Method for preparing cyclic polycarbonate oligomer mixtures

Claim 1

A method for preparing a composition comprising cyclic polycarbonate or thiol analog oligomers which comprises the steps of: I. contacting (A) a composition comprising (1) at least one compound selected from the group consisting of bishaloformates and thiol analogs thereof, said compound having the formula R(Y.sup.1 COX).sub.2, (III) or a mixture thereof with (2) at least one difunctional compound having the formula R(Y.sup.3 H).sub.2, (IV) or an alkali metal salt thereof; wherein at least about 60% of the total number of R values are aromatic organic radicals and the balance thereof are aliphatic, alicyclic or aromatic organic radicals, X is chlorine or bromine, each Y 1 is independently oxygen or sulfur and each Y 3 is independently sulfur when the corresponding R is aliphatic or alicyclic and oxygen or sulfur when the corresponding R is aromatic; with (B) at least one oleophilic aliphatic or heterocyclic tertiary amine and (C) an aqueous alkali metal hydroxide solution having a concentration of about 0.1-16M; said contact being effected under conditions resulting in high dilution of (A), or the equivalent thereof, in a substantially non-polar organic liquid which forms a two-phase system with water, and subsequently II. separating the resulting cyclic oligomer mixture from at least a portion of any high polymer and insoluble material present.

Claim 2

A method for preparing a composition comprising cyclic polycarbonate or thiol analog oligomers which comprises the steps of: I. contacting (A) a composition comprising (1) at least one compound selected from the group consisting of bishaloformates and thiol analogs thereof, said compound having the formula R(Y.sup.1 COX).sub.2, (III) or a mixture thereof with (2) at least one difunctional compound having the formula R(Y.sup.3 H).sub.2, (IV) or an alkali metal salt thereof; wherein at least about 60% of the total number of R values are aromatic organic radicals and the balance thereof are aliphatic, alicyclic or aromatic organic radicals, X is chlorine or bromine, each Y 1 is independently oxygen or sulfur and each Y 3 is independently sulfur when the corresponding R is aliphatic or alicyclic and oxygen or sulfur when the corresponding R is aromatic; with (B) at least one oleophilic aliphatic or heterocyclic tertiary amine and (C) an aqueous alkali metal hydroxide solution having a concentration of about 0.1-16M; said contact being effected under conditions resulting in high dilution of (A), or the equivalent thereof, in a substantially non-polar organic liquid which forms a two-phase system with water, and subsequently II. separating the resulting cyclic oligomer mixture from at least a portion of any high polymer and insoluble material present.

Claim 7

A method for preparing a composition comprising cyclic polycarbonate or thiol analog oligomers which comprises effecting contact in a two-phase system between (A) a composition comprising (1) at least one compound selected from the group consisting of bishaloformates and thiol analogs thereof, said compounds having the formula R(Y.sup.1 COX).sub.2, (III) or a mixture thereof with (2) at least one difunctional compound having the formula R(Y.sup.3 H).sub.2, (IV) or an alkali metal salt thereof; wherein at least about 60% of the total number of R values are aromatic organic radicals and the balance thereof are aliphatic, alicyclic or aromatic organic radicals, X is chlorine or bromine, each Y 1 is independently oxygen or sulfur and each Y 3 is sulfur when R is aliphatic or alicyclic and oxygen or sulfur when the corresponding R is aromatic; (B) at least one aliphatic or heterocyclic tertiary amine which has an organic-aqueous partition coefficient greater than 1; and (C) an aqueous alkali metal hydroxide solution having a concentration of about 0.1-10M; by gradually adding (A) and at least a portion of (B) and (C) to a substantially non-polar organic liquid which forms a two-phase system with water, or to a mixture of said liquid with water, said liquid or mixture being maintained at a temperature in the range of about 0°-50° C.; the amount of (A) used being up to about 0.7 mole for each liter of said organic liquid present in the reaction system, and the molar proportions of (A), (B) and (C) being approximately as follows: (B):(A)--0.06-2.0:1 (C):(A)--2-3:1; and recovering the cyclic oligomers thus formed.

Claim 8

A method for preparing a composition comprising cyclic polycarbonate or thiol analog oligomers which comprises effecting contact in a two-phase system between (A) a composition comprising (1) at least one compound selected from the group consisting of bishaloformates and thiol analogs thereof, said compounds having the formula R(Y.sup.1 COX).sub.2, (III) or a mixture thereof with (2) at least one difunctional compound having the formula R(Y.sup.3 H).sub.2, (IV) or an alkali metal salt thereof; wherein at least about 60% of the total number of R values are aromatic organic radicals and the balance thereof are aliphatic, alicyclic or aromatic organic radicals, X is chlorine or bromine, each Y 1 is independently oxygen or sulfur and each Y 3 is sulfur when R is aliphatic or alicyclic and oxygen or sulfur when the corresponding R is aromatic; (B) at least one aliphatic or heterocyclic tertiary amine which has an organic-aqueous partition coefficient greater than 1; and (C) an aqueous alkali metal hydroxide solution having a concentration of about 0.1-10M; by gradually adding (A) and at least a portion of (B) and (C) to a substantially non-polar organic liquid which forms a two-phase system with water, or to a mixture of said liquid with water, said liquid or mixture being maintained at a temperature in the range of about 0°-50° C.; the amount of (A) used being up to about 0.7 mole for each liter of said organic liquid present in the reaction system, and the molar proportions of (A), (B) and (C) being approximately as follows: (B):(A)--0.06-2.0:1 (C):(A)--2-3:1; and recovering the cyclic oligomers thus formed.