Process for producing functional siloxanes of controlled structure

1. A process for preparing a linear hydroxyaryloxy-functional polydialkylsiloxane of the general Formula (I)

wherein Ar is a divalent C 6 to C 30 aryl, alkylaryl or aryloxy group or a residue of a bishydroxy-functional oligomer, each occurrence of R is independently a monovalent C 1 to C 20 alkyl, alkylaryl, or aryl group, n has an average value of from 10 to 400, and m has an average value of from 1.0 to 5.0, wherein the process comprises:

reacting a linear α,ω-bisacyloxypolydiorganosiloxane of the general Formula (II) with at least one bisphenolic compound, or a bishydroxy-functional oligomer thereof, in such a molar ratio that the phenolic groups in the bisphenolic compound or the bishydroxy-functional oligomer thereof to the acyloxy groups in the α,ω-bisacyloxypolydialkylsiloxane is less than 2.0, wherein the general Formula (II) is

wherein each occurrence of R and R 1 is independently a monovalent C 1 to C 20 alkyl, alkylaryl, or aryl group, and n is between 10 and 400, in a solvent composing at least one organic acid being a C 2 to C 6 carboxylic acid.

2. The process of claim 1 wherein the linear α,ω-bisacyloxy-polydiorganosiloxane of the general Formula (II) is reacted with the bisphenolic compound, or the hydroxy-functional oligomer thereof in the presence of a catalyst, wherein the catalyst is a metal salt of an organic acid.

3. The process of claim 1 wherein the bisphenolic compound, or hydroxy-functional oligomer thereof, is selected from the group consisting of

and the corresponding hydroxy-functional polycarbonate, hydroxy-functional polysulfone and hydroxy-functional polyester oligomers thereof.

4. The process of claim 1 wherein the hydroxy-functional oligomer is a hydroxy-functional polycarbonate, a hydroxy-functional polyester, a hydroxy-functional polysulfone oligomer or a hydroxy-functional polyether ether ketone oligomer represented by Formulae (VI), (VII), (VIII) and (IX) respectively:

wherein each of Z, Z 1 , Z 2 and Z 3 is independently a divalent C6 to C30 aryl, bisarylalkyl or bisaryloxy group, Q 1 and Q 2 are hydrogen, and p is a number between 2 and 150.

5. The process of claim 1 wherein the step of reacting a linear α,ω-bisacyloxy-polydiorganosiloxane of the general Formula (II) is conducted such there is a molar ratio of the phenolic groups in the bisphenolic compound or the bishydroxy-functional oligomer thereof to the acyloxy groups in the α,ω-bisacyloxypolydialkylsiloxane of from 1.2 to less than 2.0.

6. A polydiorganosiloxane/polyorgano (A-B), block copolymer comprising (i) polydiorganosiloxane blocks A and (ii) polycarbonate, polyester, polysulfone and/or polyether ether ketone oligomer blocks B with from 2 to 500 bisoxyorgano groups, wherein the polydialkylsiloxane blocks A are represented by the general Formula (III)

wherein Ar is a divalent C6 to C30 aryl, alkylaryl or aryloxy group, each occurrence of R is independently a monovalent C1 to C20 alkyl, alkylaryl, or aryl group, n has an average value of 10 to 400, and m has an average value of 1.0 to 5.0,

and x is between 1 and 1000.

7. The polydiorganosiloxane/polyorgano (A-B) x block copolymer of claim 6 wherein each occurrence of R is independently a methyl or phenyl group.

8. The polydiorganosiloxane/polyorgano (A-B) x block copolymer of claim 6 wherein Ar is represented by one of the following structures:

9. The polydiorganosiloxane/polyorgano (A-B) x block copolymer of claim 6 wherein the blocks B are represented by the general Formula (X), (XI), (XII), or (XIII):

wherein each of Z, Z 1 , Z 2 and Z 3 is independently a divalent C6 to C30 aryl, bisarylalkyl or bisaryloxy group, p is a number between 2 and 500, and Y 1 and Y 2 are either a direct linkage or carbonate or ester linkage groups.

10. A process for the preparation of a polydialkylsiloxane/polyorgano (A-B) x block copolymer of claim 6 wherein a linear hydroxyaryloxy-functional polydialkylsiloxane of the general formula (I)

wherein Ar is a divalent C6 to C30 aryl, alkylaryl or aryloxy group, each occurrence of R is independently a monovalent C1 to C20 alkyl, alkylaryl, or aryl group, n has an average value of from 10 to 400, and m has an average value of from 1.0 to 5.0; a bisphenolic compound or its polycarbonate, polyester or polysulfone oligomers by two-phase boundary polycondensation or solventless polycondensation, transesterification or melt processes.

11. The process of claim 10 wherein the bisphenolic compound, or its polycarbonate, polyester or polysulfone oligomers, is selected from the group consisting of

and the corresponding polycarbonate, polysulfone and polyester oligomers thereof.

12. The process of claim 6 , wherein the polycarbonate, polyester, polysulfone, and polyether ether ketone oligomer blocks have the general Formula (VI), (VII), (VIII), and (IX), respectively:

wherein each of Z, Z 1 , Z 2 and Z 3 is independently a divalent C6 to C30 aryl, bisarylalkyl or bisaryloxy group, p is a number between 2 and 500, Q 1 and Q 2 are independent of one another either hydrogen or a —C(═O)—X group wherein X is a halogen, hydroxy, C1-C20 alkyloxy, alkylaryloxy, or aryloxy group.

13. The process of claim 10 , wherein chain terminating groups or condensation linkage groups are used to control the molecular weight of the block copolymer (A-B) x .

14. The process of claim 10 wherein the reaction is conducted under the conditions of a solventless polycondensation, transesterification, or melt process.

15. An article of manufacture comprising the block copolymer of claim 6 .