公开(公告)号：WO1982003868A1

公开(公告)日：1982-11-11

申请号：PCT/US1981000556

申请日：1981-04-28

Applicant: DIAMOND SHAMROCK CORP

Inventor： DIAMOND SHAMROCK CORP ,  BACZEK STANLEY K ,  MCCAIN HOWARD G

IPC: C08K05/02

CPC classification number: C08J5/2293 ,  C08J2327/18

Abstract: Normally solid copolymers of a fluorinated vinyl monomer and a perfluorinated vinyl compound having a carboxyl and/or sulfonyl group attached directly to the perfluorinated vinyl group or indirectly through an alkyl or ether linkage have been found to be soluble in low molecular weight polymers of perhalogenated alkyl ethers, low molecular weight polymers of perhalogenated alkyls and perfluoro kerosenes, each of said solvent materials having boiling points between about 200 C and 350 C. The copolymeric material dissolved in accordance with the instant invention can readily be resolidified by solvent removal and hydrolyzed or converted to the salt form to become a cation exchange material having an equivalent weight in the range of 1000 to 1600. Unreinforced sheet or shaped membrane can be formed using the dissolved copolymeric material and may be made by casting or coating on a removable backing sheet followed by removal of the solvent to result in a continuous, pore-free sheet or shaped membrane. Multiple coatings or other techniques can be used to build up the desired thickness of the membrane. Reinforced sheet or shaped membrane may be produced by similar manufacturing techniques wherein the casting or coating of the membrane is upon a reinforcing backing fabric, which can be polytetrafluoroethylene mesh or the like. Such reinforcing fabrics may be dipped into hot solutions of the copolymeric material using mandrel, frame, continuous roll coating techniques or other methods known to those familiar with the coating art. In the case of reinforced sheet material, no removable backing is necessary in preparing the reinforced membrane sheets. The copolymeric material which is used in making the sheet or shaped membrane can be a single material or it can be of various equivalent weights, structures (carboxyl or sulfonyl, mixtures of same, or the sheets or shaped membranes can be layered of the same or different materials). It is sometimes preferred to purify the surface between coatings by using Freon-type solvents in the process of making asymmetric membranes, when utilizing a multiple coating technique. Such purifications result in better bonds between the layers, especially when different materials are utilized in adjacent layers, although such is not necessary in the practice of the instant invention.

Abstract translation: 已经发现通常将含氟乙烯基单体和具有羧基和/或磺酰基的全氟化乙烯基化合物的固体共聚物直接连接到全氟化乙烯基上或通过烷基或醚键间接连接，已经被发现可溶于低卤代烷基的低分子量聚合物 醚，全卤代烷基和全氟煤油的低分子量聚合物，每种所述溶剂材料的沸点在约200℃至350℃之间。 根据本发明溶解的共聚物质可以通过溶剂去除而容易地重新固化，并水解或转化为盐形式，成为当量重量在1000至1600范围内的阳离子交换材料。非增强片或成形膜可以是 使用溶解的共聚物材料形成，并且可以通过在可移除的背衬片上浇铸或涂覆，然后除去溶剂来制备，以产生连续的，无孔的片状或成形的膜。 可以使用多重涂层或其它技术来建立膜的所需厚度。 可以通过类似的制造技术来制造增强片或成形膜，其中膜的铸造或涂层在可以是聚四氟乙烯网等的加强背衬织物上。 这种增强织物可以使用心轴，框架，连续辊涂技术或熟悉涂层领域的那些已知的其它方法浸入共聚物的热溶液中。 在增强片材的情况下，在制备增强膜片时不需要可移除的背衬。 用于制造片材或成形膜的共聚物材料可以是单一材料，也可以是各种等效的结构（羧基或磺酰基，它们的混合物，或片状或成形的膜可以分层， 不同的材料）。 有时优选在使用多重涂覆技术时，在制造不对称膜的过程中通过使用氟利昂型溶剂来净化涂层之间的表面。 这种纯化导致层之间的更好的结合，特别是当在相邻层中使用不同的材料时，尽管在本发明的实践中不是必需的。

公开(公告)号：WO1982003802A1

公开(公告)日：1982-11-11

申请号：PCT/US1981000557

申请日：1981-04-28

Applicant: DIAMOND SHAMROCK CORP

Inventor： DIAMOND SHAMROCK CORP ,  BACZEK STANLEY K ,  MCCAIN HOWARD G

IPC: B05D05/12

CPC classification number: H01M8/1004 ,  C08J5/2237 ,  C08J2327/18 ,  C25B9/10 ,  H01M2/1613 ,  H01M2/162 ,  H01M2/1626 ,  H01M2/1673 ,  H01M8/1023 ,  H01M8/1039 ,  H01M8/106 ,  H01M8/1081 ,  H01M2300/0014 ,  Y02P70/56

Abstract: Normally solid copolymers of a fluorinated vinyl monomer and a perfluorinated vinyl compound having a carboxyl and/or sulfonyl group attached directly to the perfluorinated vinyl group or indirectly through an alkyl or ether linkage have been found to be soluble in low molecular weight polymers of perhalogenated alkyl ethers, low molecular weight polymers of perhalogenated alkyls and perfluoro kerosenes, each of said solvent materials having boiling points between about 200 C and 350 C. The copolymeric material dissolved in acordance with the instant invention can readily be resolidified by solvent removal and hydrolyzed or converted to the salt form to become a cation exchange material having an equivalent weight in the range of 1000 to 1600. Membrane coated cathodes can be formed using the dissolved copolymeric material and may be made by casting or coating a foraminous cathode followed by removal of the solvent to result in a continuous, pore-free coating of membrane on the cathode. Multiple coatings or other techniques can be used to build up the desired thickness of the membrane. Reinforced membrane may be produced by similar manufacturing techniques wherein the casting or coating of the membrane is upon a reinforcing backing fabric, which can be polytetrafluoroethylene mesh or the like is first wrapped around the foraminous cathode. The copolymeric material which is used in making the membrane coated cathode can be a single material or it can be of various equivalent weights, structures (carboxyl or sulfonyl, mixtures of same, or can be layers of the same or different materials).

Abstract translation: 已经发现通常将含氟乙烯基单体和具有羧基和/或磺酰基的全氟化乙烯基化合物的固体共聚物直接连接到全氟化乙烯基上或通过烷基或醚键间接连接，已经被发现可溶于低卤代烷基的低分子量聚合物 醚，全卤代烷基和全氟煤油的低分子量聚合物，每种所述溶剂材料的沸点在约200℃至350℃之间。 根据本发明溶解的共聚物质可以通过溶剂去除而容易地重新固化，并水解或转化为盐形式成为当量重量在1000至1600范围内的阳离子交换材料。膜涂覆的阴极可以使用 溶解的共聚物材料，并且可以通过浇铸或涂覆多孔阴极，然后除去溶剂来制造，从而在阴极上形成膜的连续，无孔的涂层。 可以使用多重涂层或其它技术来建立膜的所需厚度。 加强膜可以通过类似的制造技术制造，其中膜的浇铸或涂层在加强背衬织物上，其可以是聚四氟乙烯网或类似物首先缠绕在多孔阴极上。 用于制造膜涂覆阴极的共聚物可以是单一材料，也可以是各种等效的结构（羧基或磺酰基，相同的混合物，或可以是相同或不同材料的层）。

公开(公告)号：EP0077326A4

公开(公告)日：1983-07-26

申请号：EP81901634

申请日：1981-04-28

Applicant: DIAMOND SHAMROCK CORP

Inventor： BACZEK STANLEY K ,  MCCAIN G HOWARD

IPC: C08J5/22 ,  C25B9/10 ,  H01M2/16 ,  H01M8/10 ,  B05D5/12

CPC classification number: H01M8/1004 ,  C08J5/2237 ,  C08J2327/18 ,  C25B9/10 ,  H01M2/1613 ,  H01M2/162 ,  H01M2/1626 ,  H01M2/1673 ,  H01M8/1023 ,  H01M8/1039 ,  H01M8/106 ,  H01M8/1081 ,  H01M2300/0014 ,  Y02P70/56

Abstract: Normally solid copolymers of a fluorinated vinyl monomer and a perfluorinated vinyl compound having a carboxyl and/or sulfonyl group attached directly to the perfluorinated vinyl group or indirectly through an alkyl or ether linkage have been found to be soluble in low molecular weight polymers of perhalogenated alkyl ethers, low molecular weight polymers of perhalogenated alkyls and perfluoro kerosenes, each of said solvent materials having boiling points between about 200 C and 350 C. The copolymeric material dissolved in acordance with the instant invention can readily be resolidified by solvent removal and hydrolyzed or converted to the salt form to become a cation exchange material having an equivalent weight in the range of 1000 to 1600. Membrane coated cathodes can be formed using the dissolved copolymeric material and may be made by casting or coating a foraminous cathode followed by removal of the solvent to result in a continuous, pore-free coating of membrane on the cathode. Multiple coatings or other techniques can be used to build up the desired thickness of the membrane. Reinforced membrane may be produced by similar manufacturing techniques wherein the casting or coating of the membrane is upon a reinforcing backing fabric, which can be polytetrafluoroethylene mesh or the like is first wrapped around the foraminous cathode. The copolymeric material which is used in making the membrane coated cathode can be a single material or it can be of various equivalent weights, structures (carboxyl or sulfonyl, mixtures of same, or can be layers of the same or different materials).

Abstract translation: 已发现氟化乙烯基单体和具有羧基和/或磺酰基基团的全氟化乙烯基化合物的通常固体共聚物直接连接到全氟化乙烯基基团上或通过烷基或醚键间接连接已被发现可溶于全卤代烷基的低分子量聚合物 醚，全卤代烷基和全氟代煤油的低分子量聚合物，每种所述溶剂材料的沸点在约20℃和35℃之间。 根据本发明溶解的共聚物材料可以通过溶剂去除容易地重新固化，并水解或转化成盐形式，从而变成当量重量在1000至1600范围内的阳离子交换材料。膜涂覆的阴极可以使用 溶解的共聚物材料并且可以通过铸造或涂覆多孔阴极然后除去溶剂以在阴极上产生膜的连续无孔涂层来制备。 可以使用多种涂层或其他技术来形成所需厚度的膜。 增强膜可以通过类似的制造技术制造，其中膜的铸造或涂覆在增强底布上，其可以是聚四氟乙烯网或类似物首先缠绕在多孔阴极上。 用于制造膜涂布阴极的共聚材料可以是单一材料，或者可以具有各种当量，结构（羧基或磺酰基，它们的混合物，或者可以是相同或不同材料的层）。

公开(公告)号：EP0077325A4

公开(公告)日：1983-09-20

申请号：EP81901633

申请日：1981-04-28

Applicant: DIAMOND SHAMROCK CORP

Inventor： BACZEK STANLEY K ,  MCCAIN G HOWARD

IPC: C08J5/22 ,  C08K5/02 ,  C08K5/22

CPC classification number: C08J5/2293 ,  C08J2327/18

Abstract: Normally solid copolymers of a fluorinated vinyl monomer and a perfluorinated vinyl compound having a carboxyl and/or sulfonyl group attached directly to the perfluorinated vinyl group or indirectly through an alkyl or ether linkage have been found to be soluble in low molecular weight polymers of perhalogenated alkyl ethers, low molecular weight polymers of perhalogenated alkyls and perfluoro kerosenes, each of said solvent materials having boiling points between about 200 C and 350 C. The copolymeric material dissolved in accordance with the instant invention can readily be resolidified by solvent removal and hydrolyzed or converted to the salt form to become a cation exchange material having an equivalent weight in the range of 1000 to 1600. Unreinforced sheet or shaped membrane can be formed using the dissolved copolymeric material and may be made by casting or coating on a removable backing sheet followed by removal of the solvent to result in a continuous, pore-free sheet or shaped membrane. Multiple coatings or other techniques can be used to build up the desired thickness of the membrane. Reinforced sheet or shaped membrane may be produced by similar manufacturing techniques wherein the casting or coating of the membrane is upon a reinforcing backing fabric, which can be polytetrafluoroethylene mesh or the like. Such reinforcing fabrics may be dipped into hot solutions of the copolymeric material using mandrel, frame, continuous roll coating techniques or other methods known to those familiar with the coating art. In the case of reinforced sheet material, no removable backing is necessary in preparing the reinforced membrane sheets. The copolymeric material which is used in making the sheet or shaped membrane can be a single material or it can be of various equivalent weights, structures (carboxyl or sulfonyl, mixtures of same, or the sheets or shaped membranes can be layered of the same or different materials). It is sometimes preferred to purify the surface between coatings by using Freon-type solvents in the process of making asymmetric membranes, when utilizing a multiple coating technique. Such purifications result in better bonds between the layers, especially when different materials are utilized in adjacent layers, although such is not necessary in the practice of the instant invention.

公开(公告)号：EP0039364A4

公开(公告)日：1982-02-05

申请号：EP80902258

申请日：1980-10-20

Applicant: DIAMOND SHAMROCK CORP

Inventor： BACZEK STANLEY K ,  MCCAIN G HOWARD

IPC: B01J49/00 ,  C08J5/22 ,  C08J11/08 ,  C25B13/08

CPC classification number: C08J11/08 ,  C08J5/2293 ,  C08J2371/12 ,  Y02W30/701