Method for polymerizing aromatic bischloroformate composition to polycarbonate

• US 4,737,573 A
• Filed: 10/10/1986
• Issued: 04/12/1988
• Est. Priority Date: 10/10/1986
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Pyles, Robert A., Silva, James M.
• Primary Examiner(s): ANDERSON, HAROLD
• Application Number:
  US06/917,751
• Time in Patent Office: 550 Days
• Field of Search: 528/371, 528/370, 528/198, 528/199
• US Class Current: 528/371
• CPC Class Codes: C07C 68/02 from phosgene or haloformates
• CPC Class Codes: C07C 69/96 Esters of carbonic or haloformic acids
• CPC Class Codes: C08G 64/28 and phenols
• CPC Class Codes: C08G 64/406 Purifying; Drying
• CPC Class Codes: G11B 7/253 of substrates

Abstract

Bischloroformate oligomer compositions are prepared by passing phosgene into a heterogeneous aqueous-organic mixture containing at least one dihydroxyaromatic compound, with simultaneous introduction of a base at a rate to maintain a specific pH range and to produce a specific volume ratio of aqueous to organic phase. By this method, it is possible to employ a minimum amount of phosgene. The reaction may be conducted batchwise or continuously. The bischloroformate composition may be employed for the preparation of cyclic polycarbonate oligomers or linear polycarbonate, and linear polycarbonate formation may be integrated with bischloroformate composition formation in a batch or continuous process.

Claims

1. A method for preparing a linear polycarbonate which comprises the steps of:

(A) preparing a bischloroformate oligomer composition by passing phosgene into a heterogeneous mixture consisting essentially of water, a substantially inert, substantially water-insoluble organic liquid and at least one dihydroxyaromatic compound in a tank reactor, and simultaneously introducing an aqueous alkali or alkaline earth metal base solution at a rate to maintain the aqueous phase of said mixture at a pH in the range of 8-11;

the temperature of said mixture being maintained in the range of about 15°

-50°

C., the volume ratio of aqueous to organic phase at the conclusion of phosgenation being in the range of about 0.4-1.0;

1 and the total amount of phosgene employed being at least about 1.1 mole per mole of dihydroxyaromatic compound;

said mixture being agitated under conditions sufficient to prevent segregation of the aqueous and organic liquid phases;

(B) passing an interfacial polycarbonate formation catalyst into a mixture of said bischloroformate composition, water and a substantially inert, substantially water-insoluble organic liquid in a tank reactor, with effective agitation, and simultaneously introducing an aqueous alkali or alkaline earth metal base solution at a rate to maintain the aqueous phase of said mixture at a pH in the range of about 10-14, the rate of catalyst addition being adjusted to effect polycarbonate formation under controlled conditions; and

(C) recovering said linear polycarbonate.

2. A method according to claim 1 wherein the interfacial polycarbonate formation catalyst is a tertiary amine, the organic liquid in steps A and B is methylene chloride and the base in steps A and B is sodium hydroxide.

3. A method according to claim 2 wherein the tertiary amine is triethylamine and the dihydroxyaromatic compound has the formula HO-A¹ -Y-A² -OH, wherein each of A¹ and A² is a monocyclic divalent aromatic radical and Y is a bridging radical in which one or two atoms separate A¹ from A².

4. A method according to claim 3 wherein unreacted phosgene is removed from the product of step A by at least one of (1) purging the reaction mixture with an inert gas and (2) continuing addition of base to hydrolyze said phosgene.

5. A method according to claim 3 wherein the dihydroxyaromatic compound is bisphenol A.

6. A method according to claim 5 wherein the pH in step B is in the range of about 11-12.5, and there is also added an effective amount of a monohydroxyaromatic compound to regulate polycarbonate molecular weight.

7. A method according to claim 5 wherein steps A and B are conducted batchwise in the same tank reactor.

8. A method according to claim 5 wherein steps A and B are conducted continuously in two continuous-flow stirred tank reactors in series, and in step A a portion of the dihydroxyaromatic compound and organic liquid are initially present and the remainder are added concurrently with the phosgene and base.

9. A method according to claim 4 wherein the reaction is conducted continuously, with step A being conducted in a continuous-flow stirred tank reactor in which a portion of the dihydroxyaromatic compound and organic liquid are initially present and the remainder are added concurrently with the phosgene and base, and step B in a second continuous-flow stirred tank reactor followed by a further reaction system operating under limited back-mixing conditions.

10. A method according to claim 9 wherein the further reaction system is a continuous-flow tubular reactor containing multiple reaction zones.