Method for preparation of copolyorganosiloxanecarbonates of high clarity
View Patent ↗Copolyorganosiloxanecarbonates are prepared by first preparing an oligomeric aromatic polycarbonate, such as an oligomeric bisphenol A polycarbonate, in the presence of a tertiary amine as the only catalyst species; contacting the oligomeric polycarbonate mixture with a polyorganosiloxane bis(aryl)chloroformate, such as the bischloroformate of hydroxy-terminated eugenol polydimethylsiloxane; and introducing phosgene and/or chain termination agent either continuously or in stages. A feature of the process is the presence of dihydroxyaromatic compound in only one charge, at the beginning. The products have excellent physical properties, including transparency.
1. A method for preparing a copolyorganosiloxanecarbonate which comprises:
contacting at least one dihydroxyaromnatic compound with phosgene, the molar ratio of phosgene to dihydroxyaromatic compound being in the range of about 0.3-0.85:1, in an alkaline mixed aqueous-organic liquid at a pH in the range of about 9-12, in the presence of at least one tertiary amine as the only catalytic species present and, optionally, at least one monohydroxyaromatic compound or chloroformate thereof as chain termination agent, thereby producing an oligomeric aromatic polycarbonate mixture;
combining said mixture with a reagent consisting essentially of at least one polyorganosiloxane bis(aryl)chloroformate at a pH in the range of about 10.5-13.5, optionally with additional introduction of at least one of (1) phosgene and (2) at least one monohydroxyaromatic compound or chloroformate thereof as chain termination agent, thereby forming a copolyorganosiloxanecarbonate oligomer mixture; and
adding phosgene and, optionally, chain termination agent to said copolyorganosiloxanecarbonate-containing mixture to afford a copolyorganosiloxanecarbonate of a desired molecular weight.
2. A method according to claim 1 wherein the oligomeric aromatic polycarbonate comprises structural units of the formula
wherein R1 is a divalent aromatic radical.
3. A method according to claim 2 wherein R 1 has the formula
— A 1 —Y—A 2 —, (II)
wherein each of A 1 and A 2 is a monocyclic divalent aromatic radical and Y is a single bond or a bridging radical in which one or two atoms separate A 1 from A 2 .
4. A method according to claim 3 wherein the oligomeric aromatic polycarbonate is a bisphenol A polycarbonate.
5. A method according to claim 1 wherein the polyorganosiloxane bis(aryl)chloroformate has the formula
wherein:
A 3 is an unsubstituted or substituted divalent aromatic radical,
R 2 is a C 2-8 divalent aliphatic radical,
each R 3 is independently a C 1-13 organic radical, and
n is from 1 to 1,000.
6. A method according to claim 5 wherein A 3 is 2-methoxy-1,4-phenylene with the methoxy group ortho to the oxygen atom, R 2 is trimethylene, each R 3 is methyl and n has in average value in the range of about 10-100.
7. A method according to claim 6 wherein n has an average value in the range of about 30-60.
8. A method according to claim 6 wherein the proportion of chloroformate end groups in the polyorganosiloxane bis(aryl)chloroformate, as a percentage of total end groups, is at least about 90%.
9. A method according to claim 6 wherein the polyorganosiloxane bis(aryl)chloroformate is in the form of a crude reaction mixture in solution in an organic liquid.
10. A method according to claim 1 wherein the ratio of hydroxide groups to chloroformate groups is at least about 4:1.
11. A method according to claim 10 wherein the ratio of hydroxide groups to chloroformate groups is from about 10:1 to about 3,000:1.
12. A method according to claim 1 wherein the polyorganosiloxane bis(aryl)chloroformate is added to the oligomeric aromatic polycarbonate.
13. A method according to claim 1 wherein the organic liquid is methylene chloride.
14. A method according to claim 1 wherein the tertiary amine is triethyl amine.
15. A method according to claim 1 wherein pH is controlled by addition of aqueous sodium hydroxide solution.
16. A method according to claim 1 wherein the chain termination agent is phenol, p-cumylphenol or a chloroformate thereof.
17. A method according to claim 1 wherein phosgene is introduced throughout the process.
18. A method according to claim 1 wherein phosgene is introduced during oligomeric aromatic polycarbonate preparation and after addition of the polyorganosiloxane bis(aryl)chloroformate.
19. A method according to claim 1 wherein chain termination agent is introduced throughout the process.
20. A method according to claim 1 wherein chain termination agent is introduced during oligomeric aromatic polycarbonate preparation and after addition of the polyorganosiloxane bis(aryl)chloroformate.
21. A method for preparing a copolyorganosiloxanecarbonate which comprises:
contacting bisphenol A with phosgene, the molar ratio of phosgene to bisphenol A being in the range of about 0.30-0.85:1, in an alkaline mixed aqueous-methylene chloride liquid at a pH in the range of about 9-12, in the presence triethylamine as the only catalytic species present and, optionally, at least one of phenol, p-cumylphenol and chloroformates thereof as chain termination agent, thereby producing an oligomeric aromatic polycarbonate mixture;
combining said mixture with a reagent consisting essentially of at least one polyorganosiloxane bis(aryl)chloroformate having the formula
wherein A 3 is 2-methoxy-1,4-phenylene with the methoxy group ortho to the oxygen atom, R 2 is trimethylene, each R 3 is methyl and n has an average value in the range of about 5-60, with an oligomeric bisphenol A polycarbonate in a mixed aqueous-methylene chloride liquid and in the presence of triethylamine as the only catalytic species, at a pH in the range of about 10.5-13.5, optionally with additional introduction of at least one of phosgene and phenol, p-cumylphenol or a chloroformate thereof as chain termination agent, the ratio of hydroxide groups to chloroformate groups being from about 10:1 to about 3,000:1 and the proportion of said polyorganosiloxane bis(aryl)chloroformate being such as to yield a product containing about 0.1-30.0% by weight organosiloxane units, thereby forming a copolyorganosiloxanecarbonate oligomer mixture; and
adding phosgene and, optionally, chain termination agent to said copolyorganosiloxanecarbonate-containing mixture to afford a copolyorganosiloxanecarbonate of a desired molecular weight.
22. A method according to claim 21 wherein phosgene is introduced throughout the process.
23. A method according to claim 21 wherein phosgene is introduced during oligomeric aromatic polycarbonate preparation and after addition of the polyorganosiloxane bis(aryl)chloroformate.
24. A method according to claim 21 wherein chain termination agent is introduced throughout the process.
25. A method according to claim 21 wherein chain termination agent is introduced during oligomeric aromatic polycarbonate preparation and after addition of the polyorganosiloxane bis(aryl)chloroformate.
26. A method for preparing a copolyorganosiloxanecarbonate which comprises:
contacting at least one dihydroxyaromatic compound with phosgene, the molar ratio of phosgene to dihydroxyaromatic compound being in the range of about 0.3-0.85:1, in an alkaline mixed aqueous-organic liquid at a pH in the range of about 9-12, in the presence of at least one trialkylamine as the only catalytic species present and, optionally, at least one monohydroxyaromatic compound or chloroformate thereof as chain termination agent, the amount of dihydroxyaromatic compound being at least about 90% by weight of the total to be employed, thereby producing an oligomeric aromatic polycarbonate mixture;
combining said mixture with a reagent consisting essentially of at least one polyorganosiloxane bis(aryl)chloroformate at a pH in the range of about 10.5-13.5, optionally with additional introduction of at least one of (1) phosgene and (2) at least one monohydroxyaromatic compound or chloroformate thereof as chain termination agent, thereby forming a copolyorganosiloxanecarbonate oligomer mixture;
introducing the balance, up to about 10% by weight, of said dihydroxyaromatic compound at one or more than one point subsequent to said initial introduction thereof; and
adding phosgene and, optionally, chain termination agent to said copolyorganosiloxanecarbonate-containing mixture to afford a copolyorganosiloxanecarbonate of a desired molecular weight.