Process for the modification of aromatic polymers via Friedel-Crafts reactions to produce novel polymers and the use thereof

• US 4,684,376 A
• Filed: 01/30/1986
• Issued: 08/04/1987
• Est. Priority Date: 10/03/1984
• Status: Expired due to Fees

• Current Assignee: Standard Oil Company (BP PLC)
• Original Assignee: Standard Oil Company (BP PLC)
• Inventors: Li, George S., Percec, Elena S.
• Primary Examiner(s): NOT, DEFINED
• Application Number:
  US06/824,128
• Time in Patent Office: 551 Days
• Field of Search: 525/390, 525/462, 525/397, 525/466, 525/467, 525/537, 55/16, 55/158, 55/68, 55/70, 210/500.41, 210/500.4, 210/500.27
• US Class Current: 95/47
• CPC Class Codes: B01D 71/50 Polycarbonates
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/522 Aromatic polyethers
• CPC Class Codes: B01D 71/66 Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
• CPC Class Codes: B01D 71/69 Polysulfonamides
• CPC Class Codes: C08G 65/485 Polyphenylene oxides
• CPC Class Codes: C08G 75/0286 Chemical after-treatment
• CPC Class Codes: Y10S 525/905 Polyphenylene oxide

Abstract

A process for the addition of pendant groups to polyarylenes comprises the steps of charging a reaction vessel with a solution of a polyarylene and a Friedel-Crafts catalyst; said polyarylene having the formula ##STR1## adding to the reaction vessel a pendant forming group G, wherein G is selected from the group consisting of sulfonyl halides, sulfonamide halides, alkylhalides, acylhalides and phosphorus acid halides; heating the contents of the reaction vessel to form a substituted polyarylene having the formula ##STR2## and thereafter recovering the substituted polyarylene. The substituted polyarylenes are novel and have utility as a semipermeable membrane and a process for the separation of gases therewith is also provided.

Claims

1. Novel substituted polyarylene polymers as semipermeable membranes useful for the separation of gases from a mixture containing at least two fractions into enriched fractions of each having the formula ##STR21## wherein each R is independently a C₁ to C₈ aliphatic or a C₅ to C₇ cycloaliphatic radical, an aryl radical having the formula ##STR22## wherein each R₁ is independently a C₁ to C₈ aliphatic radical and p is an integer of 0 to 4, each radical being free of a tertiary alpha-carbon atom;

A is hydrogen, halogen, an aliphatic or an aryl radical;

Y is a dilvalent oxygen or sulflur atom or a carbonate group;

n is an integer of from about 75 to about 10,000; and

wherein G is present in at least five percent of said polyarylene units and is selected from the group consisting of alkyl sulfonyl groups having the formula ##STR23## where R_a is a C₁ to C₂₀ aliphatic radical;

sulfonamide groups having the formula ##STR24## where R₂ and is a C₁ to C₂₀ aliphatic or aryl radical of the formula ##STR25## or a naphthyl radical where R₁ and p are as described above and phosphorus groups.

2. Novel substituted polyarylene polymers, as set forth in claim 1,

wherein Y is oxygen, R is methyl, A is hydrogen and said halogens are selected from the group consisting of F, Cl, Br and I.

3. Novel substituted polyarylene polymers as set forth in claim 2, wherein R_2a of said alkyl sulfonyl is hexadecyl.

4. Novel substituted polyarylene polymers as set forth in claim 2, wherein R₂ of said sulfonamide is methyl.

5. Novel substituted polyarylene polymers as set forth in claim 1, wherein the gases in said mixture are selected from the group consisting of hydrogen, helium, oxygen, nitrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, ammonia, water vapor and C₁ to C₄ hydrocarbons.

6. Novel substituted polyarylene polymers as set forth in claim 5, wherein said mixture of gases comprises carbon dioxide, methane and nitrogen.

7. A process for the separation of gases from a mixture containing at least two gases into two fractions, one fraction being enriched with at least one of said gases and the other fraction being depleted in same, comprising the step of:

contacting the gaseous mixture with a semipermeable membrane in such a manner that a portion of the gaseous mixture selectively passes through the membrane resulting in the enriched fraction being on one side of the membrane and the depleted fraction being on the other side of the membrane, said semipermeable membrane comprising

a substituted polyarylene polymer having the formula ##STR26## wherein each R is independently a C₁ to C₈ aliphatic or a C₅ to C₇ cycloaliphatic radical, an aryl radical having the formula ##STR27## wherein each R₁ is independently a C₁ to C₈ aliphatic radical and p is an integer of 0 to 4, each radical being free of a tertiary alpha-carbon atom;

A is hydrogen, halogen, an aliphatic or an aryl radical;

Y is a divalent oxygen or sulfur atom or a carbonate group;

n is an integer of from about 75 to 10,000; and

wherein G is present in at least five percent of said polyarylene units and is selected from the group consisting of alkyl sulfonyl, sulfonamide and phosphorus groups.

8. A process, as set forth in claim 7, wherein said alkyl sulfonyls have the formula ##STR28## where R_2a is a C₁ to C₂₀ aliphatic radical.

9. A process, as set forth in claim 7, wherein said sulfonamides have the formula ##STR29## where R₂ is a C₁ to C₂₀ aliphatic or aryl radical of the formula ##STR30## or a naphthyl radical where R₁ and p are as described above.

10. A process, as set forth in claim 7, wherein said phosphorus groups have the formula

11. A process, as set forth in claim 7, wherein Y is oxygen, R is methyl, A is hydrogen and said halogens are selected from the group consisting of F, Cl, Br and I.

12. A process, as set forth in claim 8, wherein R_2a of said alkyl sulfonyl is hexadecyl.

13. A process, as set forth in claim 9, wherein R₂ of said sulfonamide is methyl.

14. A process, as set forth in claim 11, wherein the gases in said mixture are selected from the group consisting of hydrogen, helium, oxygen, nitrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, ammonia, water vapor and C₁ to C₄ hydrocarbons.

15. A process, as set forth in claim 14, wherein said mixture of gases comprises carbon dioxide, methane and nitrogen.