Interfacially polymerized polyester films

• US 5,650,479 A
• Filed: 06/06/1995
• Issued: 07/22/1997
• Est. Priority Date: 06/06/1995
• Status: Expired due to Fees

• Current Assignee: Cynara Co. (Schlumberger NV)
• Original Assignee: Cynara Co. (Schlumberger NV)
• Inventors: Rickle, Gregory K., Glugla, Paul G., Bales, Stephen E., Smith, Bethanne L.
• Primary Examiner(s): BOYKIN, TERRESSA M
• Application Number:
  US08/468,839
• Time in Patent Office: 777 Days
• Field of Search: 210/500.21, 210/500.26, 95/43, 95/54, 528/176, 528/193, 528/194
• US Class Current: 528/194
• CPC Class Codes: B01D 53/228 characterised by specific membranes
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 69/1251 by interfacial polymerisation
• CPC Class Codes: B01D 71/48 Polyesters
• CPC Class Codes: C08G 63/133 Hydroxy compounds containing aromatic rings
• CPC Class Codes: C08G 63/40 Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
• CPC Class Codes: C08G 63/79 Interfacial processes, i.e. processes involving a reaction at the interface of two non-miscible liquids

Abstract

The present invention concerns a polyester gas separation membrane which is obtained by the interfacial polymerization of benzenetricarbonyl trihalide or benzene tetracarbonyl tetrahalide in a water-insoluble organic solvent in one phase and a variety of polyfunctional phenols present as the di- or tri-salt in a mixture of water and phase transfer agent and a water-soluble organic solvent in the second phase. The present invention also includes the polyester membrane itself, its methods of preparation and the use of the membranes to separate gas mixtures, such as carbon dioxide and methane, helium and methane and the like.

Claims

1. A crosslinked polyester glassy polymer in the form of a membrane produced by interfacial polymerization, said polymer including ##STR13## trifunctional groups or ##STR14## tetrafunctional groups having the general structure:

##STR15## A is selected from the group consisting of;

##STR16## A¹ is selected from the group consisting of;

##STR17## R¹, R², and R³ are each independently selected from one or more difunctional aromatic groups --O--Q¹ --O--, --O--Q² --O--, or --O--Q³ --O--, wherein Q¹, Q², and Q³ each independently contain 1-4 aromatic groups optionally connected by a direct bond, --CH₂ --, C(CH₃)₂, C(CF₃)₂, --O--, --S--, ##STR18## C═

O, --N═

N--, --CH═

CH--, --C.tbd.C--, --N(R¹²)--, wherein R¹² is CH₃ or CH₃ CH₂ --, and ##STR19## wherein the oxygen atoms are attached directly to the same or a different aromatic ring.

2. The crosslinked polyester glassy polymer of claim 1 wherein R¹, R², and R³ are identical, and Q¹, Q², and Q³ are identical.

3. The crosslinked polyester glassy polymer of claim 2 wherein the polymer is of structure I.

4. The crosslinked polyester glassy polymer of claim 3 wherein R¹, R², and R³ are selected from the group consisting of --O--Q¹ --O, --O--Q² --O--, and --O--Q³ --O wherein each Q¹, Q², and Q³ are each independently selected from:

##STR20## wherein R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently selected from H, CH₃, CH₃ CH₂, F, Cl, or Br; and

wherein R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently selected from H, CH₃, CH₃ CH₂, F, Cl, or Br; and

Y is selected from the group consisting of a direct bond, --CH₂ --, C(CH₃)₂, C(CF₃)₂, ##STR21## wherein R¹² is CH₃ or CH₃ CH₂ -- and ##STR22##

5. The crosslinked polyester glassy polymer of claim 4 wherein O--Q¹ --O--, --O--Q² --O--, and --O--Q³ --O are selected from the group consisting of:

##STR23##

6. The crosslinked polyester glassy polymer of claim 4 wherein Q¹, Q², Q³ are selected from the group consisting of ##STR24##

7. The crosslinked polyester glassy polymer of claim 2 wherein the polymer is structure II.

8. The crosslinked polyester glassy polymer of claim 7 wherein R¹, R², and R³ are selected from the group consisting of --O--Q¹ --O, --O--Q² --O--, and --O--Q³ --O wherein each Q¹, Q², and Q³ are each independently selected from:

##STR25## wherein R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently selected from H, CH₃, CH₃ CH₂, F, Cl, Br; and

Y is selected from the group consisting of a direct bond, --CH₂ --, C(CH₃)₂, C(CF₃)₂, ##STR26## --CH═

CH--, --C.tbd.C--, --N(R¹²)--, wherein R¹² is CH₃ or CH₃ CH₂ -- and ##STR27##

9. The crosslinked polyester glassy polymer of claim 8 wherein O--Q¹ --O--, and --O--Q² --O--, and --O--Q³ --O are selected from the group consisting of:

##STR28##

10. The crosslinked polyester glassy polymer of claim 9 wherein Q¹, Q², Q³ are selected from the group consisting of ##STR29##

11. The crosslinked polyester glassy polymer of claim 1 wherein the polymer is in combination with a mechanical support structure.

19. A process for the selective gas separation of a mixture of gases, which process comprises:

(a) contacting the mixture of gases under pressure with one surface of a membrane of the crosslinked polyester glassy polymer of claim 1; and

(b) removing the gas which permeates selectively through the membrane.

12. A process for producing a gas permeable crosslinked polyester glassy polymer as a membrane, which process comprises:

(a) interfacially polymerizing;

(i) an essentially monomeric aromatic group containing reactant having two or more alkali metal substituted phenoxy functional groups per reactant molecule in a mixture of water, a water soluble polar organic solvent, and a phase transfer agent, and

(ii) an aromatic triacid trihalide selected from the group consisting of;

##STR30## an aromatic tetraacid tetrahalide selected from the group consisting of;

##STR31## wherein X is chloro or bromo, in one or more water insoluble nonpolar aprotic solvents at a temperature of between about 0° and

90°

C. for between about 1 sec and 3 hr. in the presence of a phase transition catalyst, and

(b) removing the crosslinked polyester glassy polymer membrane formed at the interface surface of the immiscible liquids formed in step (a);

(c) quenching the crosslinked polyester glassy polymer membrane formed in step (b) in one or more organic solvents optionally in the presence of water at ambient conditions for between about 0.1 sec and 1 min; and

(d) drying the crosslinked polyester glassy polymer of step (c) at ambient temperature at between about 14-20 hr or at about 50°

-120°

C.

13. The process of claim 12 wherein the polymer has structure I.

14. The process of claim 13 wherein in step (a) R¹, R², and R³ are selected from the group consisting of the polyalkali metal salts of --HO--Q¹ --OH, --HO--Q² --OH--, and --HO--Q³ --OH wherein each Q¹, Q², and Q³ are each independently selected from:

##STR32## wherein R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independently selected from H, CH₃, CH₃ CH₂, F, Cl, or Br, and

Y is selected from the group consisting of a direct bond, --CH₂ --, --C(CH₃)₂, --C(CF₃)₂, ##STR33## ═

C═

O, --N═

N--, --CH═

CH--, --C.tbd.C--, --N(R¹²)--, wherein R¹² is CH₃ or CH₃ CH₂ -- and ##STR34##

15. The process of claim 14 wherein the monomeric aromatic group containing reactant have two alkali metal substituted phenoxy functional groups per reactant molecule is selected from the alkali metal salts of difunctional phenols selected from the group consisting of:

##STR35## and X is chloro.

16. The process of claim 12 wherein Q¹, Q², Q³ are selected from the group consisting of ##STR36##

17. The process of claim 12 wherein step (a) is performed in the presence of a mechanical support at the interface and the polymer and support are present in steps (b), (c), and (d).

18. The process of claim 17 wherein Q¹, Q², Q³ are selected from the group consisting of ##STR37##

20. The process of claim 18 wherein the mixture of gases in step (a) consists essentially of a mixture of gases selected from CO₂, CH₄, hydrogen, helium, nitrogen, oxygen, water, and CH₃ --CH₃.

21. A process for the selective gas separation of a mixture of gases, which process comprises:

(a) contacting the mixture of gases under pressure with one surface of a crosslinked polyester glassy polymer membrane produced by the process of claim 12; and

(b) removing the gas which permeates selectively through the membrane.

22. The process of claim 21 wherein the mixture of gases in step (a) consists essentially of a mixture of gases selected from CO₂, CH₄, hydrogen, helium, nitrogen, oxygen, water, and CH₃ CH₃.

23. The process of claim 12 which further includes after step (d):

(e) contacting the crosslinked polyester glassy polymer membrane of step (d) in a non-aqueous solvent with ultraviolet radiation in the amount of between about 0.1 to 10 J/cm².