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

• US 4,596,860 A
• Filed: 10/03/1984
• Issued: 06/24/1986
• 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:
  US06/657,137
• Time in Patent Office: 629 Days
• Field of Search: 525/390, 525/905, 525/537, 525/467, 525/462
• US Class Current: 525/390
• 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: C08G 65/485 Polyphenylene oxides
• CPC Class Codes: C08G 75/0286 Chemical after-treatment
• CPC Class Codes: Y10S 525/905 Polyphenylene oxide
• CPC Class Codes: Y10T 428/2975 Tubular or cellular

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 catalysts; 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. A process for the addition of pendant groups to polyarylene comprising the steps of charging a reaction vessel with a solution of a polyarylene and a Friedel-Crafts catalyst, said polyarylene having the formula ##STR21## wherein said each R is independently a C₁ to C₈ aliphatic or a C₅ to C₇ cycloaliphatic radical, an aryl radical having the formula ##STR22## where said each R₁ is independently a C₁ to C₈ aliphatic radical and p is an integer of 0 to 4, each said 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 and n is an integer of from about 75 to about 10,000;

adding to said reaction vessel a pendant forming group G, wherein G is derived from a compound selected from the group consisting of

sulfonyl halides having the formula ##STR23## where X is a halogen and R₂ is a C₁ to C₂₀ aliphatic or a naphthyl radical;

a sulfonamide halide having the formula ##STR24## where R₂ is as above and can be the same or different;

alkylhalides having the formula

space="preserve" listing-type="equation">R.sub.3 --X

where X is a halogen and R₃ is a C₅ to C₂₀ aliphatic radical;

acylhalides having the formula ##STR25## where X is a halogen and R₄ is a C₅ to C₂₀ aliphatic or an aryl radical of the formula ##STR26## and where R₁ and p are as described above, phosphorus acid halides having the formula

space="preserve" listing-type="equation">X.sub.q --P--(R.sub.5).sub.3-q

where X is a halogen;

R₅ is selected from the group consisting of R₄, O--R₄ and mixtures thereof and q is an integer of from 1 to 3;

heating the contents of said reaction vessel to form a substituted polyarylene having the formula ##STR27## where G is present in at least five percent of the polyarylene units and R, A, Y, G and n are as described and,

thereafter recovering said substituted polyarylene.

2. A process for the addition of pendant groups, as set forth in claim 1, wherein said polyarylene and Friedel-Crafts catalyst are dissolved in an organic solvent to form a solution.

3. A process for the addition of pendant groups, as set forth in claim 2, wherein said step of heating is conducted at a temperature range of from about 0°

to about 80°

C. and for a period of time of from about four to about 16 hours.

4. A process for the addition of pendant groups, as set forth in claim 3, wherein Y is oxygen, R is methyl and A is hydrogen.

5. A process for the addition of pendant groups, as set forth in claim 4, wherein said halogens are selected from the group consisting of F, Cl, Br and I.

6. A process for the addition of pendant groups, as set forth in claim 5, wherein G is sulfonyl, X of said sulfonyl halide is Cl and R₂ of said sulfonyl halide is hexadecyl.

7. A process for the addition of pendant groups, as set forth in claim 5, wherein G is sulfonamide, X of said sulfonamide halide is Cl and R₂ of said sulfonamide halide is methyl.

8. A process for the addition of pendant groups, as set forth in claim 5, wherein G is alkyl.

9. A process for the addition of pendant groups, as set forth in claim 5, wherein G is acyl.

10. A process for the addition of pendant groups, as set forth in claim 5, wherein G is phosphonyl.