Polybenzazole polymers containing indan moieties

• US 5,034,026 A
• Filed: 04/20/1990
• Issued: 07/23/1991
• Est. Priority Date: 04/20/1990
• Status: Expired due to Term

• Current Assignee: Toyobo Company Limited
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Summers, John D., Wessling, Ritchie A.
• Primary Examiner(s): SPITZER, ROBERT H
• Application Number:
  US07/513,316
• Time in Patent Office: 459 Days
• Field of Search: 55/16, 55/68, 55/158, 55/70, 55/73, 55/66
• US Class Current: 95/47
• CPC Class Codes: B01D 71/62 Polycondensates having nitrogen-containing heterocyclic rings in the main chain
• CPC Class Codes: C08G 73/22 Polybenzoxazoles

Abstract

Polybenzazole polymer containing indan moieties may be synthesized. Those polymers can be fabricated into membranes, which are useful for gas separations.

Claims

1. A polybenzoxazole or polybenzothiazole polymer containing a plurality of repeating units which comprise:

(1) a benzo-bis-azole moiety containing a first aromatic group fused with a first and a second azole ring, each azole ring being selected from the group consisting of oxazole and thiazole rings; and

(2) a divalent organic moiety bonded to the 2-carbon of the first azole ring, said divalent organic moiety containing an indan moiety

wherein each indan moiety contains a second aromatic ring fused to a five-membered ring which is saturated, except for the two carbon atoms which are part of the second aromatic group, and each indan moiety is linked to the rest of the polymer by a single bond to the second aromatic group and a single bond to the saturated ring.

2. The polymer of claim 1 wherein each aromatic group is a carbocyclic group comprising no more than about 18 carbon atoms.

3. The polymer of claim 2 wherein the first aromatic group is represented by either of the Formulae:

##STR17## wherein L is a carbonyl moiety, sulfonyl moiety, an oxygen atom, a lower (C_1-6) alkyl group, a halogenated lower alkyl group or a bond.

4. The polymer of claim 2 wherein each azole ring is an oxazole ring.

5. The polymer of claim 2 wherein each azole ring is a thiazole ring.

6. The polymer of claim 2 wherein the second aromatic group is a six-membered ring, and the bond to the second aromatic group is para to either the 1- or 3-carbon of the saturated ring.

7. The polymer of claim 2 wherein the bond to the saturated ring is to the 1- or 3-carbon.

8. The polymer of claim 2 wherein the indan moiety contains substituents of sufficient number and size to inhibit rotation of the indan moiety around single bonds that alters the contour of the polymer chain.

9. The polymer of claim 8 wherein one of the 1- and 3-carbons of the indan moiety has two lower alkyl substituents and the other has one lower alkyl substituent and a bond linking it to other mer units in the polymer.

10. The polymer of claim 9 wherein each lower alkyl substituent is a t-butyl or methyl moiety.

11. The polymer of claim 2 wherein the indan moiety in one mer unit is linked to the 2-carbon of an azole ring in an adjacent mer unit by a divalent linking moiety that does not interfere with the synthesis, fabrication and use of the polymer.

12. The polymer of claim 11 wherein the linking moiety is as a p-phenylene or 4,4'"'"'-biphenylene moiety.

13. The polymer of claim 2 wherein each indan-containing mer unit is represented by the Formula:

##STR18## wherein each R and R'"'"' is independently a hydrogen atom or a lower alkyl group, each Z is an oxygen or a sulfur atom, and A is a bond or divalent linking moiety which does not interfere with the synthesis, fabrication or use of the polymer.

14. The polymer of claim 13 which is represented by the Formula:

##STR19##

15. The polymer of claim 13 which is represented by one of the Formulae:

##STR20##

16. The polymer of claim 15 wherein at least about 50 percent of the mer units in the polymer contain an indan moiety.

17. A membrane comprising a polybenzoxazole or polybenzothiazole polymer that contains a plurality of repeating units which comprise a moiety represented by the Formula:

##STR21## wherein;

each Ar is an aromatic group, each Z is independently an oxygen atom or a sulfur atom,

each R is a hydrogen atom or substituent that does not interfere with the synthesis, fabrication or use of the membrane, and

each A is bond or a divalent linking moiety that does not interfere with the synthesis, fabrication or use of the membrane.

18. The membrane of claim 17 wherein each R is a hydrogen atom, a lower alkyl group or a halogen.

19. The membrane of claim 17 wherein each aromatic group is a six-membered carbocyclic ring.

20. The membrane of claim 17 wherein A is a para-ordered aromatic group.

21. The membrane of claim 17 wherein the membrane is either a flat membrane at least about 10 microns thick and at most about 510 microns thick or a hollow fiber or tube whose walls are at least about 10 microns thick and at least about 200 microns thick.

22. The membrane of claim 21 wherein the polymer contains a plurality of mer units represented by the Formula:

##STR22## wherein each R and R'"'"' is independently a hydrogen atom, a lower alkyl group or a halogen.

23. The membrane of claim 22 wherein essentially all of the mer units in the polymer are mer units illustrated in claim 22.

24. The membrane of claim 21 wherein the polymer contains a plurality of mer units represented by the one of Formulae:

##STR23## wherein each R is a methyl, t-butyl, phenyl or cyclohexyl moiety.

25. The membrane of claim 24 wherein each R is a methyl group or a t-butyl group.

26. The membrane of claim 24 wherein each Z is an oxygen atom.

27. The membrane of claim 24 wherein each Z is a sulfur atom.

28. The membrane of claim 24 wherein at least about 50 percent of the mer units in the polymer are mer units illustrated in claim 24.

29. The membrane of claim 21 wherein at least about 50 percent of the mer units in the polybenzoxazole or polybenzothiazole polymer contain indan moieties.

30. The membrane of claim 21 wherein essentially all of the mer units in the polybenzoxazole or polybenzothiazole polymer contain indan moieties.

31. The membrane of claim 21 wherein the membrane is an isotropic membrane.

32. The membrane of claim 31 wherein the membrane is a hollow fiber or tube, and the membrane walls are at most about 100 microns thick.

33. The membrane of claim 32 which has an outer diameter of between about 30 microns and about 800 microns.

34. The membrane of claim 31 wherein the membrane is a flat film membrane.

35. The membrane of claim 17 wherein the membrane is a composite membrane that contains (a) a discriminating layer containing the polybenzoxazole or polybenzothiazole polymer and (b) a supporting layer.

36. The membrane of claim 35 wherein the discriminating layer is between about 0.01 microns and about 10 microns thick.

37. The membrane of claim 36 wherein the membrane is a hollow fiber having an outer diameter of at least about 30 microns and at most about 800 microns.

38. The membrane of claim 21 wherein the membrane is an asymmetric membrane.

39. The membrane of claim 38 wherein the membrane is a hollow fiber having an outer diameter of at least about 30 microns and at most about 800 microns.

40. The membrane of claim 17 wherein the separation factor of the membrane is at least about 5 for separating oxygen from nitrogen at about 30°

C.

41. The membrane of claim 17 wherein the separation factor of the membrane is at least about 300 for separating hydrogen or helium from methane at about 30°

C.

42. The membrane of claim 17 wherein the separation factor of the membrane is at least about 20 for separating carbon dioxide from methane at about 30°

C.

43. A process for separating a mixture of gases, said process comprising the step of placing the mixture of gases in a higher pressure zone which is divided from a lower pressure zone by a membrane of claim 17 under conditions such that at least one gas permeates through the membrane at a faster rate that another gas in the mixture.

44. The process of claim 43 wherein the pressure in the higher pressure zone is between about 50 psi and about 500 psi higher than the pressure in the lower pressure zone.

45. The process of claim 43 wherein the mixture of gases contains at least two gases selected from the group consisting of hydrogen, helium, oxygen, nitrogen, carbon monoxide, carbon dioxide, water vapor, hydrogen sulfide, ammonia, and light hydrocarbons.

46. The process of claim 43 wherein the membrane contains a discriminating portion in which at least about 50 percent of the mer units are represented by the Formula:

##STR24## wherein each R and R'"'"' is a hydrogen, methyl, t-butyl, phenyl or cyclohexyl moiety.

47. An apparatus comprising:

(1) a higher pressure zone which can maintain a mixture of gases at a relatively high pressure;

(2) a membrane of claim 17;

(3) a low pressure pressure zone,

said elements being arranged such that at least one gas in the high pressure zone enters the low pressure zone by permeating through the membrane but by no other pathway.

48. The apparatus of claim 47, wherein the membrane is a hollow fiber, the high pressure zone is on the inside of the fiber, and the low pressure zone is on the outside of the fiber.

49. The apparatus of claim 47, wherein the membrane is a hollow fiber, the high pressure zone is on the outside of the fiber, and the low pressure zone is on the inside of the fiber.

50. The apparatus of claim 47 wherein the membrane is a flat sheet that separates a vessel into the high pressure zone and the low pressure zone.

51. The apparatus of claim 47 wherein the high pressure zone contains at least two gases, of which at least one is selected from the group consisting of hydrogen, helium, oxygen, nitrogen, carbon monoxide, carbon dioxide, water vapor, hydrogen sulfide, ammonia, and light hydrocarbons.

52. The apparatus of claim 47 wherein the membrane contains a discriminating portion in which at least about 50 percent of the mer units are represented by the Formula:

##STR25## wherein each R and R'"'"' is a hydrogen, methyl, t-butyl, phenyl or cyclohexyl moiety.