメタクリル酸メチル、ポリ塩化ビニル、ポリエーテルイミド、ポリスルフォン、ポリエーテルスルフォン、ポリエーテルニトリル、アクリロニトリル−ブタジエン−スチレンコポリマー（ＡＢＳ）、各種熱可塑性エラストマー、液晶ポリマー、生分解性ポリマー等を例示できる。なお、本発明に供するポリマーとしては、シートやフィルム、繊維に限らず、柱状、球状等、他の形状の成形品であってもよい。
【００２０】
次に、多孔体製造過程について説明する。超臨界流体を用いたポリマー多孔体の製造は、二酸化炭素や窒素、アルゴン等の不活性ガスを加圧下にてポリマーに含浸させるガス含浸過程、圧力を減少させる圧力減少過程（圧力解放過程）、気泡核を成長させる発泡過程、より構成される。具体的には、ガラス転移温度の−１００℃以上、＋１００℃未満の温度で前駆体流体を浸透させた後、温度を保持したまま急速減圧することで気泡を形成させ、金属担持ポリマー多孔体を得ればよい。超臨界流体はポリマーの可塑化効果をもつため、超臨界流体が浸透したポリマーは通常よりも遥かに温和な条件で可塑化し、粘度が低下する。このため、通常のガラス転移温度以下の温度においても発泡が可能となる。また、加熱温度は低い方がエネルギーコスト面で有利であるため、ガラス転移温度＋５０℃未満の温度がより好ましい。さらに若しくは、加圧下でポリマーに前駆体流体を浸透させた後、降圧し、次いでポリマーのガラス転移温度の−１００℃以上、＋１００℃未満の温度まで加熱することにより気泡を成長させてもよく、これも本発明において好ましい一様態である。該超臨界発泡法は、熱力学的不安定な状態から核を形成し、この核を膨張成長させることで気泡を形成するものであり、ガスの熱力学的不安定性が相分離を誘起することにより今までにない微孔質の多孔体が得られるという利点がある。また、有機溶剤を用いる発泡法や相分離法と異なり環境に優しく、かつ、腐食性ガスや不純物による多孔体の汚染が起こらない。
【００２１】
本発明で使用する超臨界流体としては、上記のように金属前駆体の溶解能力をもち、かつ超臨界状態においてポリマーに浸透するものであれば特に限定する必要はないが、これらの要求を満たすものとしては二酸化炭素が好ましい。二酸化炭素は、臨界温度、圧力ともに低いため超臨界状態を得やすく、水に次いで安価であり、無毒、難燃性、無腐食性であるため取り扱い易く、かつ環境に対する負荷が少ない。また、二酸化炭素はポリマーへの含浸量が多く、含浸速度も速い。
【００２２】
二酸化炭素は臨界圧力が７．４８ＭＰａ、臨界温度が３１．１℃であり、圧力７．４８ＭＰａ、温度３１．１℃以上の超臨界状態にすると、二酸化炭素への金属前駆体の溶解度およびポリマーへの二酸化炭素の浸透度が著しく増大し、高濃度の金属担持が可能となる上、ポリマー中への含浸速度が速まる。また、ポリマーへの二酸化炭素の浸透度の増大によって気泡核が多量に発生し、その気泡核が成長してできる気泡の密度が空隙率が同じであっても大きくなり、非常に微細な気泡を得ることができる。従って本発明において、圧力は臨界圧力である７．４８ＭＰａ以上が好ましく、７．５〜２０．０ＭＰａが特に好ましい。過度の加圧は工業的に多量なエネルギーコストを要し、安全面、経済面においても多大な負荷がかかるため、好ましくない。また、亜臨界条件すなわち臨界点付近の条件下の二酸化炭素流体である亜臨界二酸化炭素流体を用いることも本発明において可能な一態様である。本発明において亜臨界二酸化炭素流体とは圧力７．０ＭＰａ以上、かつ温度２５℃以上であって、超臨界状態ではない二酸化炭素流体を示す。
【００２３】
超臨界流体への金属前駆体の溶解および前駆体流体のポリマーへの浸透の実施形態としては、例えば金属前駆体とポリマーを耐圧容器に入れ、容器内を超臨界流体で満たすことで行うことができる。ここで併せて機械的撹拌手段を利用して超臨界流体を撹拌することで、金属前駆体の溶解および前駆体流体の浸透を促進することができる。また、金属前駆体を超臨界流体に溶解させるのに、金属前駆体と超臨界流体の組み合わせによっては非常に長い時間を要することがある。この場合、別な圧力容器内で予め金属前駆体を超臨界流体に溶解させ、その耐圧容器から、ポリマー基材を入れた耐圧容器に前駆体流体を導入することで、工程に要する時間を短縮することができる。さらに、前駆体流体を、ポリマーを入れた耐圧容器に連続的に流通させて接触させることも、工程を簡略化する上で有効である。また、押出成形機を用いた連続成形プロセスを用いてもよい。この場合、ポリマーを押出機中に供給し溶融させ、溶融したポリマー中へ前駆体流体を送液、合流させた後、急激な圧力低下により発泡させればよい。さらに同様にして、射出成形機やブロー成形機等を用いた連続発泡成形プロセスも可能である。
【００２４】
上記本発明の方法により、金属が高分散担持された金属担持ポリマー多孔体を、非常に簡便に、かつ環境に負荷をかけずに得ることができる。すなわち、従来は２段階工程で行われていたポリマー多孔体製造と多孔体への金属担持とを、超臨界二酸化炭素に金属前駆体の溶剤ならびに発泡剤としての二つの働きをもたせることにより同時工程で行うことができる。このことにより、金属担持ポリマー多孔体の製造工程は大幅に簡略化され、それに伴って製造コストも大幅に削減される。また、上記連続成形プロセスを用いれば、大量に製造することも可能である。
【００２５】
上記発明の方法より得られた多孔体の空隙率は１０％以上７０％未満の範囲内であることが好ましく、ポリマーへの超臨界流体の含浸量・速度、または降圧速度、または気泡を成長させる際の加熱温度・時間等により、用途に応じて容易に制御することができる。空隙率が１０％未満であると担持金属が外界と接触し難くなり有効な比表面積を最大限に活用できないことがある。また７０％以上であると「す」の状態となり、金属を高分散担持させるための微多孔体としての機能低下の原因となる上、構造材料としての機械物性も低下することがある。本発明の方法では、ガスの熱力学的不安定性による相分離を利用して多孔体を製造するため、従来の有機溶剤を用いた発泡法では得られない微孔質の多孔体が得られる。さらに発泡剤の残存による多孔体の汚染可能性がないため、低汚染性の要求が高い電子部品用途などにも適用可能である。
【００２６】
金属粒径は１ｎｍ以上１００ｎｍ未満の大きさが好ましく、先に示したように温度、圧力、エントレーナー、金属前駆体量により制御が可能である。粒径が１００ｎｍ以上であると、金属の機能性が発現しにくくなることがある。本発明の金属担持方法は従来の方法とは全く異なり予めポリマー中へ金属を浸透させるため、細孔の入口近傍により多くの金属が担持されるようなことは起こらず、多孔体内部も含め全体にわたって均一に担持することが可能である。また、金属微粒子の担体への保持性の観点からは金属が担体内部に保持されていることが好ましいが、本発明では一度金属が担体内部に浸透するため、その後の発泡条件によって金属の担持深さをコントロールすることも可能である。
【００２７】
このようにして得られた金属担持ポリマー多孔体は、触媒、電池用電極材料、メンブレンリアクター、導電性または帯電防止プラスチック、電磁気シールド材料等の各種の機能性材料として非常に有用である。
【００２８】
【実施例】
以下、実施例により本発明を更に具体的に説明するが、本発明はこれにより何等限定を受けるものではない。
【００２９】
［実施例１］
幅１０ｍｍ、長さ６０ｍｍ、厚さ５ｍｍのポリカーボネート成形品（帝人化成製、ＡＤ５５０３、Ｔｇ＝１４７℃）と白金アセチルアセトナート２０ｍｇを容積１００ｍＬの耐圧容器に入れ、１５０℃、２５ＭＰａの二酸化炭素雰囲気中に５時間保持することにより、白金が溶存した超臨界二酸化炭素流体をポリカーボネートに含浸させた。その後減圧することで気泡を成長させ、白金担持ポリカーボネート多孔体を得た。走査型電子顕微鏡（ＳＥＭ）画像より、得られた多孔体の孔径は０．５〜２μｍであり、空隙率は４０％であった。また、透過型電子顕微鏡（ＴＥＭ）により、白金がポリカーボネート多孔体表面に、多孔内部も含め均一に分散して存在していることが確認され、その粒径は２０〜５０ｎｍであった。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a porous metal-carrying polymer, and more particularly, to use a supercritical fluid as a solvent and a foaming agent for a metal precursor to produce a porous metal-carrying polymer having a metal dispersed and supported on pore surfaces. The present invention relates to a method and a porous metal-carrying polymer in which a metal is dispersed to the inside of micropores obtained by the method.
[0002]
[Prior art]
The metal-supported porous material is useful as various functional materials such as a catalyst, an electrode material for a battery, a membrane reactor, a conductive or antistatic plastic, and an electromagnetic shielding material, and it is desired to establish a production method thereof. A catalyst is a typical example of such a functional material, and it is desirable to increase the specific surface area by highly dispersing a metal in order to increase the reactivity. In addition, if the dispersion is high, it is possible to prevent the metals from aggregating and growing as particles during the pretreatment or the reaction, and the durability of the activity is also improved. Here, in order to highly disperse and support the carrier, the carrier is preferably a microporous body having a large specific surface area. Conventionally, the use of inorganic materials such as silica gel, activated carbon, and alumina has been widely studied. However, since these inorganic materials are basically powders themselves, they are difficult to form and work. Therefore, not only inorganic materials but also microporous polymer carriers have been attracting attention for use as films, membranes and nonwoven fabrics.
[0003]
The manufacturing process of the porous metal-supported polymer generally includes a two-step process of manufacturing the porous polymer and supporting the metal on the polymer. That is, it is manufactured by supporting metal fine particles on the surface (hole wall surface) of a separately prepared porous polymer support.
[0004]
Examples of the method for producing the polymer porous body include a foaming method such as a foaming agent decomposition method and a solvent diffusion method, and a phase separation method. The foaming method uses a low boiling organic compound such as chlorofluorocarbons or methylene chloride as a foaming agent. Therefore, in addition to the high cost, there is a danger of flammability and toxicity, and there is a possibility of causing a problem of air pollution. For example, chlorofluorocarbon-based gases such as dichlorodifluoromethane are being completely eliminated from the environmental problem of depletion of the ozone layer. In addition, the phase separation method often used in the production of microporous materials is not only environmentally unfavorable because it uses an organic solvent and the like, but also because the polymer component is eluted and removed with a solvent to form pores, the pores are enlarged. It becomes a state of "su", which causes a decrease in the function as a microporous body for highly dispersing and supporting a metal.
[0005]
In addition, as a method of supporting a metal on these polymer porous bodies, a method of supporting the metal using a solution in which the metal is dissolved is generally used. A chemical solution such as an aqueous solution of a metal halide or a nitrate is used. The carrier is adsorbed or impregnated under atmospheric pressure and fixed. However, it is extremely difficult with the above-mentioned adsorption or impregnation method to fix a metal chemical uniformly over the entire surface of a porous body having a high specific surface area. That is, these chemicals cannot easily reach the inside of the pores of the microporous body, and more chemicals tend to be fixed near the entrance of the pores. As a method for supporting other metal ultrafine particles, a method of stably supporting various metal ions by electroless plating (chemical plating) has been reported (see Patent Document 1). However, this method is complicated and the metal deposition easily covers the pores as in the impregnation method.Therefore, the concentration of the plating solution is reduced, and the air in the pores is subjected to a vacuum treatment in advance to reduce the concentration. Complicated condition control such as pulling out is necessary.
[0006]
As described above, in the conventional method for producing a porous metal-supported polymer, the porous body production process and the metal-supporting process each have problems, and the entire process is long and complicated, resulting in high costs. As a method for producing a metal-supporting porous body in a simultaneous step, a metal / organic polymer composite made of metal fine particles and a block copolymer is made porous by microphase separation, and only one phase contains metal / fine organic particles. A method for producing an organic polymer composite has been reported (see Patent Document 2). However, this method is also unfavorable for the environment because it uses a large amount of an organic solvent such as chloroform, benzene, and hexane. From the above, firstly, there has been a strong demand for a method for producing a porous metal-carrying polymer which is simple and inexpensive and does not impose an environmental burden.
[0007]
[Patent Document 1]
JP-A-10-330528 (pages 1-4)
[0008]
[Patent Document 2]
JP-A-10-330492 (pages 1-6)
[0009]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art and to provide a method for easily and efficiently producing a porous metal-carrying polymer without imposing any burden on the environment. Another object of the present invention is to provide a porous metal-carrying polymer in which a metal is dispersed on the surface of micropores obtained by the method.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on a method for producing a metal-supported porous body, and as a result, have found that the above object can be achieved by infiltrating and foaming a supercritical fluid in which a metal precursor is dissolved into a polymer and foaming the polymer. The invention has been completed. The most remarkable point in the present invention is that the supercritical fluid simultaneously has two functions, that is, a solvent for the metal precursor and a blowing agent. This makes it possible to obtain a metal-supported polymer porous body very simply and simultaneously.
[0011]
That is, the present invention is as follows.
1. A method for producing a polymer porous body in which metal is dispersed and supported, wherein a polymer is arranged in a precursor fluid composed of a supercritical fluid or a subcritical fluid and a metal precursor, and the precursor fluid is impregnated in the polymer. Thereafter, foaming is performed to obtain a porous polymer body in which a metal is dispersed and supported on the pore surface.
2. The method for producing a porous metal-carrying polymer according to the above, wherein the metal precursor is an organometallic compound.
3. The method for producing a porous metal-carrying polymer according to the above, wherein the organometallic compound is a metal acetylacetonate or alkoxide.
4. The method for producing a porous metal-carrying polymer according to the above, wherein the polymer is a thermoplastic polymer.
5. The method for producing a porous metal-carrying polymer described above, wherein the foaming is performed under a temperature condition of a glass transition temperature of the polymer of −100 ° C. or more and less than + 100 ° C.
6. The method for producing a porous metal-carrying polymer according to the above, wherein a supercritical fluid of carbon dioxide is used as the supercritical fluid.
7. The method for producing a porous metal-carrying polymer according to the above, wherein a supercritical fluid of carbon dioxide is used at a pressure of 7.5 to 20.0 MPa.
8. A metal-carrying polymer obtained by disposing a polymer in a precursor fluid in which a metal precursor is dissolved in a supercritical fluid or a subcritical fluid, allowing the fluid to permeate, foaming, and dispersing and supporting the metal on the pore surface Porous body.
9. The porous metal-carrying polymer according to the above, wherein the porosity is in the range of 10% or more and less than 70%.
10. The metal-supported polymer porous body according to the above, wherein the supported metal has a particle size of 1 nm or more and less than 100 nm.
11. A functional material comprising the porous metal-carrying polymer described above.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to a completely novel method for producing a porous metal-supported polymer having the features described above, and a porous metal-supported polymer. The embodiment will be described below.
[0013]
A precursor fluid composed of a supercritical fluid or subcritical fluid and a metal precursor will be described. The precursor fluid is obtained by dissolving a metal precursor in a supercritical fluid or a subcritical fluid. A supercritical fluid refers to a substance that has exceeded the critical temperature and critical pressure and has both liquid and gas characteristics.However, supercritical fluids that have the ability to dissolve metals include carbon dioxide, nitrous oxide, ethane, ethylene, Methanol, ethanol and the like can be mentioned. The dissolving ability of the supercritical fluid can be adjusted by temperature, pressure, entrainer, etc., and by adjusting the dissolving ability and the amount of the metal precursor, the concentration of the metal supported on the porous body, the dispersion state, the particle size, etc. Can be controlled. The term “dissolution of a metal precursor” as used in the present invention means that a supercritical fluid containing a metal precursor is observed as one phase, which is referred to as a precursor fluid.
[0014]
As the metal precursor used in the present invention, any one that can be dissolved in the above-described supercritical fluid can be used, but an organometallic compound is preferable, and particularly, acetylacetonate or alkoxide of a metal is preferably used. This is preferable because of its high solubility in a critical fluid. For example, the following equation (1)
[0015]
Embedded image
[0016]
Embedded image
(C m H 2m + 1 O) n Me (2)
(Where Me is a metal element, m is 1 to 10, and n is 1 to 8)
And the like. In the formula (2), m = 1 to 4 and n = 1 to 5 are preferable. Me can be selected from a wide range of s-block metal elements, d-block metal elements, p-block metal elements, and f-block metal elements. Specifically, Pt, Pd, Rh, Ti, Si , Au, Al, Zr, Ce, W, Ga, Mo, Nb, Sn, Hf, K, Na, Mg, Ca, Ba, Co, Ni and the like.
[0017]
As the organometallic compound, specifically, acetylacetonate such as platinum acetylacetonate, palladium acetylacetonate, rhodium acetylacetonate, zirconium acetylacetonate, iridium acetylacetonate, titanium, isopropoxide, tungsten ethoxy And alkoxides such as, for example, bis-acetate triphenyl phosphate palladium and palladium acetate.
[0018]
Examples of the entrainer for controlling the solubility of the metal precursor in the supercritical fluid and the dispersion and support state of the metal include alcohols such as methanol, ethanol and propanol, ketones such as acetone and ethyl methyl ketone, benzene and toluene. And aromatic hydrocarbons such as xylene.
[0019]
The polymer used in the present invention is not particularly limited, but a thermoplastic polymer is preferred. In the present invention, an alloy of a plurality of thermoplastic polymers may be used according to the purpose. For example, as a polymer, polycarbonate, polyamide, polyimide, polyarylate, polyethylene, polystyrene, polypropylene, polymethylpentene, polyacetal, polyether, polyethylene terephthalate, polymethyl methacrylate, polyvinyl chloride, polyetherimide, polysulfone, polyether Examples include sulfone, polyether nitrile, acrylonitrile-butadiene-styrene copolymer (ABS), various thermoplastic elastomers, liquid crystal polymers, biodegradable polymers, and the like. The polymer used in the present invention is not limited to a sheet, a film, or a fiber, and may be a molded article having another shape such as a columnar shape or a spherical shape.
[0020]
Next, the porous body manufacturing process will be described. The production of a polymer porous body using a supercritical fluid includes a gas impregnation process in which an inert gas such as carbon dioxide, nitrogen, or argon is impregnated into a polymer under pressure, a pressure reduction process in which pressure is reduced (pressure release process), It consists of a foaming process of growing cell nuclei. Specifically, after infiltrating the precursor fluid at a temperature of −100 ° C. or higher and lower than + 100 ° C. of the glass transition temperature, bubbles are formed by rapidly reducing the pressure while maintaining the temperature, thereby forming a porous metal-carrying polymer. Just get it. Since the supercritical fluid has a plasticizing effect on the polymer, the polymer impregnated with the supercritical fluid plasticizes under much milder conditions than usual, and the viscosity decreases. For this reason, foaming is possible even at a temperature lower than the normal glass transition temperature. Since a lower heating temperature is more advantageous in terms of energy cost, a temperature lower than the glass transition temperature + 50 ° C is more preferable. Further alternatively, after infiltrating the precursor fluid into the polymer under pressure, the pressure may be reduced, and then the polymer may be heated to a glass transition temperature of −100 ° C. or higher and lower than + 100 ° C. to grow bubbles, This is also a preferred embodiment in the present invention. In the supercritical foaming method, a nucleus is formed from a thermodynamically unstable state, and bubbles are formed by expanding and growing the nucleus.The thermodynamic instability of gas induces phase separation. Thereby, there is an advantage that an unprecedented microporous body can be obtained. Unlike the foaming method and the phase separation method using an organic solvent, the method is environmentally friendly and does not cause contamination of the porous body by corrosive gas or impurities.
[0021]
The supercritical fluid used in the present invention does not need to be particularly limited as long as it has a dissolving ability of the metal precursor as described above and penetrates the polymer in the supercritical state, but satisfies these requirements. Carbon dioxide is preferred. Carbon dioxide is low in both critical temperature and pressure so that it is easy to obtain a supercritical state, is second only to water, and is inexpensive. Since it is nontoxic, flame-retardant, and non-corrosive, it is easy to handle and has little environmental impact. In addition, carbon dioxide impregnates the polymer in a large amount and has a high impregnation rate.
[0022]
Carbon dioxide has a critical pressure of 7.48 MPa and a critical temperature of 31.1 ° C. When it is brought into a supercritical state at a pressure of 7.48 MPa and a temperature of 31.1 ° C. or higher, the solubility of the metal precursor in carbon dioxide and the polymer The carbon dioxide permeation of the polymer significantly increases, a high concentration of metal can be supported, and the rate of impregnation into the polymer is increased. In addition, a large amount of bubble nuclei are generated due to an increase in the degree of penetration of carbon dioxide into the polymer, and the density of the bubbles formed by the growth of the bubble nuclei increases even if the porosity is the same. Obtainable. Therefore, in the present invention, the pressure is preferably equal to or higher than the critical pressure of 7.48 MPa, particularly preferably 7.5 to 20.0 MPa. Excessive pressurization undesirably requires a large amount of energy cost industrially and places a large load on safety and economy. It is also possible in the present invention to use a subcritical carbon dioxide fluid that is a carbon dioxide fluid under subcritical conditions, that is, a condition near a critical point. In the present invention, the subcritical carbon dioxide fluid refers to a carbon dioxide fluid that has a pressure of 7.0 MPa or more and a temperature of 25 ° C. or more and is not in a supercritical state.
[0023]
As an embodiment of dissolution of the metal precursor in the supercritical fluid and penetration of the precursor fluid into the polymer, for example, the metal precursor and the polymer are placed in a pressure-resistant container, and the container is filled with the supercritical fluid. it can. In this case, the supercritical fluid is stirred by using the mechanical stirring means, so that the dissolution of the metal precursor and the permeation of the precursor fluid can be promoted. In addition, it may take a very long time to dissolve the metal precursor in the supercritical fluid depending on the combination of the metal precursor and the supercritical fluid. In this case, the time required for the process is reduced by dissolving the metal precursor in a supercritical fluid in advance in another pressure vessel and introducing the precursor fluid from the pressure vessel to the pressure vessel containing the polymer substrate. can do. Further, it is also effective to continuously flow the precursor fluid into the pressure-resistant container containing the polymer to make the precursor fluid come into contact with the pressure-resistant container in order to simplify the process. Further, a continuous molding process using an extruder may be used. In this case, the polymer may be fed into the extruder and melted, and the precursor fluid may be fed into the melted polymer and merged, and then foamed due to a rapid pressure drop. In the same manner, a continuous foam molding process using an injection molding machine, a blow molding machine, or the like is also possible.
[0024]
According to the method of the present invention, a metal-supported polymer porous body on which a metal is highly dispersed and supported can be obtained very simply and without imposing any load on the environment. That is, the production of the porous polymer and the loading of the metal on the porous body, which were conventionally performed in a two-step process, are carried out simultaneously by making the supercritical carbon dioxide have two functions as a solvent and a foaming agent for the metal precursor. Can be done with This greatly simplifies the manufacturing process of the porous metal-carrying polymer, and accordingly significantly reduces the manufacturing cost. Further, if the above-mentioned continuous molding process is used, it is possible to produce a large amount.
[0025]
The porosity of the porous body obtained by the method of the present invention is preferably in the range of 10% or more and less than 70%, and the impregnation amount / rate of the supercritical fluid into the polymer, or the pressure reduction rate, or the growth of bubbles. It can be easily controlled according to the application by the heating temperature and time. If the porosity is less than 10%, the supported metal may not easily come into contact with the outside world, and the effective specific surface area may not be fully utilized. On the other hand, if it is 70% or more, it will be in a state of "su", which may cause a decrease in the function as a microporous body for highly dispersing and supporting a metal, and may also deteriorate the mechanical properties as a structural material. In the method of the present invention, a porous body is produced by utilizing phase separation due to thermodynamic instability of gas, so that a microporous porous body that cannot be obtained by a conventional foaming method using an organic solvent is obtained. Furthermore, since there is no possibility of contamination of the porous body due to the remaining foaming agent, the present invention can be applied to electronic parts and the like that require a high degree of low contamination.
[0026]
The metal particle size is preferably 1 nm or more and less than 100 nm, and can be controlled by the temperature, pressure, entrainer, and amount of metal precursor as described above. When the particle size is 100 nm or more, the functionality of the metal may not be easily exhibited. Since the metal supporting method of the present invention is completely different from the conventional method, the metal is pre-permeated into the polymer, so that more metal is not supported near the entrance of the pore, and the whole including the inside of the porous body does not occur. It is possible to carry uniformly. Further, it is preferable that the metal is held inside the carrier from the viewpoint of the retention of the metal fine particles on the carrier. However, in the present invention, the metal once permeates the inside of the carrier. It is also possible to control the length.
[0027]
The porous metal-carrying polymer obtained in this way is very useful as various functional materials such as catalysts, electrode materials for batteries, membrane reactors, conductive or antistatic plastics, and electromagnetic shielding materials.
[0028]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
[0029]
[Example 1]
A polycarbonate molded product having a width of 10 mm, a length of 60 mm, and a thickness of 5 mm (manufactured by Teijin Chemicals Ltd., AD5503, Tg = 147 ° C) and 20 mg of platinum acetylacetonate are placed in a pressure-resistant container having a volume of 100 mL. For 5 hours to impregnate the polycarbonate with a supercritical carbon dioxide fluid in which platinum was dissolved. Thereafter, the pressure was reduced to grow bubbles, and a platinum-supported polycarbonate porous body was obtained. From a scanning electron microscope (SEM) image, the pore size of the obtained porous body was 0.5 to 2 μm, and the porosity was 40%. Further, it was confirmed by a transmission electron microscope (TEM) that platinum was uniformly dispersed on the surface of the porous polycarbonate body including the inside of the porous body, and the particle diameter was 20 to 50 nm.
Claims (11)
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| JP2007119900A (en) * | 2005-09-06 | 2007-05-17 | Central Res Inst Of Electric Power Ind | Composite material of metal and porous substrate, and production method therefor |
| JP2007326094A (en) * | 2005-11-29 | 2007-12-20 | Denso Corp | Method for manufacturing mesoporous structure |
| JP2007332242A (en) * | 2006-06-14 | 2007-12-27 | National Institute Of Advanced Industrial & Technology | Method for producing inorganic substance polymer composite and inorganic substance polymer composite |
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| JP2007119900A (en) * | 2005-09-06 | 2007-05-17 | Central Res Inst Of Electric Power Ind | Composite material of metal and porous substrate, and production method therefor |
| JP2007326094A (en) * | 2005-11-29 | 2007-12-20 | Denso Corp | Method for manufacturing mesoporous structure |
| JP2007332242A (en) * | 2006-06-14 | 2007-12-27 | National Institute Of Advanced Industrial & Technology | Method for producing inorganic substance polymer composite and inorganic substance polymer composite |
| JP2008045013A (en) * | 2006-08-14 | 2008-02-28 | National Institute Of Advanced Industrial & Technology | Light-transmitting flexible heat insulating material and method for producing the same |
| JP2009138160A (en) * | 2007-12-10 | 2009-06-25 | National Institute Of Advanced Industrial & Technology | Method for manufacturing microfoam |
| JP2009172782A (en) * | 2008-01-22 | 2009-08-06 | National Institute Of Advanced Industrial & Technology | Method of manufacturing inorganic material-polymer composite with molding machine and inorganic material-polymer composite |
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