Novel multicomponent fluid separation membranes

• US 5,085,676 A
• Filed: 12/04/1990
• Issued: 02/04/1992
• Est. Priority Date: 12/04/1990
• Status: Expired due to Term

• Current Assignee: L'Air Liquide SA
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Manos, Phillip, Hayes, Richard A., Ekiner, Okan M.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US07/622,419
• Time in Patent Office: 427 Days
• Field of Search: 55/16, 55/68, 55/158, 264/41, 210/500.23, 210/500.37, 210/500.38, 210/500.39, 210/500.41
• US Class Current: 96/13
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/1212 Coextruded layers
• CPC Class Codes: B01D 71/56 Polyamides, e.g. polyester-amides
• CPC Class Codes: B01D 71/64 Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: B01D 71/641 Polyamide-imides
• CPC Class Codes: B01D 71/643 Polyether-imides
• CPC Class Codes: C08L 2666/18 Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 79/08 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08L 81/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers

Abstract

A process for preparing multicomponent gas separation membranes is disclosed. The process involves casting two or more solutions of polymer, and partially removing solvent from the side of the cast polymer that is to form the gas separation layer of the membrane. The membrane is then quenched to freeze its structure and then the remainder of the solvent removed to form the gas separation membrane.

Claims

1. A multicomponent membrane comprising,

a porous polymeric substrate and a polyamide separating layer for separating gases, wherein said polyamide has the formula ##STR28## where R is one of either ##STR29## or mixtures thereof where Z'"'"', Z", and Z"'"'"' are independently a carbon-carbon single bond, ##STR30## or mixtures thereof, Ar is ##STR31## where Z is a carbon-carbon single bond, ##STR32## or mixtures thereof, n is an integer such that the polymer is of film-forming molecular weight, --X, --X₁, --X₂ and --X₃ are independently hydrogen, alkyl groups of 1 to 6 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, and --Y, --Y₁, --Y₂, --Y₃, --Y₄, --Y₅, --Y₆, --Y₇, --Y₈, --Y₉, --Y10, --Y11, --Y₁₂, --Y₁₃, --Y₁₄, --Y₁₅ independently are X, X₁, X₂, X₃, halogen, or alkyl groups of 1 to 6 carbon atoms.

2. The multicomponent membrane of claim 1 wherein said substrate is selected from the group of polysulfones, polyether sulfones, polyetherimide, polyimide, polyamide, polyesters, or mixtures thereof.

3. The multicomponent membrane of claim 1 wherein Ar is ##STR33## or mixtures thereof.

4. The membrane of claim 3 wherein --R-- is a mixture of ##STR34##

5. The membrane of claim 3 wherein --R-- is a mixture of ##STR35##

6. The multicomponent membrane of claim 1 wherein R is ##STR36##

7. The multicomponent membrane of claim 1 where R is ##STR37##

8. The membrane of claim 1 wherein R is ##STR38##

9. The membrane of claim 1 wherein --R-- is ##STR39##

10. The membrane of claim 1 wherein --R-- is ##STR40##

11. The membrane of claim 1 wherein --R-- is ##STR41##

12. The membrane of claim 1 wherein --R-- is ##STR42##

13. The membrane of claim 1 wherein --R-- is a mixture of ##STR43##

14. The membrane of claim 1 wherein --R-- is a mixture of ##STR44##

15. The membrane of claim 1 wherein --R-- is a mixture of ##STR45##

16. The membrane of claim 1 wherein --R-- is ##STR46##

17. The membrane of claim 1 wherein --R-- is a mixture of ##STR47##

18. The membrane of claim 1 wherein --R-- is ##STR48##

19. The membrane of claim 1 wherein --R-- is a mixture of ##STR49##

20. A multicomponent membrane comprising a porous polymeric substrate and a polyimide separating layer for separating gases wherein said polyimide is an aromatic polyimide comprising repeating units of the formula:

##STR50## wherein R and R'"'"' are selected from the group ##STR51## where --Z-- is a carbon-carbon single bond, ##STR52## alkylene groups of 1 to 5 carbon atoms, --Ar-- is ##STR53## for mixtures thereof where Z'"'"', Z", Z"'"'"' independently are a carbon-carbon single bond, ##STR54## or alkylene groups of 1 to 5 carbon atoms, X, X₁, X₂ and X₃ are independently, hydrogen, alkyl groups of 1 to 5 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or groups, --Y, --Y₁, --Y₂, --Y₃, --Y₄, --Y₅, --Y₆, --Y₇, --Y₈, --Y₉, --Y₁₀, --Y₁₁, --Y₁₂, --Y₁₃, --Y₁₄, and --Y₁₅ independently are --X, --X₁, --X₂, --X₃ or halogen, --Ar'"'"'-- is ##STR55## or mixtures thereof where Z'"'"' has the above-defined meaning, m is 0 to 100 mole percent, n is 0 to 100 mole percent, and (m+n)=100%.

21. The membrane of claim 20 wherein m is 20 to 100 mole percent and n is 20 to 100 mole percent.

22. The membrane of claim 20 wherein said polymeric substrate is selected from the group of polysulfones, polyether sulfones, polyetherimide, polyimide, polyamide, polyesters, or mixtures thereof.

23. The membrane of claim 20 wherein R is ##STR56##

24. The membrane of claim 20 wherein --Ar-- is a mixture of ##STR57##

25. The membrane of claim 20 wherein --Ar-- is ##STR58## or mixtures thereof.

26. The membrane of claim 20 wherein --Ar-- is ##STR59##

27. The membrane of claim 20 wherein --Ar-- is ##STR60##

28. The membrane of claim 20 wherein --Ar-- is ##STR61##

29. The membrane of claim 20 wherein --Ar-- is ##STR62##

30. The membrane of claim 20 wherein --Ar-- is ##STR63##

31. The membrane of claim 20 wherein --Ar-- is ##STR64##

32. The membrane of claim 20 wherein --Ar-- is ##STR65##

33. The membrane of claim 20 wherein R is ##STR66##

34. The membrane of claim 33 wherein --Ar-- is a mixture of ##STR67##

35. The membrane of claim 33 wherein --Ar-- is ##STR68##

36. A process for manufacture of a multicomponent gas separation membrane, comprising providing a solution of a film forming polymer as a first supporting layer, said film forming polymer of said solution being selected from the group of polysulfones, polyether sulfones, polyetherimides, polyimides, polyamide, copolymers thereof, and blends thereof, applying to a surface of said first supporting layer a second solution of a film forming polymer to provide a separating layer to form a nascent membrane of at least two layers, said film forming polymer of said second solution being selected from the group of polyetherimide, polyimide, polyamide, polyesters, polycarbonates, copolycarbonate esters, polyphenylene oxides, polyamideimides, cellulose acetates, ethyl cellulose and mixtures thereof, coagulating said nascent membrane, and drying said nascent membrane to form a multicomponent gas separation membrane.

37. The process of claim 36 wherein said providing of said first layer and said applying of said second solution is performed by coextruding said first solution and said second solution.

38. The process of claim 37 wherein said coextruding yields a membrane in the form of a hollow fiber having said separating layer on the exterior of said fiber.

39. The process of claim 38 wherein said separating layer is in the form of an asymmetric membrane.

40. The process of claim 38 wherein said first layer is from about 25 to about 300 microns in thickness.

41. The process of claim 40 wherein said separating layer is from about 0.05 to about 150 microns in thickness.

42. The process of claim 41 wherein said separating layer is from about 0.05 to about 25 microns in thickness.

43. The process of claim 37 wherein said second solution contains from about 5 to about 50 weight percent film forming polymer.

44. The process of claim 37 wherein said first solution contains from about 15 to about 50 weight percent film forming polymer.

45. The process of claim 36 wherein said nascent membrane is dried to remove solvent from said separating layer prior to said coagulating.

46. The process of claim 36 wherein said film forming polymer of said first solution is selected from the group of polyether sulfones, polysulfones, polyimides, or mixtures thereof, and said film forming polymer of said second solution is a polyamide.

47. The process of claim 46 wherein said polyamide has the formula:

##STR69## where R is one of either ##STR70## of mixtures thereof where Z'"'"', Z", Z"'"'"' are independently a carbon-carbon single bond, ##STR71## or mixtures thereof, Ar is ##STR72## where Z is a carbon-carbon single bond, ##STR73## or mixtures thereof, n is an integer such that the polymer is of film-forming molecular weight, --X, --X₁, --X₂ and --X₃ are independently hydrogen, alkyl groups of 1 to 6 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, and --Y, --Y₁, --Y₂, --Y₃, --Y₄, --Y₅, --Y₆, --Y₇, --Y₈, --Y₉, --Y₁₀, --Y₁₁, --Y₁₂, --Y₁₃, --Y₁₄, --Y₁₅ independently are X, X₁, X₂, X₃, halogen, or alkyl groups of 1 to 6 carbon atoms.

48. The process of claim 47 wherein Ar is ##STR74## or mixtures thereof.

49. The process of claim 48 wherein R is ##STR75##

50. The process of claim 48 wherein --R-- is ##STR76##

51. The process of claim 48 wherein --R-- is ##STR77##

52. The process of claim 48 wherein --R-- is ##STR78##

53. The process of claim 48 wherein --R-- is ##STR79##

54. The process of claim 48 wherein --R-- is ##STR80##

55. The process of claim 48 wherein --R-- is a mixture of ##STR81##

56. The process of claim 48 wherein --R-- is a mixture of ##STR82##

57. The process of claim 48 wherein --R-- is a mixture of ##STR83##

58. The process of claim 48 wherein --R-- is ##STR84##

59. The process of claim 48 wherein --R-- is a mixture of ##STR85##

60. The process of claim 48 wherein --R-- is ##STR86##

61. The process of claim 48 wherein --R-- is a mixture of ##STR87##

62. The process of claim 48 wherein --R-- is a mixture of ##STR88##

63. The process of claim 48 wherein --R-- is a mixture of ##STR89##

64. The process of claim 36 wherein said polyimide is an aromatic polyimide comprising repeating units of the formula:

##STR90## wherein R and R'"'"' are selected from the group ##STR91## where --Z-- is ##STR92## a carbon-carbon single bond or alkylene groups of 1 to 5 carbon atoms, --Ar-- is one of either ##STR93## or mixtures thereof where Z'"'"', Z", Z"'"'"' independently are a carbon-carbon single bond, ##STR94## or alkylene groups of 1 to 5 carbon atoms, X, X₁, X₂ and X₃ are independently, hydrogen, alkyl groups of 1 to 5 carbon atoms, alkoxy groups of 1 to 5 carbon atoms, phenyl or phenoxy groups, --Y, --Y₁, --Y₂, --Y₃, --Y₄, --Y₅, --Y₆, --Y₇, --Y₈, --Y₉, --Y₁₀, --Y₁₁, --Y₁₂, --Y₁₃, --Y₁₄, and --Y₁₅ independently are --X, --X₁, --X₂, --X₃ or halogen, --Ar'"'"'-- is ##STR95## or mixtures thereof where Z'"'"' has the above-defined meaning, m is 0 to 100 mole percent, n is 0 to 100 mole percent, and (m+n)=100%.

65. The process of claim 64 wherein n is 0 to 20 percent and m is 0 to 80-100 percent.

66. The process of claim 64 wherein R is ##STR96##

67. The process of claim 66 wherein --Ar-- is a mixture of ##STR97##

68. The process of claim 66 wherein --Ar-- is ##STR98##

69. The process of claim 66 wherein --Ar-- is ##STR99##

70. The process of claim 66 wherein --Ar-- is ##STR100##

71. The process of claim 66 wherein --Ar-- is ##STR101##

72. The process of claim 66 wherein --Ar-- is ##STR102##

73. The process of claim 66 wherein --Ar-- is ##STR103##

74. The process of claim 66 wherein --Ar-- is ##STR104##

75. The process of claim 66 wherein --Ar-- is a mixture of ##STR105##

76. The process of claim 64 wherein R is ##STR106##

77. The process of claim 76 wherein --Ar-- is a mixture of ##STR107##

78. The process of claim 76 wherein --Ar-- is ##STR108##