JP6060448B2 - 親水性改質フッ素化膜(ii) - Google Patents
親水性改質フッ素化膜(ii) Download PDFInfo
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- JP6060448B2 JP6060448B2 JP2015209925A JP2015209925A JP6060448B2 JP 6060448 B2 JP6060448 B2 JP 6060448B2 JP 2015209925 A JP2015209925 A JP 2015209925A JP 2015209925 A JP2015209925 A JP 2015209925A JP 6060448 B2 JP6060448 B2 JP 6060448B2
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- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- B01D67/0095—Drying
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
-
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- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
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- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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- B01D71/06—Organic material
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- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- C08G2261/126—Copolymers block
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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Description
[0001]フルオロポリマー膜、例えば多孔質PTFE膜の機械的強度、耐薬品性又は化学的不活性、非付着性、優れた誘電特性、高温での熱的安定性、及び低摩擦係数を含む特性によって、フルオロポリマー膜は様々な用途に対して非常に魅力あるものになる。しかし、ある種の用途に対しては、その本質的な特性に影響することなく、PTFE表面を改質することが便益となるであろう。特定の用途に対する膜の適合性を改善するために、PTFE膜の表面特性及び化学的性質を改質することが試みられてきた。例えば、表面被覆、混合、例えば、膜を波長250〜450nmのUV放射に曝す広帯域紫外線放射又はBBUV、及びプラズマ処理などの高エネルギー表面改質、遊離基、及びオゾンエッチング、原子層蒸着、及び改質PTFE様ポリマーの合成などが試みられた。しかし、大抵の試みは、BBUV及びプラズマなどの高エネルギー処理に集中した。これら表面改質法の正確なメカニズムは報告されていないが、C−C結合の強度はF−F結合よりも約40%低いことが知られているため、結合切断による遊離基形成からもたらされると考えられる。遊離基の大部分が、C−C切断又はポリマー主鎖切断からもたらされている場合、PTFE膜の機械的安定性及び化学的安定性を損なう恐れがある。またプラズマ処理は、膜表面に限られるため、長時間では膜を不安定にさせることも知られている。
[0003]本発明は、多孔質フルオロポリマー支持体、及びコポリマーを含む被覆を含む、親水性複合多孔質膜であって、コポリマーが繰返し単位A及びBを含み、Aは次式のものであり、
Bは次式のものであり、
コポリマーは、ブロックコポリマー又はランダムコポリマーであり、
xは3〜約10であり、
n及びmは、コポリマーに存在する繰返し単位A及びBの数であり、1〜約1000の範囲であり、但し、nとmの合計が10以上であり、
コポリマーは、任意選択で架橋結合されている、親水性複合多孔質膜を提供する。
[0013]一実施形態によれば、本発明は、多孔質フルオロポリマー支持体、及びコポリマーを含む被覆を含む、親水性複合多孔質膜であって、コポリマーが繰返し単位A及びBを含み、Aは次式のものであり、
Bは次式のものであり、
式中、
コポリマーは、ブロックコポリマー又はランダムコポリマーであり、
xは3〜約10であり、
n及びmは、コポリマーに存在する繰返し単位A及びBの数であり、1〜約1000の範囲であり、但し、nとmの合計が10以上であり、
コポリマーは、任意選択で架橋結合されている、親水性複合多孔質膜を提供する。
Bは次式のものであり、
ここで、*は、キレート官能基又はイオン交換官能基の結合点であり、コポリマーは、ブロックコポリマー又はランダムコポリマーであり、xは3〜約10であり、n及びmは、コポリマーに存在する繰返し単位A及びBの数であり、1〜約1000の範囲であり、但し、nとmの合計が10以上であり、
コポリマーは、任意選択で架橋結合されている、親水性複合多孔質膜を提供する。
[0020]上記実施形態のコポリマーの例として、
が挙げられる。
がある。
(i)開環メタセシス重合(ROMP)触媒によって触媒させて、5−(モノメトキシトリエチレングリコール)ノルボルネン(NTEG)を重合して、ホモポリマー、ポリNTEGを得るステップと、
(ii)(i)で得られたホモポリマーの分子鎖末端で、ROMP触媒によって触媒させて、5−(パーフルオロヘキシル)ノルボルネン又は5−(パーフルオロデシル)ノルボルネンを逐次重合するステップとを含む、コポリマー、ポリ(NTEG−b−NPF6)又はポリ(NTEG−b−NPF10)を調製する方法を提供する。
Bは次式のものであるステップと、
コポリマーをメルカプト酢酸、メルカプトエチルスルホン酸塩、又はチオグリセロールと反応させるステップと
を含む、上記のイオン交換官能基又はキレート官能基を有するコポリマーを調製する方法をさらに提供する。
[0044](i)多孔質フルオロポリマー支持体を用意するステップと、
[0045](ii)上記の溶媒及びコポリマーを含む溶液で、多孔質フルオロポリマー支持体を被覆するステップと、
[0046](iii)(ii)からの被覆された支持体を乾燥させて、溶液から溶媒の少なくとも一部を取り除くステップと、任意選択で、
[0047](iv)被覆された膜に存在するコポリマーを架橋結合させるステップと
を含む、多孔質フルオロカーボン支持体を親水性改質する方法をさらに提供する。
[0063]材料:以下の材料を購入し、そのまま使用した。
[0066]本実施例は、ジクロロ[1,3−ビス(2,4,6−トリメチルフェニル)−2−イミダゾリジニリデン](ベンジリデン)ビス(3−ブロモピリジン)ルテニウム(II)(G3)触媒の調製を説明する。
[0068]本実施例は、本発明の一実施形態の、ホモポリマー及びコポリマーの、ゲル浸透クロマトグラフィーによる特性決定を説明する。
[0070]移動相:ジクロロメタン(DCM)
[0071]移動相温度:30℃
[0072]UV波長:245nm
[0073]使用するカラム:3本のPSS SVD Lux分析カラム(スチレン−ジビニルベンゼンコポリマー網目構造)、直径5μm、孔径が1000A、100,000A、及び1,000,000Aであるビーズを固定相として有するカラム、及びガードカラム
[0074]流量:1mL/分
[0075]GPCシステム:UV検出器及びRI検出器を備える、Waters HPLC Alliance e2695システム
[0076]MALSシステム:664.5nmのレーザーを作動させる、8個の検出器を備えるDAWN HELEOS8システム
[0077]本実施例は、本発明の一実施形態のNPF6モノマーを調製する工程を説明する。
[0080]本実施例は、本発明の一実施形態のNPF10モノマーを調製する工程を説明する。
[0083]本実施例は、トリエチレングリコールモノメチルエーテルトシラート(TEG−OTs)を調製する工程を説明する。
[0089]本実施例は、本発明の一実施形態の、コポリマーの合成及び特性を説明する。
1H−NMR(300MHz,CDCl3):δ(ppm) 6.0〜6.35(s,広幅)、5.5〜6.0(s,広幅)、4.5〜5.2(s,広幅)、4.3〜4.5(s,広幅)、3.5〜3.8(m,広幅)、3.0〜3.3(s,広幅、2.0〜2.4(s,広幅)、1.5〜1.7(s,広幅)、1.0〜1.3(s)。
[0095]本実施例は、ポリ(NTEG−b−NPF6)コポリマーをUV架橋結合させる方法、及び本発明の一実施形態の、コポリマーの特性を説明する。
[0098]本実施例は、本発明の一実施形態の、他のコポリマーの合成及び特性を説明する。
[0106]本実施例は、本発明の一実施形態の、フルオロポリマー膜内のコポリマー、ポリ(NTEG−r−NPF6)を架橋結合させる方法を説明する。被覆工程を図4に示す。得られた結果を表4に示す。
[0108]本実施例は、本発明の一実施形態の、他のコポリマーの合成及び特性を説明する。
[0119]本実施例は、本発明の一実施形態のキレート特性及び/又はイオン交換特性をもたらすために、コポリマー、ポリ(NTEG−b−NPF6)を化学的改質する方法を説明する。
ポリ(NTEG−b−NPF6)(0.99g)、チオグリコール酸(MAcOH、0.9g)、及びAIBN(79.8mg)をTHF33mlに溶解させ、窒素下、55℃で26時間反応させた。反応混合物を水中に注ぎ込んだ。得られた沈殿物をTHFに再度溶解させ、再びヘプタンから沈殿させて、暗褐色の固体を得た。
ポリ(NTEG−b−NPF6)(0.99g)、2−メルカプトエタンスルホン酸ナトリウム(MeSNa、1.6g)及びAIBN(79.8mg)をTHF33mlに溶解させ、窒素下、55℃で26時間反応させた。反応混合物を水に注ぎ込んだ。得られた沈殿物を、THFに再度溶解させ、再びヘプタンから沈殿させて、黄色がかった固体を得た。
ポリ(NTEG−b−NPF6)(0.99g)、1−チオグリセロール(1.05g)、及びAIBN(79.8mg)をTHF33mlに溶解させ、窒素下、55℃で26時間反応させた。反応混合物を水に注ぎ込んだ。得られた沈殿物を、THFに再度溶解させ、再びヘプタンから沈殿させて、くすんだ白色の固体を得た。
Claims (17)
- 多孔質フルオロポリマー支持体、及びコポリマーを含む被覆を含む、親水性複合多孔質膜であって、コポリマーが繰返し単位A及びBを含み、Aは次式のものであり、
Bは次式のものであり、
コポリマーは、ブロックコポリマー又はランダムコポリマーであり、
xは3〜約10であり、
n及びmは、コポリマーに存在する繰返し単位A及びBの数であり、1〜約1000の範囲であり、但し、nとmの合計が10以上であり、
コポリマーは、任意選択で架橋結合されている、親水性複合多孔質膜。 - コポリマーが、アリール基及びアルコキシ基から選択される、分子鎖末端基を有する、請求項1に記載の親水性複合多孔質膜。
- コポリマーが、以下の式
の1つである、請求項1又は2に記載の親水性複合多孔質膜。 - 次式のブロックコポリマーである、
請求項3に記載の親水性複合多孔質膜。 - 次式のランダムコポリマーである、
請求項3に記載の親水性複合多孔質膜。 - 多孔質フルオロポリマー支持体、及びコポリマーを含む被覆を含む、親水性複合多孔質膜であって、コポリマーが、繰返し単位A及びB、並びに1つ又は複数の繰返し単位Aに結合した1つ又は複数のキレート官能基又はイオン交換官能基を含み、Aは次式のものであり、
Bは次式のものであり、
ここで、
*は、キレート官能基又はイオン交換官能基の結合点であり、
コポリマーは、ブロックコポリマー又はランダムコポリマーであり、
xは3〜約10であり、
n及びmは、コポリマーに存在する繰返し単位A及びBの数であり、1〜約1000の範囲であり、但し、nとmの合計が10以上であり、
コポリマーは、任意選択で架橋結合されている、親水性複合多孔質膜。 - コポリマーが、アリール基及びアルコキシ基から選択される分子鎖末端基を有する、請求項6に記載の親水性複合多孔質膜。
- キレート官能基又はイオン交換官能基が、カルボキシルアルキルチオ、スルホニルアルキルチオ、及びグリセリルチオの各基、並びにその組み合わせから選択される、請求項6又は7に記載の親水性複合多孔質膜。
- コポリマーが次式のものである、
請求項6〜8のいずれか一項に記載の親水性複合多孔質膜。 - (i)多孔質フルオロポリマー支持体を用意するステップと、
(ii)溶媒及びコポリマーを含む溶液で、多孔質フルオロポリマー支持体を被覆するステップであって、コポリマーは繰返し単位A及びBを有し、Aは次式のものであり、
Bは次式のものであり、
コポリマーは、ブロックコポリマー又はランダムコポリマーであり、
xは3〜約10であり、
n及びmは、コポリマーに存在する繰返し単位A及びBの数であり、1〜約1000の範囲であり、但し、nとmの合計が10以上である、ステップと、
(iii)(ii)からの被覆支持体を乾燥させて、前記コポリマーを含む溶液から溶媒の少なくとも一部を取り除くステップと、任意選択で、
(iv)被覆膜に存在する前記コポリマーを架橋結合させるステップと
を含む、多孔質フルオロポリマー支持体を親水性改質する方法。 - コポリマーが次式のものである、
請求項10に記載の多孔質フルオロポリマー支持体を親水性改質する方法。 - (i)多孔質フルオロポリマー支持体を用意するステップと、
(ii)溶媒及びコポリマーを含む溶液で、多孔質フルオロポリマー支持体を被覆するステップであって、コポリマーは繰返し単位A及びB、並びに1つ又は複数の繰返し単位Aに結合した、1種又は複数の、キレート官能基又はイオン交換官能基を有し、Aは次式のものであり、
Bは次式のものであり、
式中、
*は、キレート官能基又はイオン交換官能基の結合点であり、
コポリマーは、ブロックコポリマー又はランダムコポリマーであり、
xは3〜約10であり
n及びmは、コポリマーに存在する繰返し単位A及びBの数であり、1〜約1000の範囲であり、但し、nとmの合計が10以上である、ステップと、
(iii)(ii)から被覆支持体を乾燥させて、前記コポリマーを含む溶液から、溶媒の少なくとも一部を取り除くステップと、任意選択で、
(iv)被覆膜中に存在する前記コポリマーを架橋結合させるステップと
を含む、多孔質フルオロポリマー支持体を親水性改質する方法。 - コポリマーが次式のものである、
請求項12に記載の多孔質フルオロポリマー支持体を親水性改質する方法。 - 請求項10〜13のいずれか一項に記載の多孔質フルオロポリマー支持体を親水性改質する方法によって製造される、親水性多孔質膜。
- 前記多孔質フルオロポリマー支持体が、PTFE、PVDF、PVF(ポリフッ化ビニル)、PCTFE(ポリクロロトリフルオロエチレン)、FEP(フッ素化エチレンプロピレン)、ETFE(ポリエチレンテトラフルオロエチレン)、ECTFE(ポリ(エチレンクロロトリフルオロエチレン))、PFPE(パーフルオロポリエーテル)、PFSA(パーフルオロスルホン酸)、及びパーフルオロポリオキセタンから選択される、請求項1〜9のいずれか一項に記載の親水性複合多孔質膜、又は請求項14に記載の親水性改質多孔質フルオロポリマー膜。
- 請求項1〜9、14若しくは15のいずれか一項に記載の親水性多孔質膜に流体を通すステップを含む、流体を濾過する方法。
- 平面、平坦なシート、ひだ状、管状、らせん状、又は中空繊維の形状に形成される、請求項1〜9、14若しくは15のいずれか一項に記載の親水性複合多孔質膜。
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