Aromatic carbonates

• US 4,096,168 A
• Filed: 10/12/1976
• Issued: 06/20/1978
• Est. Priority Date: 10/12/1976
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Hallgren, John E.
• Primary Examiner(s): Roberts, Elbert L.
• Assistant Examiner(s): Eakin, Molly C.
• Application Number:
  US05/731,493
• Time in Patent Office: 616 Days
• Field of Search: 260/463, 260/47 XA
• US Class Current: 558/268
• CPC Class Codes: B01J 2531/821 Ruthenium
• CPC Class Codes: B01J 2531/822 Rhodium
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 2531/825 Osmium
• CPC Class Codes: B01J 2531/827 Iridium
• CPC Class Codes: B01J 2531/828 Platinum
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/20 Carbonyls
• CPC Class Codes: C07C 68/00 Preparation of esters of carbonic or haloformic acids
• CPC Class Codes: C07C 69/96 Esters of carbonic or haloformic acids
• CPC Class Codes: C08G 64/36 using carbon monoxide

Abstract

An aromatic carbonate process comprising contacting a phenol, carbon monoxide, a base, a Group VIIIB element selected from ruthenium, rhodium, palladium, osmium, iridium or platinum having an oxidation state of plus one. The resulting aromatic mono- and polycarbonates are useful in the preparation of polycarbonates or as polycarbonates, per se, respectively, which can be molded or formed into films, sheets, fibers, laminates or reinforced plastics by conventional techniques.

Claims

1. An improved aromatic carbonate process wherein an aromatic carbonate is formed in the substantial absence of an aromatic salicylate which comprises contacting a phenol with carbon monoxide, a base, and a Group VIIIB element selected from ruthenium, rhodium, palladium, iridium, osmium or platinum having an oxidation state of plus one.

2. The claim 1 process, wherein said element is present in an ionic form.

3. The claim 1 process, further comprising contacting a Group VIIIB element selected from ruthenium, rhodium, palladium, osmium, iridium, or platinum having an oxidation state of at least ×

2 with carbon monoxide and a phenol, prior to contacting the resulting admixture with a base.

4. The claim 1 process, wherein said base is a sterically hindered amine.

5. The claim 1 process, wherein said element is associated with a carbonyl group.

6. The claim 1 process, wherein said element is associated with a halide.

7. The claim 1 process, wherein said element is associated with an inorganic halide compound.

8. The claim 1 process, wherein methylene chloride is employed as a solvent, the base is diisopropylmonoethylamine, the phenol is a phenol, and Group VIIIB element is polypalladium(I)monocarbonyl chloride.

9. The claim 1 process, wherein methylene chloride is employed as a solvent, the base is diisopropylmonoethylamine, the phenol is bis(4-hydroxyphenyl)propane-2,2 and the Group VIIIB element is polypalladium(I)monocarbonyl chloride.

10. The claim 1 process, wherein methylene chloride is employed as a solvent, the base is 2,2,6,6,N-pentamethylpiperidine the phenol is bis(4-hydroxyphenyl)propane-2,2, the Group VIIIB element is polypalladium(I)monocarbonyl bromide.

11. The claim 1 process, wherein methylene chloride is employed as a solvent, the base is 2,2,6,6,N-pentamethylpiperidine, the phenol is a phenol, the Group VIIIB element is platinum in the form of bis(tetrapropylammonium)dicarbonyltetrachloroplatinite(I).

12. The claim 1 process, further comprising, after the preparation of the aromatic carbonate, separating at least a portion of any resulting Group VIIIB element or compound from said carbonate, oxidizing at least a portion of said resulting Group VIIIB element or compound to an oxidation state greater than zero, and recycling at least a portion of said oxidized element in said aromatic carbonate process.

13. An improved aromatic polycarbonate process wherein an aromatic polycarbonate is formed in the substantial absence of an aromatic salicylate which comprises contacting an aromatic polyphenol with carbon monoxide in the presence of a base and a Group VIIIB metal selected from the class consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum having an oxidation state of plus one.

14. An improved aromatic polycarbonate process wherein an aromatic polycarbonate is formed in the substantial absence of an aromatic salicylate which comprises contacting an aromatic bisphenol of the formula:

##STR10## where independently each R¹ and R² is hydrogen, C_1-4 alkyl or phenyl and independently each R³ and R⁴ is hydrogen or C_1-4 alkyl, with carbon monoxide in the presence of a base and a Group VIIIB metal selected from the class consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum having an oxidation state of plus one.

15. The claim 14 process, wherein R¹ and R² are methyl and at least one of R³ and R⁴ is hydrogen.

16. The claim 15 process, wherein the base is a tertiary amine.

17. The claim 16 process, carried out in the presence of an inert solvent.

18. An improved aromatic polycarbonate process wherein a polycarbonate is formed in substantial absence of an aromatic salicylate which comprises contacting an aromatic bisphenol of the formula:

##STR11## with carbon monoxide in the presence of a base and a Group VIIIB metal selected from the class consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum having an oxidation state of plus one.

19. An improved aromatic monocarbonate process wherein an aromatic monocarbonate is formed in substantial absence of an aromatic salicylate which comprises contacting an aromatic phenol of the formula:

space="preserve" listing-type="equation">R.sub.a (OH).sub.x,

where R_a represents an aromatic radical wherein the -OH radical is attached directly to an aromatic ring carbon atom and x is the number 1, with carbon monoxide, a base, and a Group VIIIB element selected from the class consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum having an oxidation state of plus one.

20. The claim 19 process, wherein R_a is selected from carbo- or heteromonocyclic, polycyclic or fused polycyclic radicals.

21. The claim 20 process, wherein the base is a tertiary amine.

22. The claim 21 process, carried out in the presence of an inert solvent.

23. An improved aromatic monocarbonate process wherein an aromatic monocarbonate is formed in substantial absence of an aromatic salicylate which comprises contacting a phenol of the formula:

##STR12## with carbon monoxide, a base, and a Group VIIIB element selected from the class consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum having an oxidation state of plus one.