JP3172746B2 - Gas separation membrane with ester substituent - Google Patents
Gas separation membrane with ester substituentInfo
- Publication number
- JP3172746B2 JP3172746B2 JP14306195A JP14306195A JP3172746B2 JP 3172746 B2 JP3172746 B2 JP 3172746B2 JP 14306195 A JP14306195 A JP 14306195A JP 14306195 A JP14306195 A JP 14306195A JP 3172746 B2 JP3172746 B2 JP 3172746B2
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- Prior art keywords
- carbon dioxide
- group
- mol
- separation membrane
- alkyl
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Description
【０００１】[0001]
【産業上の利用分野】この発明は、高い二酸化炭素分離
係数と優れた二酸化炭素透過係数とを示すエステル置換
基を有する気体分離膜に係り、その高い二酸化炭素分離
性能により火力発電所、製鉄所高炉等の二酸化炭素固定
発生源からの二酸化炭素の分離回収や、天然ガスからの
二酸化炭素の除去等の用途に好適に用いられる気体分離
膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas separation membrane having an ester substituent exhibiting a high carbon dioxide separation coefficient and an excellent carbon dioxide permeation coefficient. The present invention relates to a gas separation membrane suitably used for applications such as separation and recovery of carbon dioxide from a fixed carbon dioxide source such as a blast furnace and removal of carbon dioxide from natural gas.
【０００２】[0002]
【従来の技術】二酸化炭素を選択的に分離できる気体分
離膜として、ポリアミドイミド膜（特開平１−１０３６
０９号公報）、ビシクロ型ポリイミド膜（特開平１−２
４９１２２号及び特開平１−２４５８３０号の各公
報）、あるいは、フッ素含有ポリイミド膜〔岡本ら、高
分子学会予稿集３８（７），１９５５（１９８９）〕等
が知られている。しかしながら、より低いエネルギーコ
ストで二酸化炭素を分離するために、より優れた二酸化
炭素の分離性能を有する気体分離膜の開発が要請されて
いる。2. Description of the Related Art As a gas separation membrane capable of selectively separating carbon dioxide, a polyamideimide membrane (Japanese Patent Laid-Open No. 1-1036) is known.
No. 09), a bicyclo-type polyimide film (Japanese Unexamined Patent Publication No.
49122 and JP-A-1-245830), or a fluorine-containing polyimide film [Okamoto et al., Proceedings of the Society of Polymer Science, 38 (7), 1955 (1989)]. However, in order to separate carbon dioxide at a lower energy cost, development of a gas separation membrane having better carbon dioxide separation performance is required.
【０００３】[0003]
【発明が解決しようとする課題】ところで、優れた二酸
化炭素の分離性能を有する気体分離膜とは、高い二酸化
炭素透過係数と高い二酸化炭素分離係数（二酸化炭素の
透過係数と窒素等の分離対象ガスの透過係数との比）と
を有する気体分離膜ということであり、この要件を満た
す分離膜は高分子膜に二酸化炭素透過係数を選択的に向
上させる化学構造を導入することで得られる。By the way, a gas separation membrane having excellent carbon dioxide separation performance means a high carbon dioxide permeation coefficient and a high carbon dioxide separation coefficient (a carbon dioxide permeation coefficient and a gas to be separated such as nitrogen). The ratio of the gas separation membrane to the gas separation membrane) can be obtained by introducing a chemical structure that selectively improves the carbon dioxide permeability coefficient into the polymer membrane.
【０００４】また、高分子膜における気体の透過係数
（透過性）は、気体の高分子膜への溶解度係数（溶解
性）と高分子膜中での拡散係数（拡散性）との積で表さ
れる。それ故、二酸化炭素の透過係数（透過性）を分離
対象ガスに対して選択的に向上させるためには、二酸化
炭素の高分子膜に対する溶解度係数（溶解性）及び／又
は拡散係数（拡散性）選択的に向上させればよいことに
なる。The gas permeability coefficient (permeability) of a polymer membrane is expressed as the product of the solubility coefficient (solubility) of gas in the polymer membrane and the diffusion coefficient (diffusivity) in the polymer membrane. Is done. Therefore, in order to selectively improve the permeability coefficient (permeability) of carbon dioxide with respect to the gas to be separated, the solubility coefficient (solubility) and / or diffusion coefficient (diffusivity) of carbon dioxide with respect to the polymer membrane is required. It is only necessary to improve selectively.
【０００５】ところで、二酸化炭素は、分子内で分極し
ているので、極性を有する化学構造と親和性を有するこ
とが考えられ、従って、気体分離膜を形成する高分子材
料に極性置換基を導入することにより、二酸化炭素の透
過係数（透過性）を分離対象ガスに対して選択的に向上
させることができ、高い二酸化炭素透過係数と高い二酸
化炭素／窒素分離係数とを兼ね備えて優れた二酸化炭素
の分離性能を有する気体分離膜が得られるものと考えら
れる。また、代表的な極性置換基としてカルボン酸基
（−ＣＯＯＨ）やスルホン酸基（−ＳＯ3 Ｈ）が挙げら
れる。Since carbon dioxide is polarized in a molecule, it is considered that carbon dioxide has an affinity for a polar chemical structure. Therefore, a polar substituent is introduced into a polymer material forming a gas separation membrane. By doing so, it is possible to selectively improve the permeation coefficient (permeability) of carbon dioxide with respect to the gas to be separated, and to provide both a high carbon dioxide permeation coefficient and a high carbon dioxide / nitrogen separation coefficient to provide excellent carbon dioxide. It is considered that a gas separation membrane having a separation performance of Representative polar substituents include a carboxylic acid group (—COOH) and a sulfonic acid group (—SO 3 H).
【０００６】従って、気体分離膜を形成する高分子材料
中にこのようなカルボン酸基やスルホン酸基を導入する
ことにより、優れた二酸化炭素の分離性能を有する気体
分離膜が得られることが期待される。そして、このカル
ボン酸基やスルホン酸基を有する二酸化炭素分離膜とし
て、カルボン酸化ポリイミド、スルホン酸化ポリスルホ
ンが知られているが、これらカルボン酸基やスルホン酸
基を導入することにより、かえって二酸化炭素の透過係
数が低下することが報告されている〔化学工学会第２５
回秋季大会講演要旨集第３分冊第９６頁（１９９２
年）〕。Accordingly, it is expected that a gas separation membrane having excellent carbon dioxide separation performance can be obtained by introducing such a carboxylic acid group or a sulfonic acid group into a polymer material forming a gas separation membrane. Is done. As the carbon dioxide separation membrane having a carboxylic acid group or a sulfonic acid group, a carboxylated polyimide or a sulfonated polysulfone is known. However, by introducing these carboxylic acid groups or sulfonic acid groups, carbon dioxide is instead removed. It has been reported that the permeability coefficient decreases [Chemical Engineering Society No. 25
Proceedings of the 3rd Autumn Meeting, 3rd volume, 96 pages (1992)
Year)〕.
【０００７】そこで、本発明者らは、気体分離膜を形成
する高分子材料中にカルボン酸基やスルホン酸基を導入
することにより、かえって二酸化炭素の透過係数が低下
する原因について鋭意検討した結果、この高分子材料中
に導入されたカルボン酸基やスルホン酸基がそれらの間
で互いに水素結合を形成し、このために高分子主鎖の分
子運動性が低下し、この高分子材料中での二酸化炭素の
拡散性が低下し、結果として二酸化炭素の透過係数が低
下したものと考察し、従って、二酸化炭素の溶解度係数
を向上させる極性置換基としては、水素結合等の疑似架
橋結合を形成しない構造で、しかも、適度な強さの極性
を有することが必要であるとの結論に到達した。[0007] The inventors of the present invention have conducted intensive studies on the cause of the carbon dioxide permeability coefficient being reduced by introducing a carboxylic acid group or a sulfonic acid group into the polymer material forming the gas separation membrane. However, the carboxylic acid groups and sulfonic acid groups introduced into the polymer material form hydrogen bonds with each other, thereby reducing the molecular mobility of the polymer main chain, and It is considered that the diffusivity of carbon dioxide has decreased, and as a result, the permeability coefficient of carbon dioxide has decreased, and therefore, as a polar substituent that improves the solubility coefficient of carbon dioxide, a pseudo-crosslinking bond such as a hydrogen bond is formed. It has been concluded that it is necessary to have a structure that does not have such a property and have a polarity of an appropriate strength.
【０００８】本発明者らは、このような観点で、水素結
合等の疑似架橋結合を形成しない構造であって、かつ、
適度な強さの極性を有して二酸化炭素の分離性能を向上
させるのに有効な極性置換基について種々検討した結
果、炭素数４以下のアルキルのカルボン酸エステル基及
びスルホン酸エステル基が最適であることを突き止め、
本発明を完成した。[0008] From such a viewpoint, the present inventors have a structure which does not form a pseudo cross-link such as a hydrogen bond, and
As a result of various studies on polar substituents having an appropriate strength of polarity and improving carbon dioxide separation performance, alkyl carboxylate and sulfonate groups having 4 or less carbon atoms are most suitable. Find out that there is
The present invention has been completed.
【０００９】従って、本発明の目的は、高い二酸化炭素
分離係数と高い二酸化炭素透過係数とを有して優れた二
酸化炭素の分離性能を有し、より低いエネルギーコスト
で窒素等の分離対象ガスから二酸化炭素を分離し回収あ
るいは除去することができる気体分離膜を提供すること
にある。Accordingly, an object of the present invention is to provide a high carbon dioxide separation coefficient and a high carbon dioxide permeation coefficient to have excellent carbon dioxide separation performance, and to reduce the cost of separating gas such as nitrogen from nitrogen or the like at a lower energy cost. An object of the present invention is to provide a gas separation membrane capable of separating and collecting or removing carbon dioxide.
【００１０】[0010]
【課題を解決するための手段】すなわち、本発明は、繰
り返し単位の少なくとも５モル％以上が下記一般式
（１）That is, in the present invention, at least 5 mol% or more of the repeating unit has the following general formula (1):
【化２】 （但し、式中Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 は水素原子、ア
ルキル基又はハロゲン基の何れかを示し、互いに同じで
あってもまた異なっていてもよく、また、Ｒ5 及びＲ6
は水素原子、スルホン酸基、カルボキシル基、炭素数４
以下のアルキルのカルボン酸エステル基又は炭素数４以
下のアルキルのスルホン酸エステル基の何れかを示し、
互いに同じであってもまた異なっていてもよい）で表さ
れる嵩高い構造部分を有し、かつ、繰り返し単位の１０
モル％以上が置換基として炭素数４以下のアルキルのカ
ルボン酸エステル基及び／又はスルホン酸エステル基
（以下、これらを単に「エステル置換基」ということが
ある）を有する高分子材料を用いるエステル置換基を有
する気体分離膜である。Embedded image (However, wherein R 1, R 2, R 3 and R 4 represents a hydrogen atom, one alkyl group or halogen group, which may be the or different and the same as each other, also, R 5 and R 6
Is a hydrogen atom, sulfonic acid group, carboxyl group, carbon number 4
Shows any of the following alkyl carboxylic acid ester groups or alkyl C 4 or less alkyl sulfonic acid ester group,
Which may be the same as or different from each other), and a repeating unit of 10
Ester substitution using a polymer material having an alkyl carboxylate group and / or a sulfonic acid ester group in which at least mol% is a substituent having 4 or less carbon atoms (hereinafter, these may be simply referred to as “ester substituents”). It is a gas separation membrane having a group.
【００１１】本発明において、エステル置換基が導入さ
れて気体分離膜の高分子材料となる高分子としては、高
分子の繰り返し単位中に少なくとも５モル％以上、好ま
しくは１０モル％以上、より好ましくは５０モル％以上
の上記一般式（１）で表される嵩高い構造部分を有する
ものであれば、特に限定されるものではないが、例え
ば、芳香族ポリイミド、芳香族ポリスルホン、芳香族ポ
リカーボネート、芳香族ポリエステル、芳香族ポリユリ
ア等を挙げることができ、特に芳香族ポリイミドにおい
てこのエステル置換基導入効果が大きい。In the present invention, the polymer into which the ester substituent is introduced to become a polymer material of the gas separation membrane is at least 5 mol%, preferably at least 10 mol%, more preferably at least 10 mol% in the repeating unit of the polymer. Is not particularly limited as long as it has a bulky structural portion represented by the above general formula (1) of 50 mol% or more. For example, aromatic polyimide, aromatic polysulfone, aromatic polycarbonate, Aromatic polyesters, aromatic polyureas and the like can be mentioned. Particularly, an aromatic polyimide has a large effect of introducing the ester substituent.
【００１２】ここで、例えば「高分子の繰り返し単位中
に１０モル％の嵩高い構造部分」という意味は、高分子
の繰り返し単位１０個当たり１個の嵩高い構造部分が存
在するという意味である。そして、一般式（１）で表さ
れる嵩高い構造は、高分子マトリックス中に適当な大き
さの空孔を形成せしめる作用を有し、本発明のエステル
置換基導入効果を大きくすると考えられるほか、高分子
材料に優れた溶媒溶解性や耐熱性を付与する作用を有す
る。[0012] Here, for example, the meaning of "a bulky structural portion of 10 mol% in a polymer repeating unit" means that there is one bulky structural portion per 10 polymer repeating units. . The bulky structure represented by the general formula (1) has an effect of forming pores of an appropriate size in the polymer matrix, and is considered to increase the effect of introducing an ester substituent of the present invention. It has an effect of imparting excellent solvent solubility and heat resistance to the polymer material.
【００１３】そして、このような高分子中に導入される
エステル置換基は、炭素数４以下のアルキルのカルボン
酸エステル基又は炭素数４以下のアルキルのスルホン酸
エステル基若しくはこれらカルボン酸エステル基とスル
ホン酸エステル基の両者であり、アルキルの炭素数が多
くて嵩高い構造ではガスの拡散係数が低下し、また、炭
素数が５以上になると二酸化炭素の透過性が低下し、実
用的でなくなる。このようなエステル置換基の具体例と
しては、例えば、カルボン酸メチルエステル基、カルボ
ン酸エチルエステル基、カルボン酸ｎ−プロピルエステ
ル基、スルホン酸メチルエステル基、スルホン酸エチル
エステル基、スルホン酸ｎ−プロピルエステル基等が挙
げられる。The ester substituent introduced into such a polymer may be an alkyl carboxylate group having 4 or less carbon atoms, a sulfonate ester group of an alkyl having 4 or less carbon atoms, or any of these carboxylic acid ester groups. It is both a sulfonic acid ester group, and in a bulky structure having a large number of carbon atoms in the alkyl, the gas diffusion coefficient is reduced, and when the number of carbon atoms is 5 or more, the permeability of carbon dioxide is reduced, which is not practical. . Specific examples of such ester substituents include, for example, carboxylic acid methyl ester group, carboxylic acid ethyl ester group, carboxylic acid n-propyl ester group, sulfonic acid methyl ester group, sulfonic acid ethyl ester group, sulfonic acid n- And a propyl ester group.
【００１４】また、高分子中へのエステル置換基の導入
量は、高分子の繰り返し単位中１０モル％以上でこのエ
ステル置換基導入効果が認められるが、好ましくは３０
モル％以上、より好ましくは５０モル％以上であるのが
よい。ここで、例えば「高分子の繰り返し単位中に１０
モル％のエステル置換基」という意味は、高分子の繰り
返し単位１０個当たり１個のエステル置換基が存在する
という意味である。導入量の上限は、二酸化炭素の分離
性能の観点からは特に認められず、高分子の製造が可能
であれば、高分子の繰り返し単位中により多くのエステ
ル置換基を導入してもよい。The effect of introducing the ester substituent can be recognized when the amount of the ester substituent introduced into the polymer is 10 mol% or more in the repeating unit of the polymer.
It is preferably at least 50 mol%, more preferably at least 50 mol%. Here, for example, “10 in the repeating unit of the polymer”
By "mol% of ester substituents" is meant that there is one ester substituent per 10 repeating units of the polymer. The upper limit of the amount introduced is not particularly recognized from the viewpoint of carbon dioxide separation performance, and if a polymer can be produced, more ester substituents may be introduced into the repeating unit of the polymer.
【００１５】このエステル置換基が導入された高分子材
料を製造する方法としては、このようなエステル置換基
を有するモノマーを用いて高分子材料を製造する方法
や、製造された高分子材料に化学反応でカルボン酸基や
スルホン酸基を導入し、これらカルボン酸基やスルホン
酸基を炭素数４以下のアルコールでエステル化する方法
が挙げられる。前者の方法は、エステル置換基を有する
モノマーを用意する必要があるが、高分子反応に比べて
反応性に富み、より多くの置換基を高分子材料に導入す
ることが可能である点で好ましく、また、後者の方法
は、非対称膜や複合膜等の表面改質技術として有効であ
る。ここで、非対称膜や複合膜とは、高分子材料を実用
的な気体分離膜に成形した形状であり、この形状の気体
分離膜が多く市販されている。As a method for producing the polymer material into which the ester substituent is introduced, there are a method for producing a polymer material using a monomer having such an ester substituent, and a method for producing a polymer material by chemical reaction. A method of introducing a carboxylic acid group or a sulfonic acid group by a reaction and esterifying the carboxylic acid group or the sulfonic acid group with an alcohol having 4 or less carbon atoms can be mentioned. In the former method, it is necessary to prepare a monomer having an ester substituent, but it is preferable in that it is rich in reactivity as compared with a polymer reaction, and it is possible to introduce more substituents into a polymer material. The latter method is effective as a surface modification technique for an asymmetric membrane or a composite membrane. Here, the asymmetric membrane or the composite membrane has a shape in which a polymer material is formed into a practical gas separation membrane, and many gas separation membranes having this shape are commercially available.
【００１６】[0016]
【実施例】以下、実施例及び比較例に基づいて、本発明
を具体的に説明する。なお、以下の実施例及び比較例に
おいて、気体の透過係数は検出器にガスクロマトグラフ
ィを用いた減圧式気体透過速度測定装置を用い、供給ガ
スとして混合ガス（二酸化炭素１０％、窒素９０％）を
用いて、測定温度２５℃及び圧力差１．５気圧で測定し
た。気体透過係数の単位はバレル（barrer）＝１０-10
ｃｍ3（ＳＴＰ）ｃｍ／ｃｍ2 ・ｓｅｃ・ｃｍＨｇであ
り、分離係数は気体透過係数の比である。The present invention will be specifically described below based on examples and comparative examples. In the following Examples and Comparative Examples, the gas permeability coefficient was measured by using a pressure-reducing gas transmission rate measuring device using gas chromatography as a detector, and using a mixed gas (carbon dioxide 10%, nitrogen 90%) as a supply gas. The measurement was performed at a measurement temperature of 25 ° C. and a pressure difference of 1.5 atm. The unit of the gas permeability coefficient is barrel = 10 -10
cm 3 (STP) cm / cm 2 · sec · cmHg, and the separation coefficient is the ratio of the gas permeability coefficient.
【００１７】実施例１ ９，９−ビス（４−アミノフェニル）フルオレン−４−
カルボン酸メチルエステル８．１３ｇ（０．０２モル）
とベンゾフェノンテトラカルボン酸二無水物（ＢＤＴ
Ａ）６．４４ｇ（０．０２モル）とをＮ−メチル−２−
ピロリドン８０ｇに混ぜ、溶液温度を１８５℃に保持
し、生成する水を除去しながら反応させた。反応終了
後、反応溶液をガラスフィルターで濾過し、冷却した後
にメタノール中に注ぎ、生成物のポリイミドを析出させ
た。得られたポリイミドを洗浄したのち、真空乾燥し
た。得られたポリイミドの反応収率はほぼ１００％であ
った。Example 1 9,9-bis (4-aminophenyl) fluorene-4-
8.13 g (0.02 mol) of carboxylic acid methyl ester
And benzophenonetetracarboxylic dianhydride (BDT
A) 6.44 g (0.02 mol) of N-methyl-2-
The mixture was mixed with 80 g of pyrrolidone, the solution was kept at 185 ° C., and reacted while removing generated water. After the completion of the reaction, the reaction solution was filtered through a glass filter, and after cooling, poured into methanol to precipitate a product polyimide. After washing the obtained polyimide, it was vacuum-dried. The reaction yield of the obtained polyimide was almost 100%.
【００１８】このポリイミド０．５ｇをＮ−メチル−２
−ピロリドン１００ｍｌに溶解し、得られた溶液を３５
℃で測定した際のインヘレント粘度は０．７３ｄｌ／ｇ
であった。また、このポリイミドは、その繰り返し単位
１個中に、１個の嵩高い構造であるフェニルフルオレン
構造部分と１個のカルボン酸メチルエステル置換基とを
有しており、嵩高い構造部分は繰り返し単位中１００モ
ル％であり、また、カルボン酸メチルエステル置換基は
繰り返し単位中１００モル％であった。0.5 g of this polyimide was added to N-methyl-2
-Dissolve in 100 ml of pyrrolidone and dilute the resulting solution with 35
0.73 dl / g inherent viscosity as measured at ° C
Met. Further, this polyimide has one bulky phenylfluorene structure portion and one carboxylic acid methyl ester substituent in one repeating unit thereof, and the bulky structure portion is a repeating unit And the carboxylic acid methyl ester substituent was 100 mol% in the repeating unit.
【００１９】更に、得られたポリイミドの１７．５重量
％Ｎ−メチル−２−ピロリドン溶液を調製し、この溶液
をガラス板上に均一の厚さで流延し、その後に乾燥器で
溶媒を除去してポリイミド膜を形成し、得られたポリイ
ミド膜の二酸化炭素／窒素分離性能を調べた。結果は、
二酸化炭素透過係数１１バレル、窒素透過係数０．１８
バレル、及び二酸化炭素／窒素分離係数６０であった。Further, a 17.5% by weight N-methyl-2-pyrrolidone solution of the obtained polyimide was prepared, and this solution was cast on a glass plate to have a uniform thickness. After removal, a polyimide film was formed, and the carbon dioxide / nitrogen separation performance of the obtained polyimide film was examined. Result is,
Carbon dioxide permeability coefficient 11 barrels, nitrogen permeability coefficient 0.18
The barrel and carbon dioxide / nitrogen separation factor were 60.
【００２０】実施例２ 窒素導入管、Ｄｅａｎ−Ｓｔａｒｋトラップ、還流冷却
器、攪拌装置を備えた１０００ｍｌの４つ口フラスコに
９，９−ビス（４−ヒドロキシフェニル）フルオレン−
４−カルボン酸メチルエステル４０．８ｇ（０．１０モ
ル）、４，４’−ジクロロジフェニルスルホン２８．７
ｇ（０．１０モル）、炭酸カリウム１５．２（０．１１
モル）、Ｎ，Ｎ−ジメチルアセトアミド３２０ｇ及びト
ルエン４５０ｍｌを仕込み、窒素雰囲気下に攪拌しなが
ら加熱して反応させた。反応は、還流温度を１２０℃に
抑えて１晩加熱を続け、次いで水分を共沸留去させたの
ち、トルエンを抜いて溶媒の温度を１５０℃まで上昇さ
せ、そのまま水分の共沸留去を１５時間続けた。反応終
了後、反応溶液を冷却し、濾過して過剰の炭酸カリウム
や生成した塩化カリウムを除去し、次いで水中に注入し
てポリスルホンを析出させ、これを濾過して乾燥させ、
ポリスルホンを得た。得られたポリスルホンの反応収率
はほぼ１００％であった。EXAMPLE 2 9,9-Bis (4-hydroxyphenyl) fluorene was placed in a 1000 ml four-necked flask equipped with a nitrogen inlet tube, a Dean-Stark trap, a reflux condenser, and a stirrer.
4-carboxylic acid methyl ester 40.8 g (0.10 mol), 4,4'-dichlorodiphenyl sulfone 28.7
g (0.10 mol), potassium carbonate 15.2 (0.11 mol)
Mol), N, N-dimethylacetamide (320 g) and toluene (450 ml) were charged and reacted while heating under a nitrogen atmosphere while stirring. In the reaction, the reflux temperature was kept at 120 ° C., and heating was continued overnight. Then, after water was azeotropically distilled off, toluene was removed, the temperature of the solvent was raised to 150 ° C., and the water was azeotropically distilled off. Continued for 15 hours. After completion of the reaction, the reaction solution was cooled and filtered to remove excess potassium carbonate and generated potassium chloride, and then poured into water to precipitate polysulfone, which was filtered and dried,
Polysulfone was obtained. The reaction yield of the obtained polysulfone was almost 100%.
【００２１】このポリスルホン０．５ｇをＮ−メチル−
２−ピロリドン１００ｍｌに溶解し、得られた溶液を３
５℃で測定した際のインヘレント粘度は０．６５ｄｌ／
ｇであった。また、このポリスルホンは、その繰り返し
単位１個中に、１個の嵩高い構造であるフェニルフルオ
レン構造部分と１個のカルボン酸メチルエステル置換基
とを有しており、嵩高い構造部分は繰り返し単位中１０
０モル％であり、また、カルボン酸メチルエステル置換
基は繰り返し単位中１００モル％であった。0.5 g of the polysulfone was added to N-methyl-
Dissolved in 100 ml of 2-pyrrolidone,
The inherent viscosity measured at 5 ° C. is 0.65 dl /
g. Further, this polysulfone has one bulky phenylfluorene structure portion and one carboxylate methyl ester substituent in one repeating unit thereof, and the bulky structure portion is a repeating unit. Medium 10
0 mol%, and the carboxylic acid methyl ester substituent was 100 mol% in the repeating unit.
【００２２】更に、得られたポリスルホンの１７．５重
量％Ｎ−メチル−２−ピロリドン溶液を調製し、この溶
液をガラス板上に均一の厚さで流延し、その後に乾燥器
で溶媒を除去してポリスルホン膜を形成し、得られたポ
リスルホン膜の二酸化炭素／窒素分離性能を調べた。結
果は、二酸化炭素透過係数１２バレル、窒素透過係数
０．２２バレル、及び二酸化炭素／窒素分離係数５５で
あった。Further, a 17.5% by weight solution of the obtained polysulfone in N-methyl-2-pyrrolidone was prepared, and the solution was cast on a glass plate at a uniform thickness. After removal, a polysulfone membrane was formed, and the carbon dioxide / nitrogen separation performance of the obtained polysulfone membrane was examined. The results were a carbon dioxide permeability coefficient of 12 barrels, a nitrogen permeability coefficient of 0.22 barrels, and a carbon dioxide / nitrogen separation coefficient of 55.
【００２３】比較例１ ９，９−ビス（４−アミノフェニル）フルオレン−４−
カルボン酸６．９７ｇ（０．０２モル）とベンゾフェノ
ンテトラカルボン酸二無水物（ＢＤＴＡ）６．４４ｇ
（０．０２モル）とをＮ−メチル−２−ピロリドン８０
ｇに混ぜ、溶液温度を１８５℃に保持し、生成する水を
除去しながら反応させた。反応終了後、反応溶液をガラ
スフィルターで濾過し、冷却した後にメタノール中に注
ぎ、生成物のポリイミドを析出させた。得られたポリイ
ミドを洗浄したのち、真空乾燥した。得られたポリイミ
ドの反応収率はほぼ１００％であった。Comparative Example 1 9,9-bis (4-aminophenyl) fluorene-4-
6.97 g (0.02 mol) of carboxylic acid and 6.44 g of benzophenonetetracarboxylic dianhydride (BDTA)
(0.02 mol) and N-methyl-2-pyrrolidone 80
g, keeping the solution temperature at 185 ° C., and reacting while removing the generated water. After the completion of the reaction, the reaction solution was filtered through a glass filter, and after cooling, poured into methanol to precipitate a product polyimide. After washing the obtained polyimide, it was vacuum-dried. The reaction yield of the obtained polyimide was almost 100%.
【００２４】このポリイミド０．５ｇをＮ−メチル−２
−ピロリドン１００ｍｌに溶解し、得られた溶液を３５
℃で測定した際のインヘレント粘度は０．６７ｄｌ／ｇ
であった。また、このポリイミドは、その繰り返し単位
１個中に１個の嵩高い構造であるフェニルフルオレン構
造部分を有しているが、エステル置換基は存在せず、ま
た、この嵩高い構造部分は繰り返し単位中１００モル％
であった。0.5 g of this polyimide was added to N-methyl-2
-Dissolve in 100 ml of pyrrolidone and dilute the resulting solution with 35
0.67 dl / g inherent viscosity as measured at ° C
Met. Further, this polyimide has one bulky phenylfluorene structure portion in one repeating unit thereof, but has no ester substituent, and this bulky structure portion has a repeating unit. 100 mol% in
Met.
【００２５】更に、得られたポリイミドの１７．５重量
％Ｎ−メチル−２−ピロリドン溶液を調製し、この溶液
をガラス板上に均一の厚さで流延し、その後に乾燥器で
溶媒を除去してポリイミド膜を形成し、得られたポリイ
ミド膜の二酸化炭素／窒素分離性能を調べた。結果は、
二酸化炭素透過係数１０バレル、窒素透過係数０．２０
バレル、及び二酸化炭素／窒素分離係数５０であった。Further, a 17.5% by weight N-methyl-2-pyrrolidone solution of the obtained polyimide was prepared, and the solution was cast on a glass plate to have a uniform thickness. After removal, a polyimide film was formed, and the carbon dioxide / nitrogen separation performance of the obtained polyimide film was examined. Result is,
Carbon dioxide permeability coefficient 10 barrels, nitrogen permeability coefficient 0.20
The barrel and carbon dioxide / nitrogen separation factor were 50.
【００２６】上記実施例１のエステル置換基を有するポ
リイミドと比較例１のエステル置換基を有しないポリイ
ミドにおける二酸化炭素／窒素分離係数はそれぞれ６０
と５０であり、二酸化炭素／窒素分離係数６０である実
施例１のポリイミドは、比較例１のポリイミドに比べて
二酸化炭素の分離性能が大幅に向上しており、より少な
いエネルギー消費で同量の二酸化炭素を分離し回収ある
いは除去できることが判明した。The carbon dioxide / nitrogen separation coefficients of the polyimide having an ester substituent of Example 1 and the polyimide having no ester substituent of Comparative Example 1 were 60, respectively.
The polyimide of Example 1 having a carbon dioxide / nitrogen separation coefficient of 60 has a significantly improved carbon dioxide separation performance as compared with the polyimide of Comparative Example 1, and has the same amount of energy with less energy consumption. It has been found that carbon dioxide can be separated and recovered or removed.
【００２７】[0027]
【発明の効果】本発明のエステル置換基を有する気体分
離膜は、高い二酸化炭素分離係数と高い二酸化炭素透過
係数とを有して優れた二酸化炭素の分離性能を有し、よ
り低いエネルギーコストで窒素等の分離対象ガスから二
酸化炭素を分離し回収あるいは除去することができるの
で、火力発電所、製鉄所高炉等の二酸化炭素固定発生源
からの二酸化炭素の分離回収や、天然ガスからの二酸化
炭素の除去等の用途に好適である。The gas separation membrane having an ester substituent of the present invention has a high carbon dioxide separation coefficient and a high carbon dioxide permeation coefficient, has excellent carbon dioxide separation performance, and has a lower energy cost. Since carbon dioxide can be separated and recovered or removed from the gas to be separated such as nitrogen, carbon dioxide can be separated and recovered from fixed carbon dioxide sources such as thermal power plants and steelworks blast furnaces, and carbon dioxide can be separated from natural gas. It is suitable for applications such as removal of water.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 風間 伸吾 東京都港区西新橋２−８−11、第７東洋 海事ビル８Ｆ、財団法人地球環境産業技 術研究機構 ＣＯ２ 固定化等プロジェ クト室内 (72)発明者 原谷 賢治 茨城県つくば市東１−１、工業技術院 物質工学工業技術研究所内 審査官 真々田 忠博 (56)参考文献 特開 平６−91145（ＪＰ，Ａ) 特開 平５−317668（ＪＰ，Ａ) 特開 平８−24603（ＪＰ，Ａ) 特開 平８−24602（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 71/82 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shingo Kazama 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo, 8th floor of the 7th Oriental Maritime Building, Institute for Global Environmental Technology, CO2 fixed project room ( 72) Inventor Kenji Haraya 1-1, Higashi 1-1, Tsukuba City, Ibaraki Prefecture, Examiner at the Institute of Materials Science and Technology, National Institute of Advanced Industrial Science and Technology Tadahiro Sanada (56) References JP-A-6-91145 (JP, A) JP-A-5-317668 ( JP, A) JP-A-8-24603 (JP, A) JP-A-8-24602 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01D 71/82
Claims (1)
が下記一般式（１） 【化１】 （但し、式中Ｒ1 、Ｒ2 、Ｒ3 及びＲ4 は水素原子、ア
ルキル基又はハロゲン基の何れかを示し、互いに同じで
あってもまた異なっていてもよく、また、Ｒ5 及びＲ6
は水素原子、スルホン酸基、カルボキシル基、炭素数４
以下のアルキルのカルボン酸エステル基又は炭素数４以
下のアルキルのスルホン酸エステル基の何れかを示し、
互いに同じであってもまた異なっていてもよい）で表さ
れる嵩高い構造部分を有し、かつ、繰り返し単位の１０
モル％以上が置換基として炭素数４以下のアルキルのカ
ルボン酸エステル基及び／又はスルホン酸エステル基を
有する高分子材料を用いることを特徴とするエステル置
換基を有する気体分離膜。[Claim 1] At least 5 mol% or more of the repeating unit has the following general formula (1): (However, wherein R 1, R 2, R 3 and R 4 represents a hydrogen atom, one alkyl group or halogen group, which may be the or different and the same as each other, also, R 5 and R 6
Is a hydrogen atom, sulfonic acid group, carboxyl group, carbon number 4
Shows any of the following alkyl carboxylic acid ester groups or alkyl C 4 or less alkyl sulfonic acid ester group,
Which may be the same as or different from each other), and a repeating unit of 10
A gas separation membrane having an ester substituent, wherein a polymer material having an alkyl carboxylate group and / or a sulfonic acid ester group having 4 or less carbon atoms as a substituent is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14306195A JP3172746B2 (en) | 1995-06-09 | 1995-06-09 | Gas separation membrane with ester substituent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14306195A JP3172746B2 (en) | 1995-06-09 | 1995-06-09 | Gas separation membrane with ester substituent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08332362A JPH08332362A (en) | 1996-12-17 |
| JP3172746B2 true JP3172746B2 (en) | 2001-06-04 |
Family
ID=15330009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14306195A Expired - Lifetime JP3172746B2 (en) | 1995-06-09 | 1995-06-09 | Gas separation membrane with ester substituent |
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| Country | Link |
|---|---|
| JP (1) | JP3172746B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6247246B1 (en) | 1998-05-27 | 2001-06-19 | Denver Instrument Company | Microwave moisture analyzer: apparatus and method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6656252B2 (en) | 2001-08-22 | 2003-12-02 | Daiso Co., Ltd. | Polymer separation membrane |
-
1995
- 1995-06-09 JP JP14306195A patent/JP3172746B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6247246B1 (en) | 1998-05-27 | 2001-06-19 | Denver Instrument Company | Microwave moisture analyzer: apparatus and method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08332362A (en) | 1996-12-17 |
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