JPH05279447A - Silicon-based block copolymer and membrane made thereof - Google Patents
Silicon-based block copolymer and membrane made thereofInfo
- Publication number
- JPH05279447A JPH05279447A JP4077338A JP7733892A JPH05279447A JP H05279447 A JPH05279447 A JP H05279447A JP 4077338 A JP4077338 A JP 4077338A JP 7733892 A JP7733892 A JP 7733892A JP H05279447 A JPH05279447 A JP H05279447A
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- Prior art keywords
- group
- block copolymer
- formula
- general formula
- component
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、新規なシリコン系ブロ
ック共重合体及びそれからなる、気体透過係数の大きな
分離膜に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicone block copolymer and a separation membrane comprising the same, which has a large gas permeability coefficient.
【０００２】[0002]
【従来の技術】ジメチルシロキサン／ビスフェノールＡ
ポリカーボネートから成る気体分離膜がＪ．Ｍｅｍｂ．
Ｓｃｉ．，１（１９７６）９９−１０８に記載されてい
る。2. Description of the Related Art Dimethylsiloxane / Bisphenol A
A gas separation membrane made of polycarbonate is described in J. Memb.
Sci. , 1 (1976) 99-108.
【０００３】また、一般式（５）で示されるオルガノポ
リシロキサンFurther, the organopolysiloxane represented by the general formula (5)
【化４】 （式中Ｒ6 は一価アリール基、飽和脂肪族基、不飽和脂
肪族基等、Ｙ′は−Ｒ7 と一般式（６）で示されるジヒドロキシ化合物 ＨＯ−Ｚ−ＯＨ ・・・（６） （式中Ｚは二価炭化水素基、オキシアリーレンオキシ基
等）と、イソシアネートからなるシリコンポリカーボネ
ートが特公昭４５−２０５１０号公報に記載されてい
る。[Chemical 4] (In the formula, R 6 is a monovalent aryl group, a saturated aliphatic group, an unsaturated aliphatic group, etc., and Y ′ is —R 7 And a dihydroxy compound represented by the general formula (6): HO-Z-OH (6) (wherein Z is a divalent hydrocarbon group, an oxyaryleneoxy group, etc.) and a silicone polycarbonate composed of an isocyanate. No. 20510.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、前記の
文献で提案されている膜や共重合体は、気体透過速度が
低く、また溶融成形温度が高いという問題点を有する。However, the membranes and copolymers proposed in the above documents have the problems of low gas permeation rate and high melt-forming temperature.
【０００５】本発明は合成の容易なブロック共重合体及
び気体透過係数が大きい選択透過膜、複合膜を提供する
ことにある。An object of the present invention is to provide a block copolymer which can be easily synthesized, a selective permeable membrane having a large gas permeability coefficient, and a composite membrane.
【０００６】[0006]
【課題を解決するための手段】本発明の要旨は、一般式
（１）又は（２）で示されるシロキサンジオールThe gist of the present invention is to provide a siloxane diol represented by the general formula (1) or (2).
【化５】 （式中Ｒ1 ，Ｒ2 は二価の炭化水素基、Ｒ3 はメチル基
もしくはフェニル基、ｌは８以上の整数を表す）[Chemical 5] (Wherein R 1 and R 2 are divalent hydrocarbon groups, R 3 is a methyl group or a phenyl group, and l is an integer of 8 or more)
【化６】 （式中Ｒ3 はメチル基もしくはフェニル基、ｍは８以上
の整数を表す）及び一般式（３）で示されるジイソシア
ネート ＯＣＮ−Ｒ4 −ＮＣＯ ・・・ （３） （式中Ｒ4 は脂肪族基、脂環族基もしくは芳香族基を表
す）及び一般式（４）で示されるカーボネートジオール[Chemical 6] (Wherein R 3 represents a methyl group or a phenyl group, m represents an integer of 8 or more) and the diisocyanate OCN-R 4 -NCO represented by the general formula (3) (3) (wherein R 4 is a fat Group group, alicyclic group or aromatic group) and a carbonate diol represented by the general formula (4)
【化７】 （式中Ｒ5 は脂肪族基、ｎは３以上の整数を表す）を反
応させて得られるウレタン結合を有するシリコン系ブロ
ック共重合体にある。[Chemical 7] (In the formula, R 5 is an aliphatic group, n is an integer of 3 or more), and is a silicone-based block copolymer having a urethane bond.
【０００７】さらにはシリコン系ブロック共重合体から
なる選択透過膜もしくはシリコン系ブロック共重合体
を、厚さ方向に連続した微細孔を有する多孔膜の表面に
設けた複合膜にある。Further, the present invention is a composite membrane in which a permselective membrane made of a silicon block copolymer or a silicon block copolymer is provided on the surface of a porous membrane having continuous fine pores in the thickness direction.
【０００８】一般式（１）で示されるシロキサンジオー
ルのＲ1 ，Ｒ2 は好しくは炭素数１〜５の炭化水素基で
ある。R 1 and R 2 of the siloxane diol represented by the general formula (1) are preferably hydrocarbon groups having 1 to 5 carbon atoms.
【０００９】一般式（１）又は（２）で示される化合物
でｌもしくはｍは好しくは１０〜２０００、より好しく
は１０〜６０の整数である。８未満の場合は透過速度係
数が低くなって好しくない。In the compound represented by the general formula (1) or (2), 1 or m is preferably 10 to 2000, more preferably 10 to 60. When it is less than 8, the transmission rate coefficient is low, which is not preferable.
【００１０】一般式（３）で示されるジイソシアネート
化合物としては、例えばテトラメチレンジイソシアネー
ト、ヘキサメチレンジイソシアネート、ｍ−キシレンジ
イソシアネート、ｐ−フェニレンジイソシアネート、４
, ４′−ジフェニルメタンジイソシアネート等が挙げら
れる。Examples of the diisocyanate compound represented by the general formula (3) include tetramethylene diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-phenylene diisocyanate, 4
, 4'-diphenylmethane diisocyanate and the like.
【００１１】一般式（４）で示される分子末端にヒドロ
キシル基を有するカーボネートジオールのｎは好しくは
５〜２５の整数である。ｎが３未満の場合は、製膜性が
わるくなり好しくない。In the carbonate diol having a hydroxyl group at the molecular end represented by the general formula (4), n is preferably an integer of 5 to 25. When n is less than 3, the film-forming property becomes poor, which is not preferable.
【００１２】本発明において、分子末端にカルビノール
基もしくはヒドロキシル基を有するシロキサンジオール
と、分子末端にヒドロキシル基を有するカーボネートジ
オールとの反応生成物におけるシロキサンの割合は、２
０〜８０ｗｔ％の範囲にあることが好しく、より好しく
は４０〜６０ｗｔ％の範囲である。８０ｗｔ％を越え
て、シロキサンジオールを混合した場合は、製膜性がわ
るくなるので好しくない。又２０ｗｔ％末端の場合は、
気体透過係数が低くなるので好しくない。In the present invention, the ratio of siloxane in the reaction product of the siloxane diol having a carbinol group or hydroxyl group at the molecular end and the carbonate diol having a hydroxyl group at the molecular end is 2
It is preferably in the range of 0 to 80 wt%, and more preferably in the range of 40 to 60 wt%. Mixing siloxanediol in an amount of more than 80 wt% is not preferable because the film-forming property becomes poor. In the case of 20 wt% end,
It is not preferable because it has a low gas permeability coefficient.
【００１３】本発明におけるウレタン結合を有するシリ
コン系ブロック共重合体は、下記の方法により製造する
ことができる。まず有機溶媒中にジイソシアネート化合
物を溶解し、窒素気流中で分子末端にカルビノール基又
はヒドロキシル基を有するシロキサンジオールを２時間
反応させ、分子両末端にイソシアネートを有する中間生
成物を得る。The silicon block copolymer having a urethane bond in the present invention can be produced by the following method. First, a diisocyanate compound is dissolved in an organic solvent, and a siloxane diol having a carbinol group or a hydroxyl group at a molecular end is reacted in a nitrogen stream for 2 hours to obtain an intermediate product having an isocyanate at both ends of the molecule.
【００１４】反応温度は６０℃から９０℃より好しくは
７０℃から８０℃の範囲が良い。触媒としてはジラウリ
ン酸ジブチル錫又は錫ジオクトエート等およびトリエチ
ルアミン等の公知の触媒が用いられる。The reaction temperature is preferably 60 to 90 ° C, more preferably 70 to 80 ° C. As the catalyst, known catalysts such as dibutyltin dilaurate or tin dioctoate and triethylamine are used.
【００１５】次いで分子末端にヒドロキシル基を有する
カルボジオールを加えて反応させ、ウレタン結合を有す
るシリコン系ブロック共重合体を得ることができる。Then, a carbodiol having a hydroxyl group at the terminal of the molecule is added and reacted to obtain a silicon block copolymer having a urethane bond.
【００１６】本発明におけるウレタン結合を有するシリ
コン系ブロック共重合体の製造に用いられる有機溶媒の
例としては、メチルエチルケトン、メチルイソブチルケ
トン、シクロヘキサノン、ジオキサン、テトラヒドロフ
ラン等あるいはこれらとＮ−メチル−２−ピロリドン、
Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセ
トアミド、ジメチルスルホキシド、ジエチルホルムアミ
ドとの混合溶剤が用いられる。Examples of the organic solvent used in the production of the silicone block copolymer having a urethane bond in the present invention include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dioxane, tetrahydrofuran, and N-methyl-2-pyrrolidone. ,
A mixed solvent of N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and diethylformamide is used.
【００１７】このようにして得られたウレタン結合を有
するシリコン系ブロック共重合体は、公知の方法により
平膜、管状膜、中空糸膜に製膜される。例えば、本発明
の共重合体を適当な溶剤に溶解した高分子溶液あるいは
重合溶液をそのままガラス板上に流延し、溶媒を蒸発さ
せることにより、非多孔質の選択透過平膜を得ることが
可能である。The urethane block-containing silicone block copolymer thus obtained is formed into a flat membrane, a tubular membrane or a hollow fiber membrane by a known method. For example, a polymer solution or a polymerization solution obtained by dissolving the copolymer of the present invention in a suitable solvent is directly cast on a glass plate, and the solvent is evaporated to obtain a non-porous permselective flat membrane. It is possible.
【００１８】又中空糸等の多孔質膜に該共重合体の高分
子溶液あるいは重合溶液をコーティングすることによ
り、多孔質膜表面に分離機能を有する複合膜を得ること
ができる。By coating a porous membrane such as a hollow fiber with a polymer solution or polymerization solution of the copolymer, a composite membrane having a separating function on the surface of the porous membrane can be obtained.
【００１９】[0019]
【実施例】以下、実施例により本発明を具体的に説明す
る。 「部」は重量部をあらわす。 実施例１ ４，４′−ジフェニルメタンジイソシアネート１０．１
部を７０℃のテトラヒドロフランとＮ，Ｎ′−ジメチル
アセトアミドの混合溶媒１００部に溶解し、窒素気流中
にて数平均分子量１０００の（３−オキサヘキサノー
ル）ジメチルシロキサン２０部とジラウリン酸ジブチル
錫、トリエチルアミン０．１５ｗｔ％をテトラヒドロフ
ランとＮ，Ｎ′−ジメチルアセトアミドの混合溶媒１２
０部に溶解したものを添加して、２時間攪拌した。EXAMPLES The present invention will be specifically described below with reference to examples. "Parts" represent parts by weight. Example 1 4,4'-diphenylmethane diisocyanate 10.1
Parts were dissolved in 100 parts of a mixed solvent of tetrahydrofuran and N, N′-dimethylacetamide at 70 ° C., and 20 parts of (3-oxahexanol) dimethylsiloxane having a number average molecular weight of 1000, dibutyltin dilaurate, and triethylamine in a nitrogen stream. 0.15 wt% is a mixed solvent of tetrahydrofuran and N, N'-dimethylacetamide 12
What was melt | dissolved in 0 part was added, and it stirred for 2 hours.
【００２０】次いで平均分子量１０００の１，６−ヘキ
サンカルボネートジオール２０部をテトラヒドロフラン
とＮ，Ｎ′−ジメチルアセトアミドの混合溶媒１５０部
に溶解したものを添加して１８時間反応させた。得られ
た溶液を水、メタノールで洗浄し、ウレタン結合を有す
るシリコン系ブロック共重合体を８０．４ｗｔ％の収率
で得た。Then, a solution prepared by dissolving 20 parts of 1,6-hexanecarbonate diol having an average molecular weight of 1000 in 150 parts of a mixed solvent of tetrahydrofuran and N, N'-dimethylacetamide was added and reacted for 18 hours. The obtained solution was washed with water and methanol to obtain a silicon block copolymer having a urethane bond in a yield of 80.4 wt%.
【００２１】実施例２ ４，４′−ジフェニルメタンジイソシアネート１０．１
部を７０℃のテトラヒドロフランとＮ，Ｎ′−ジメチル
アセトアミドの混合溶媒１５０部に溶解し、窒素気流中
にて、数平均分子量１８００の（３−オキサヘキサノー
ル）ジメチルシロキサン３６部とジラウリン酸ジブチル
錫、トリエチルアミン０．１５ｗｔ％をテトラヒドロフ
ランとＮ，Ｎ′−ジメチルアセトアミドの混合溶媒１２
０部に溶解したものを添加して、３時間攪拌した。Example 2 4,4'-diphenylmethane diisocyanate 10.1
Parts were dissolved in 150 parts of a mixed solvent of tetrahydrofuran and N, N′-dimethylacetamide at 70 ° C., and in a nitrogen stream, 36 parts of (3-oxahexanol) dimethylsiloxane having a number average molecular weight of 1800 and dibutyltin dilaurate, Triethylamine 0.15 wt% is a mixed solvent of tetrahydrofuran and N, N′-dimethylacetamide 12
What was melt | dissolved in 0 part was added, and it stirred for 3 hours.
【００２２】次いで平均分子量２０００の１，６−ヘキ
サンカーボネートジオール４０部をテトラヒドロフラン
とＮ，Ｎ′−ジメチルアセトアミドの混合溶媒２００部
に溶解したものを添加して２０時間反応させた。得られ
た溶液を水、メタノールで洗浄し、ウレタン結合を有す
るシリコン系ブロック共重合体を７５．９ｗｔ％の収率
で得た。Then, 40 parts of 1,6-hexanecarbonate diol having an average molecular weight of 2000 was dissolved in 200 parts of a mixed solvent of tetrahydrofuran and N, N'-dimethylacetamide, and the reaction was carried out for 20 hours. The obtained solution was washed with water and methanol to obtain a silicon block copolymer having a urethane bond in a yield of 75.9 wt%.
【００２３】実施例３ ４，４′−ジフェニルメタンジイソシアネート１０．１
部を７０℃のテトラヒドロフランとＮ，Ｎ′−ジメチル
アセトアミドの混合溶媒２００部に溶解し、窒素気流中
にて、数平均分子量３２００の（３−オキサヘキサノー
ル）ジメチルシロキサン６４部とジラウリン酸ジブチル
錫、トリエチルアミン０．１５ｗｔ％をテトラヒドロフ
ランとＮ，Ｎ′−ジメチルアセトアミドの混合溶媒１２
０部に溶解したものを添加して、４時間攪拌した。Example 3 4,4'-diphenylmethane diisocyanate 10.1
Parts were dissolved in 200 parts of a mixed solvent of tetrahydrofuran and N, N′-dimethylacetamide at 70 ° C., and 64 parts of (3-oxahexanol) dimethylsiloxane having a number average molecular weight of 3200 and dibutyltin dilaurate were added in a nitrogen stream. Triethylamine 0.15 wt% is a mixed solvent of tetrahydrofuran and N, N′-dimethylacetamide 12
What was melt | dissolved in 0 part was added, and it stirred for 4 hours.
【００２４】次いで平均分子量２０００の１，６−ヘキ
サンカ−ボネートジオール４０部をテトラヒドロフラン
とＮ，Ｎ’−ジメチルアセトアミドの混合溶媒２００部
に溶解したものを添加して２４時間反応させた。得られ
た溶液を水、メタノールで洗浄し、ウレタン結合を有す
るシリコン系ブロック共重合体を７１．５ｗｔ％の収率
で得た。Then, a solution prepared by dissolving 40 parts of 1,6-hexanecarbonate diol having an average molecular weight of 2000 in 200 parts of a mixed solvent of tetrahydrofuran and N, N'-dimethylacetamide was added and reacted for 24 hours. The obtained solution was washed with water and methanol to obtain a silicon block copolymer having a urethane bond in a yield of 71.5 wt%.
【００２５】実施例４ 実施例１〜３で調製した共重合体をアセトンに溶解し、
ガラス板上に流延しアセトンを蒸発させることにより１
２０μｍの厚みの均質なフィルムを作製した。このフィ
ルムを用いて、酸素ガス及び窒素ガスの透過係数を測定
したところ、表１のような結果であり、極めてガス透過
性に優れるものであった。Example 4 The copolymers prepared in Examples 1 to 3 were dissolved in acetone,
1 by casting on a glass plate and evaporating acetone
A homogeneous film with a thickness of 20 μm was produced. When the permeation coefficients of oxygen gas and nitrogen gas were measured using this film, the results are as shown in Table 1 and were extremely excellent in gas permeability.
【表１】 [Table 1]
【００２６】実施例５ ポリプロピレン多孔質中空糸膜（内径２００μｍ，膜厚
２５μｍ，平均孔径０．１μｍ）の膜上に実施例１で調
製した共重合体をコーティングした。Example 5 The copolymer prepared in Example 1 was coated on a polypropylene porous hollow fiber membrane (inner diameter 200 μm, film thickness 25 μm, average pore diameter 0.1 μm).
【００２７】酸素ガスの気体透過量を測定したところ、
６．９×１０-5ｃｃ／ｃｍ2 ・ｓｅｃ．ｃｍＨｇで、酸
素ガスと窒素ガスの分離係数は２．２であり、膜に欠陥
は無かった。気体透過量から計算される膜のコーティン
グ厚みは、０．４３μｍであった。When the gas permeation amount of oxygen gas was measured,
6.9 × 10 −5 cc / cm 2 · sec. In cmHg, the separation coefficient between oxygen gas and nitrogen gas was 2.2, and there was no defect in the film. The coating thickness of the membrane calculated from the gas permeation amount was 0.43 μm.
【００２８】[0028]
【発明の効果】本発明のウレタン結合を有するシリコン
系ブロック共重合体は、気体の透過性能に優れかつ良好
な製膜性と膜強度を保持するものであり、気体分離用途
や浸透気化分離等に極めて有用な材料である。EFFECT OF THE INVENTION The silicone block copolymer having a urethane bond of the present invention is excellent in gas permeation performance and retains good film forming property and film strength, and is used for gas separation and pervaporation separation. It is a very useful material.
Claims (3)
ール 【化１】 （式中Ｒ1 ，Ｒ2 は二価の炭化水素基、Ｒ3 はメチル基
もしくはフェニル基、ｌは８以上の整数を表す）又は一
般式（２）で示されるシロキサンジオール 【化２】 （式中Ｒ3 はメチル基もしくはフェニル基、ｍは８以上
の整数を表す）及び一般式（３）で示されるジイソシア
ネート ＯＣＮ−Ｒ4 −ＮＣＯ ・・・（３） （式中Ｒ4 は脂肪族基、脂環族基もしくは芳香族基を表
す）及び一般式（４）で示されるカーボネートジオール 【化３】 （式中Ｒ5 は脂肪族基、ｎは３以上の整数を表す）を反
応させて得られるウレタン結合を有するシリコン系ブロ
ック共重合体。1. A siloxane diol represented by the general formula (1): (Wherein R 1 and R 2 are divalent hydrocarbon groups, R 3 is a methyl group or a phenyl group, and l is an integer of 8 or more) or a siloxane diol represented by the general formula (2): (Wherein R 3 represents a methyl group or a phenyl group, m represents an integer of 8 or more) and the diisocyanate OCN-R 4 -NCO (3) represented by the general formula (3) (wherein R 4 is a fat A group, an alicyclic group or an aromatic group) and a carbonate diol represented by the general formula (4): (In the formula, R 5 is an aliphatic group, and n is an integer of 3 or more), and is a silicone-based block copolymer having a urethane bond.
合体からなる選択透過膜。2. A permselective membrane comprising the silicon block copolymer according to claim 1.
合体を、厚さ方向に連続した微細孔を有する多孔膜の表
面に設けた複合膜。3. A composite film in which the silicon block copolymer according to claim 1 is provided on the surface of a porous film having fine pores continuous in the thickness direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4077338A JPH05279447A (en) | 1992-03-31 | 1992-03-31 | Silicon-based block copolymer and membrane made thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4077338A JPH05279447A (en) | 1992-03-31 | 1992-03-31 | Silicon-based block copolymer and membrane made thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05279447A true JPH05279447A (en) | 1993-10-26 |
Family
ID=13631137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4077338A Pending JPH05279447A (en) | 1992-03-31 | 1992-03-31 | Silicon-based block copolymer and membrane made thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05279447A (en) |
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- 1992-03-31 JP JP4077338A patent/JPH05279447A/en active Pending
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