阅读说明：本技术 含苯基的官能聚硅氧烷和由其制备的聚碳酸酯-聚硅氧烷共聚物 (Phenyl-containing functional polysiloxanes and polycarbonate-polysiloxane copolymers prepared therefrom ) 是由 鹿沼浩二 堀江丰 A·米特塔 L·萨曼塔拉 I·拉马克里斯南 熊部尚文 N·P·伊耶 于 2014-05-30 设计创作，主要内容包括：本发明涉及含苯基的官能聚硅氧烷和由其制备的具有改善的光学透明度和更好的低温抗冲击性的聚碳酸酯-聚硅氧烷共聚物组合物。(The present invention relates to phenyl-containing functional polysiloxanes and polycarbonate-polysiloxane copolymer compositions prepared therefrom having improved optical clarity and better low temperature impact resistance.)

1. A copolymer of formula (I):

wherein R is₄Independently a direct bond or C2-C15 alkylene; r₅Selected from alkyl, aryl or substituted aryl of up to 15 carbon atoms; r₆Is an aliphatic hydrocarbon group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms; r₇Is phenyl; r₈Selected from alkyl and aryl groups having up to 15 carbon atoms; r₉Is an aliphatic group having 1 to 6 carbon atoms, a monovalent aromatic group having 6 to 15 carbon atoms, an alkoxy group having 6 to 15 carbon atoms; aryloxy of up to 12 carbon atoms; having the formula-Si- (R)₁₂)₃Wherein R is₁₂Is an alkyl group having 1 to 6 carbon atoms, an unsaturated group having 2 to 12 carbon atoms, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r₁₀Is hydrogen, halogen, aliphatic having 1 to 6 carbon atoms, aromatic having 6 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms or aryloxy having up to 12 carbon atoms;

wherein R is₈And R₉Are different groups;

wherein x ranges from 1 to 130;

y ranges from 1 to 15;

z ranges from 0 to 15;

n ranges from 1 to 15;

x + y ranges from 1 to 130;

y + z > 0; and x + y + z is not more than 130;

the ratio of y to x is 0.008-0.190;

a is in the range of from 99 to 75 wt%, based on the total weight of the copolymer; and

b is in the range of from 1 to 25 wt% based on the total weight of the copolymer.

2. The copolymer of claim 1, wherein the halogen is selected from Cl, Br, or F.

3. The copolymer of claim 1, wherein R₆Independently a methyl or vinyl group.

4. The copolymer of claim 1, wherein x is in the range of from 40 to 80.

5. The copolymer of claim 1, wherein y ranges from 1 to 12.

6. The copolymer of claim 1, wherein z ranges from 0 to 12.

7. The copolymer of claim 1, wherein z is 2 to 12.

8. The copolymer of claim 1, wherein n is 1 to 6.

9. The copolymer of claim 1, wherein n is 2.

10. The copolymer of claim 1, wherein the ratio of y to x is from 0.01 to 0.1765.

11. The copolymer of claim 1, wherein the ratio of y to x is 0.095 or 0.19.

12. The copolymer of claim 1, wherein the copolymer has the structure of formula (II):

wherein

x ranges from 1 to 130;

y ranges from 1 to 12;

z ranges from 2 to 12;

x+y+z≤130；

the ratio of y to x is 0.008-0.190;

a is in the range of from 80 to 99 wt%, based on the total weight of the copolymer; and

b is in the range of from 1 to 20 wt% based on the total weight of the copolymer.

13. A polymer blend composition comprising:

a polycarbonate homopolymer; and

the copolymer of any one of claims 1-12.

14. A process for producing a copolymer of formula (I),

wherein R is₄Independently a direct bond or C2-C15 alkylene; r₅Selected from alkyl, aryl or substituted aryl of up to 15 carbon atoms; r₆Is an aliphatic hydrocarbon group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms; r₇Is phenyl; r₈Selected from alkyl and aryl groups having up to 15 carbon atoms; r₉Is an aliphatic group having 1 to 6 carbon atoms, a monovalent aromatic group having 6 to 15 carbon atoms, an alkoxy group having 6 to 15 carbon atoms; aryloxy of up to 12 carbon atoms; having the formula-Si- (R)₁₂)₃Wherein R is₁₂Is an alkyl group having 1 to 6 carbon atoms, an unsaturated group having 2 to 12 carbon atoms, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r₁₀Is hydrogen, halogen, aliphatic radical having 1 to 6 carbon atoms, aromatic radical having 6 to 8 carbon atoms, alkoxy radical having 1 to 6 carbon atoms or has up to 12 carbonsAn aryloxy group of atoms;

wherein R is₈And R₉Are different groups;

wherein x ranges from 1 to 130;

y ranges from 1 to 15;

z ranges from 0 to 15;

n ranges from 1 to 15;

x + y ranges from 1 to 130;

y + z > 0; and x + y + z is not more than 130;

the ratio of y to x is 0.008-0.190;

a is in the range of from 99 to 75 wt%, based on the total weight of the copolymer; and

b is in the range of from 1 to 25 wt%, based on the total weight of the copolymer

Wherein the process comprises reacting bisphenol a with a difunctional polydiorganosiloxane compound having the formula below in the presence of a carbonating agent selected from phosgene or triphosgene to produce a copolymer of formula (I):

wherein R is₁₁Is a hydroxyl group.

15. A method of producing the polymer blend composition of claim 13, comprising blending the polycarbonate copolymer of formula (I) with a polycarbonate homopolymer.

16. An article of manufacture comprising the polymer blend composition of claim 13.

17. The article of claim 16 selected from the group consisting of mobile phone housings, frozen food service equipment, helmets, automobile and motorcycle windshields, and automobile sunroofs, dashboards, headlights, or electronic screens.

18. A difunctional polydiorganosiloxane having the structure:

wherein R is₄Independently a direct bond or C2-C15 alkylene; r₅Selected from alkyl, aryl or substituted aryl of up to 15 carbon atoms; r₆Is an aliphatic hydrocarbon group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms; r₇Is phenyl; r₈Selected from alkyl and aryl groups having up to 15 carbon atoms; r₉Is an aliphatic group having 1 to 6 carbon atoms, a monovalent aromatic group having 6 to 15 carbon atoms, an alkoxy group having 6 to 15 carbon atoms; aryloxy of up to 12 carbon atoms; having the formula-Si- (R)₁₂)₃Wherein R is₁₂Is an alkyl group having 1 to 6 carbon atoms, an unsaturated group having 2 to 12 carbon atoms, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r₁₀Is hydrogen, halogen, aliphatic having 1 to 6 carbon atoms, aromatic having 6 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms or aryloxy having up to 12 carbon atoms; r₁₁Is a hydroxyl group;

wherein R is₈And R₉Are different groups;

wherein x ranges from 1 to 130;

y ranges from 1 to 15;

z ranges from 0 to 15;

n ranges from 1 to 15;

x + y ranges from 1 to 130;

y + z > 0; and x + y + z is not more than 130; and

the ratio of y to x is 0.008-0.190.

19. The bifunctional polydiorganosiloxane of claim 18, wherein said halogen is selected from Cl, Br, or F.

20. The bifunctional polydiorganosiloxane of claim 18, wherein x is in the range of from 40 to 80.

21. The bifunctional polydiorganosiloxane of claim 18, wherein y is 1 to 12.

22. The bifunctional polydiorganosiloxane of claim 18, wherein z ranges from 2 to 12.

23. The bifunctional polydiorganosiloxane of claim 18, wherein n ranges from 1 to 6.

24. The bifunctional polydiorganosiloxane of claim 18, wherein the ratio of y to x is from 0.01 to 0.1765.

25. The bifunctional polydiorganosiloxane of claim 18, wherein the ratio of y to x is 0.095 or 0.19.

26. The bifunctional polydiorganosiloxane of claim 18, wherein R is₉Is Si (Ph)₃，R₈Is methyl, z is 2-12, and n ═ 2.

Technical Field

The present invention relates to phenyl-containing functional polysiloxanes and polycarbonate-polysiloxane copolymers prepared therefrom.

Background

Polycarbonate polymers are useful in the manufacture of articles and components for a wide range of applications, including automotive parts such as headlamps and windshields, and medical devices. However, many polycarbonate polymers are brittle, particularly at low temperatures. Polycarbonate copolymers containing polysiloxane blocks have shown, inter alia, excellent low temperature impact properties, improved solvent resistance, inherent flame retardancy, improved hydrolysis resistance and heat aging characteristics, and excellent processability. However, due to the large refractive index difference between the polycarbonate and polysiloxane blocks, the resulting copolymers are typically opaque unless the siloxane regions are very small. Although smaller domains can be created by using siloxane blocks with shorter D lengths (typically <30), the low temperature impact resistance improvement in such copolymer compositions suffers.

Eugenol-terminated polymers are known in the art for various purposes such as heat resistance, improved ductility and thermal processing, solvent resistance, and the like. Eugenol is also known to be useful as an end-capping compound for polysiloxane polymers. For example, US5661202, EP0570208a2, US7709581B2, US2008/0081860a1 disclose eugenol-terminated fluids having different substituents in the backbone or pendant thereto.

Copolymers of polycarbonate and polysiloxane are also known in the art. For example, US 6576735 discloses the preparation of polycarbonate-polysiloxane copolymer compositions from 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene as monomer and a phenyl-containing siloxane. The polycarbonate prepared from the 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene monomer results in a rigid structure compared to the polycarbonate prepared from bisphenol-a. Silicone-containing comonomers have been accepted to impart plasticity. US 7498388B2 discloses the use of eugenol-terminated siloxanes with shorter D chains to prepare PC-polysiloxane copolymer compositions having a siloxane concentration of 3-5 wt%, a lower B-Y span (B-Y span) (difference between yellowness transmission index and yellowness reflection index), yielding 100% ductility only up to-30C. The resulting polymer exhibits reduced "edge haze" during the formation of the molded article.

Several attempts have been made to prepare transparent (low haze) polycarbonate-polysiloxane copolymers using eugenol-terminated siloxanes (D length-45-50). For example, US 5530083 discloses a multi-step process for preparing transparent polycarbonate-polysiloxane copolymers. In the first step, oligomeric bisphenol polycarbonates are prepared by phosgenating bisphenol-A using a phase transfer catalyst. In the second step, a bisphenol chloroformate is reacted with a bis (hydroxyaryl) siloxane in the absence of phosgene. EP1654301a1 discloses the preparation of siloxane bischloroformates in one step and the addition of siloxane-BCF to the polycarbonate synthesis process in the presence of a recoverable catalyst.

There is a need for polycarbonate-polysiloxane copolymer compositions with improved optical clarity (high% transmission and low haze) and better low temperature impact resistance. The present invention is believed to provide an answer to that need.

Disclosure of Invention

Often for increased utility, polysiloxane-polycarbonate copolymers are prepared and blended with other homopolycarbonates and copolycarbonates for use as impact modifiers. Because these block copolymers are stable at high temperatures, they provide the best low temperature ductility and the best thermal stability of any impact modifier used in polycarbonates. The addition of these block copolymers to polycarbonate blends was found to increase low temperature ductility and reduce heat aged impact loss. Polycarbonate siloxane block copolymers based on functional siloxanes will have greatly improved performance benefits when blended with polycarbonate homopolymers or copolymers.

The present invention provides functional polycarbonate-polysiloxane copolymers that can have excellent refractive index and ductility characteristics while maintaining high transparency and low haze, and methods for preparing the same. The functional polycarbonate-polysiloxane copolymer can also have an excellent balance of clarity, temperature resistance, chemical resistance, and mechanical strength. In one aspect, the invention relates to a copolymer of formula (I):

wherein:

a is a hydroxyphenyl moiety derived from a compound having the structure (S):

wherein R is₁Is hydrogen, halogen (e.g., Cl, Br, or F), aliphatic group having 1 to 6 carbon atoms, aromatic group having 6 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, or aryloxy group having 6 to about 10 carbon atoms(ii) a And R is₂Is hydroxy, amino, acyl chloride or acyl thioahalide; and X is selected from:

wherein R is₃Independently selected from the group consisting of hydrogen, halogen, alkyl of 1 to 18 carbon atoms, aryl of 3 to 14 carbon atoms, aryloxy of 6 to 10 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 10 carbon atoms, cycloalkyl of 6 to 20 carbon atoms, cycloalkoxy of 6 to 20 carbon atoms, alkenyl of 2 to 10 carbon atoms, aralkoxy of 7 to 12 carbon atoms, nitro, aldehyde, cyano and carboxyl;

b is a difunctional polydiorganosiloxane moiety derived from a compound having the structure:

wherein R is₄Independently is a direct bond or substituted or unsubstituted C₁-C₁₅Alkyl or C₂-C₁₅Alkylene, optionally containing a heteronuclear atom selected from N, O, S and P; r₅Selected from the group consisting of alkyl, aryl, and substituted aryl of up to about 12 carbon atoms; r₆And R₇Each independently an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms; r₈Selected from alkyl and aryl groups having up to 15 carbon atoms; r₉Is an aliphatic radical having from 1 to 6 carbon atoms, a monovalent or divalent aromatic radical having from 6 to 15 carbon atoms, an alkoxy radical having up to 15 carbon atoms, an aryloxy radical having from 6 to 15 carbon atoms or has the formula-Si- (R)₁₂)₃Wherein R is₁₂Is an alkyl group having 1 to 6 carbon atoms, an unsaturated group having 2 to about 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r₁₀Is hydrogen, halogen, aliphatic having 1 to 6 carbon atoms, aromatic having 6 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms or aryloxy having up to 12 carbon atoms; r₁₁Is a hydroxyl group,Amine groups, acid anhydride groups or halogenated thioacyl groups;

wherein R is₆And R₇Are different radicals, wherein R₆Or R₇Is phenyl, and wherein R₈And R₉Are different groups; x ranges from 1 to 130; y ranges from 1 to 15; z ranges from 0 to 15 and preferably 2-12; n ranges from 1 to 15; y + z>0 and x + y + z<130, wherein the ratio of x to y is from 0.01 to 0.1765; a is in the range of from 99 to 75 wt%, based on the total weight of the copolymer; and b is in the range of from 1 to 25 wt% based on the total weight of the copolymer.

In another aspect, the present invention relates to a polymer blend composition comprising a polycarbonate homopolymer and a copolymer of formula (I).

In another aspect, the invention relates to a copolymer of formula (II)

Wherein

x ranges from 1 to 130;

y ranges from 1 to 12;

z ranges from 0 to 12, and preferably 2-12;

wherein y + z > 0; and x + y + z < (130);

wherein the ratio of x to y is from 0.01 to 0.1765;

a is in the range of from 80 to 99 wt%, based on the total weight of the copolymer; and

b is in the range of from 1 to 20 wt% based on the total weight of the copolymer.

In another aspect, the present invention relates to a polymer blend composition comprising a polycarbonate homopolymer and a copolymer of formula (II).

In another aspect, the present invention relates to a method of producing a copolymer of formula (I) comprising reacting a dihydroxybenzene compound of formula (S) with a difunctional polydiorganosiloxane compound of the following structure in the presence of phosgene to produce a copolymer of formula (I):

in yet another aspect, the present invention relates to a method of producing a polymer blend composition comprising blending a polycarbonate copolymer of formula (I) with a polycarbonate homopolymer.

In a preferred aspect, the present invention relates to a copolymer of formula (I):

wherein:

a is a hydroxyphenyl moiety derived from a compound having the structure (S):

wherein R is₁Is hydrogen, halogen, aliphatic having 1 to 6 carbon atoms, aromatic having 6 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms or aryloxy having up to 12 carbon atoms; r₂Is hydroxy, amino, acyl chloride or acyl thioahalide; and X is selected from:

wherein R is₃Independently selected from the group consisting of hydrogen, halogen, alkyl of 1 to 18 carbon atoms, aryl of up to 14 carbon atoms, aryloxy of 6 to 10 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 10 carbon atoms, cycloalkyl of 6 to 20 carbon atoms, cycloalkoxy of 6 to 20 carbon atoms, alkenyl of 2 to 10 carbon atoms, aralkoxy of up to about 15 carbon atoms, nitro, aldehyde, cyano and carboxyl;

b is a difunctional polydiorganosiloxane moiety derived from a compound having the structure:

wherein R is₄Independently is a direct bond or substituted or unsubstituted C₁-C₁₅Alkyl or C₂-C₁₅Alkylene, optionally containing a heteronuclear atom selected from N, O, S and P; r₅Selected from alkyl, aryl and substituted aryl groups of up to 15 carbon atoms; r₆And R₇Each independently an aliphatic or aromatic hydrocarbon group having 1 to 15 carbon atoms; r₈Selected from alkyl and aryl groups having up to 15 carbon atoms; r₉Is an aliphatic radical having from 1 to 6 carbon atoms, a monovalent or divalent aromatic radical having from 6 to 15 carbon atoms, an alkoxy radical having from 6 to 15 carbon atoms, an aryloxy radical having up to 12 carbon atoms, having the formula-Si- (R)₁₂)₃Wherein R is₁₂Is an alkyl group having 1 to 6 carbon atoms, an unsaturated group having 2 to 12 carbon atoms, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r₁₀Is hydrogen, halogen, aliphatic group having 1 to 6 carbon atoms, aromatic group having 6 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, or aryloxy group; r₁₁Is hydroxyl, amino, anhydride or sulfuryl halide;

wherein R is₆Is phenyl, and wherein R₈And R₉Are different groups;

wherein x ranges from 1 to 130;

y＝1；

z ranges from 1 to 12;

n ranges from 1 to 15;

y + z > 0; and x + y + z < (130);

a is in the range of from 99 to 75 wt%, based on the total weight of the copolymer; and

b is in the range of from 1 to 25 wt% based on the total weight of the copolymer.

In another aspect, the present invention relates to a bifunctional polydiorganosiloxane having the structure:

wherein R is₄Independently is a direct bond or substituted or unsubstituted C₁-C₁₅Alkyl or C₂-C₁₅Alkylene, optionally containing a heteronuclear atom selected from N, O, S and P; r₅Selected from alkyl, aryl or substituted aryl of up to about 15 carbon atoms; r₆And R₇Each independently an aliphatic or aromatic hydrocarbon group having 1 to 15 carbon atoms; r₈Selected from alkyl and aryl groups having up to 15 carbon atoms; r₉Is an aliphatic group having 1 to 6 carbon atoms, a monovalent or divalent aromatic group having 6 to 15 carbon atoms, an alkoxy group having 6 to 15 carbon atoms; aryloxy having up to 12 carbon atoms; having the formula-Si- (R)₁₂)₃Wherein R is₁₂Is an alkyl group having 1 to 6 carbon atoms, an unsaturated group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; r₁₀Is hydrogen, halogen, aliphatic having 1 to 6 carbon atoms, aromatic having 6 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms or aryloxy having up to 12 carbon atoms; r₁₁Is hydroxyl, amino, anhydride or sulfuryl halide;

wherein R is₆And R₇Are different radicals, wherein R₆Or R₇Is phenyl, and wherein R₈And R₉Are different groups, wherein x ranges from 1 to 130; y ranges from 1 to 15; z ranges from 0 to 15; n ranges from 1 to 15; y + z>0; and x + y + z<130; and the ratio of x to y is from 0.01 to 0.1765.

Drawings

The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:

FIGS. 1(a) and 1(b) are electron micrographs showing the morphology of phenyl-containing functional polysiloxanes of the present invention and polycarbonate-polysiloxane copolymers; and the Transmission Electron Microscope (TEM) images shown in fig. 1(a) and 1(b) are at 200nm scale and 100nm scale magnifications, respectively. FIGS. 1(a) and 1(b) show the siloxane domains at 10-30nm in polycarbonate with the more hazy regions. Fig. 1(a) and (b) clearly show that, because of the excellent compatibility of the phenyl groups with the polycarbonate units (refractive index matching), in the case of copolymers based on functional polysiloxanes containing phenyl groups, the domains are observed as hazier domains and the domain dimensions are also observed as smaller dimensions (10-30 nm).

FIGS. 2(a) and 2(b) are electron micrographs showing the morphology of polysiloxane and polycarbonate-polysiloxane copolymer of comparative blend 1 in example 9. Transmission Electron Microscope (TEM) images shown in fig. 2(a) and (b) are at 200nm scale and 100nm scale magnifications, respectively. FIGS. 2(a) and 2(b) show that the siloxane domains are 20-45nm in polycarbonate as deeper domains compared to polycarbonate.

FIGS. 3 and 4 are dynamic mechanical analysis representations of the polycarbonate polysiloxane copolymers of the present invention based on storage modulus, loss modulus, and tan () response, as compared to polycarbonate homopolymer. The dynamic mechanical analysis data clearly shows that the polycarbonate polysiloxane copolymers based on phenyl-containing siloxanes show improved storage modulus, loss modulus and tan () response when compared to polycarbonate homopolymers.

Detailed Description

The present invention discloses the incorporation of high Refractive Index (RI) phenyl groups in eugenol-terminated polyorganosiloxane polymers, and the production of copolymers and blends of copolymers from these eugenol-terminated polyorganosiloxane polymers. It has been surprisingly found that the incorporation of eugenol-terminated polyorganosiloxane polymer results in the formation of smaller domains in the polycarbonate matrix. This result may potentially produce products with increased optical clarity (high transmission, low haze) and improved low temperature impact properties.

As indicated above, the present invention relates to a copolymer of formula (I) consisting of two copolymer blocks each containing a and B moiety respectively:

in formula (I), a is a hydroxyphenyl moiety derived from a compound having the structure (S):

wherein R is₁Is hydrogen, a halogen such as Br, Cl or F, an aliphatic group having 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryloxy group having up to 12 carbon atoms; and R₂Is a hydroxyl group, an amine group, an acyl chloride group or an acyl halide sulfide group. X is a bridging moiety, preferably selected from:

wherein R is₃Independently selected from the group consisting of hydrogen, halogen, alkyl of 1 to 18 carbon atoms, aryl of up to 14 carbon atoms, aryloxy of 6 to 10 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 10 carbon atoms, cycloalkyl of 6 to 20 carbon atoms, cycloalkoxy of 6 to 20 carbon atoms, alkenyl of 2 to 10 carbon atoms, aralkoxy of up to 15 carbon atoms, nitro, aldehyde, cyano and carboxyl. In a preferred embodiment, R₃Is an alkyl group having 3 carbon atoms.

In formula (I), B is a difunctional polydiorganosiloxane moiety derived from a compound having the structure:

wherein R is₄Independently is a direct bond or substituted or unsubstituted C₁-C₁₅Alkyl or C₂-C₁₅Alkylene, and optionally containing a heteronuclear atom selected from N, O, S and P; r₅Selected from alkyl, aryl and substituted aryl groups of up to 15 carbon atoms; r₆And R₇Each independently an aliphatic or aromatic hydrocarbon having 1 to 15 carbon atoms; r₈Selected from alkyl and aryl groups having up to 15 carbon atoms; r₉Is of 1 to 6 carbonsAn aliphatic group of atoms, a monovalent or divalent aromatic group having 6 to 15 carbon atoms, an alkoxy group having 6 to 15 carbon atoms; aryloxy of up to 12 carbon atoms; having the formula-Si- (R)₁₂)₃Wherein R is₁₂Is an alkyl group having 1 to 6 carbon atoms, an unsaturated group having 2 to 10 carbon atoms, an aromatic group having 6 to 15 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; r₁₀Is hydrogen, halogen, aliphatic having 1 to 6 carbon atoms, aromatic having 6 to 8 carbon atoms, alkoxy having 1 to 6 carbon atoms or aryloxy having up to 12 carbon atoms; r₁₁Is hydroxyl, amino, anhydride or sulfuryl halide.

R₆And R₇Are different radicals, and R₈And R₉Are different radicals, and R₆Or R₇At least one of which is phenyl. In a preferred embodiment, R₆And R₇Each independently an alkyl, aryl, substituted aryl or cycloalkyl group of up to 15 carbon atoms. In addition, x can range broadly from 1 to 100, and preferably from 20 to 80. y can range broadly from 1 to 15 and preferably from 1 to 12. z may broadly range from 0 to 15 and preferably ranges from 1 to 12. In x, y and z, y + z>0 and x + y + z<130 and the ratio of x to y is from 0.01 to 0.1765. In formula B, n may broadly range from 1 to 15, and preferably ranges from 1 to 6.

In a preferred embodiment, the copolymer of the invention has the structure of formula (II):

in formula (II), x ranges from 1 to 130; y ranges from 1 to 15; z ranges from 0 to 12, and preferably 1-12; y + z > 0; x + y + z < (130); the ratio of x to y is from 0.01 to 0.1765; a is in the range of from 80 to 99 wt%, based on the total weight of the copolymer; and b is in the range of from 1 to 20 wt%, based on the total weight of the copolymer.

The invention also relates to a polymer blend composition comprising a polycarbonate homopolymer and a copolymer of formula I. Suitable polycarbonate homopolymers include homopolymers obtained from dihydroxy benzene compounds of formula A. In one embodiment, a polycarbonate homopolymer derived from bisphenol a is used. In another embodiment, the present invention is also directed to a polymer blend composition comprising a polycarbonate homopolymer and a copolymer of formula II.

The copolymers of the present invention may be prepared by reacting a dihydroxybenzene compound of structure (S) with a difunctional polydimethylsiloxane compound of the following structure in the presence of phosgene:

in one embodiment, the dihydroxybenzene compound is bisphenol A and the difunctional polydiorganosiloxane compound is a bis-eugenol-terminated [ (polydimethyl) (polydiphenyl) ] siloxane.

A wide variety of articles of manufacture can be made using the copolymers of the present invention and particularly using polymer blend compositions (e.g., in combination with polycarbonate homopolymers) containing the copolymers of the present invention. For example, such articles include, but are not limited to, cell phone housings, frozen food service equipment, personal safety applications including helmets, automobile and motorcycle windshields, automobile sunroofs, other automotive applications including instrument panels that allow for robust airbag deployment without debris generation, and automotive headlamp or electronic screen applications where transparency, flame retardancy, and impact resistance are beneficial.