Granted Patent B2

US 9,562,159 · App. 14/790,464 · Granted Feb 7, 2017

Abstract

Claims (37)

1. A polysiloxane comprising a structure of Formula I:

wherein; R 1 and R 2 are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical; R 3 is an organic UV absorbing group derived from an allyl substituted 2-hydroxybenzophenone, allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone or allyl substituted dibenzoylresorcinol; R 4 is independently a hydrocarbon radical optionally substituted with oxygen and nitrogen, or a group of Formula II(a) or Formula II(b)

wherein A and B are a hydrocarbon radical; R 5 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; R 6 is a hydroxyl group; x is from 1 to 300; y is from 0 to 50 and z is from 1 to 50.

2. A method of preparing the polysiloxane of claim 1 comprising:

reacting a hydride terminated siloxane represented by Formula III;

wherein R 1 and R 2 are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical; wherein x is from 1 to 300 and y is from 0 to 50; with an allyl unsaturated chain containing substituted or unsubstituted hydroxyphenyl compound followed by equilibration of hydroxyphenyl compound terminated siloxane in presence of hydride substituted cyclic siloxane to obtain a hydroxyphenyl compound terminated siloxane having the formula:

wherein R 1 and R 2 are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical; R 4 is independently a hydrocarbon radical optionally substituted with oxygen and nitrogen, or a group of Formula II(a) or Formula II(b)

wherein A and B are a hydrocarbon radical; R 5 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; R 6 is independently a hydroxyl group; wherein x is from 1 to 300; y is from 0 to 50; and z is from 0 to 50;

reacting the hydroxyphenyl compound terminated siloxane with an allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone or allyl substituted dibenzoylresorcinol in the presence of a catalyst at a temperature of about 50 to 80° C., to yield the UV absorbing polysiloxane; and

purifying the UV absorbing polysiloxane.

3. The polysiloxane of claim 1 , wherein R 3 the organic UV absorbing group derived from an allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone.

4. The polysiloxane of claim 1 , wherein R 3 is the organic UV absorbing group derived from an allyl substituted compound of Formula IV:

5. The polysiloxane of claim 1 , wherein R 3 is the organic UV absorbing group derived from an allyl substituted compound of Formula V:

6. A composition comprising the polysiloxane of claim 1 and a polymer selected from the group consisting of: polycarbonate homopolymers, polycarbonate copolymers, polycarbonate-polyesters, polyesters, polysulfones, polyethersulfones, polyetheretherketones, polyimides and polyetherimides.

7. An article comprising the polyosiloxane of claim 6 .

8. A copolymer comprising at least one polysiloxane having units of Formula VI represented by:

wherein; R 1 and R 2 are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical; R 3 is an organic UV absorbing group derived from an allyl substituted 2-hydroxybenzophenone, allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone, allyl substituted 2-(2′-hydroxy-5′-methylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-tert.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-methyl-5′-tert.-butyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-cyclohexyl-phenyl)-2H-benzotriazole, allyl substituted 2′-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-isooctylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-tert.-butyl-5′-sec.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole or allyl substituted dibenzoylresorcinol; R 4 is a hydrocarbon radical optionally substituted with oxygen and nitrogen, or a group of Formula II(a) or Formula II(b)

wherein A and B are a hydrocarbon radical; R 5 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; x is from 1 to 300; y is from 0 to 50 and z is from 1 to 50.

9. The copolymer of claim 8 , further comprising structural units of Formula VII:

wherein each R 7 is a hydrocarbon radical having 1 to 60 carbon atoms, of Formula VIII;

wherein R 8 is independently; a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; and V is selected from the group consisting of:

wherein R 10 and R 11 are independently; a hydrogen, halogen, an alkyl group having from 1 to 18 carbon atoms, an aryl group having from 3 to 14 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbon atoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, or a carboxyl group.

10. The copolymer of claim 9 , wherein R 10 is alkyl group of from 1 to 6 carbon atoms.

11. A composition comprising the copolymer of claim 8 and a polymer selected from the group consisting of a polycarbonate homopolymer, a polycarbonate copolymer, a polycarbonate-polyester, a polyester, a polysulfone, a polyethersulfone, a polyetheretherketone, a polyimide, a polyetherimide, or a combination thereof.

12. The copolymer of claim 8 , wherein R 3 is the organic UV absorbing group is derived from an allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone.

13. The copolymer of claim 8 , wherein R 3 is the organic UV absorbing group derived from an allyl substituted compound of Formula IV:

14. The copolymer of claim 8 , wherein R 3 is the organic UV absorbing group derived from an allyl substituted compound of Formula V:

15. An article comprising the copolymer of claim 8 .

16. The article of claim 15 , wherein said article is selected from the group consisting of panels, films and casts.

17. A method of preparing a polysiloxane copolymer, comprising polymerizing an organosiloxane represented by Formula I:

wherein R 1 and R 2 are independently a hydrocarbon radical, an unsaturated radical, an alkoxy radical, an aryl radical or an alkenyloxy radical; R 3 is an organic UV absorbing group derived from an allyl substituted 2-hydroxy-4-methoxybenzophenone, allyl substituted 2-hydroxy-4-methoxy-2′-carboxybenzophenone, allyl substituted 2,4-dihydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxybenzophenone, allyl substituted 2,2′-dihydroxybenzophenone, allyl substituted 2,2′,4,4′-tetrahydroxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-diethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dipropoxybenzophenone, allyl substituted 2,2′-dihydroxy-4,4′-dibutoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-ethoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-propoxybenzophenone, allyl substituted 2,2′-dihydroxy-4-methoxy-4′-butoxybenzophenone, allyl substituted 2-(2′-hydroxy-5′-methylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-tert.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-methyl-5′-tert.-butyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-cyclohexyl-phenyl)-2H-benzotriazole, allyl substituted 2′-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-5′-isooctylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′-tert.-butyl-5′-sec.-butylphenyl)-2H-benzotriazole, allyl substituted 2-(2′-hydroxy-3′,5′-dimethyl-phenyl)-2H-benzotriazole or allyl substituted dibenzoylresorcinol; R 4 is hydrocarbon radical optionally substituted with oxygen and nitrogen, a group of Formula II(a) or Formula II(b)

wherein A and, B are a hydrocarbon radical; R 5 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; R 6 is a hydroxyl group; x is from 1 to 300; y is from 0 to 50 and z is from 1 to 50, with a compound represented by Formula VIII:

where R 8 is independently a hydrogen, a halogen, an aliphatic group having from 1 to 6 carbon atoms, an aromatic group having 6 to 8 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or an aryloxy group; and R 9 is a hydroxyl group; and V is selected from the group consisting of:

wherein R 10 and R 11 are independently a hydrogen, halogen, an alkyl group having from 1 to 18 carbon atoms, an aryl group having from 3 to 14 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, an alkoxy group having from 1 to 10 carbon atoms, a cycloalkyl group having from 6 to 20 carbon atoms, a cycloalkoxy group having from 6 to 20 carbon atoms, an alkenyl group having from 2 to 10 carbon atoms, an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, or a carboxyl group; in the presence of a carbonate precursor.

18. The method of claim 17 , wherein the carbonate precursor is selected from the group consisting of phosgene, diphosgene, diarylcarbonate, bis(methylsalicyl)carbonate, and a combination thereof.

19. The method of claim 17 , wherein the polymerizing step is an interfacial polymerization process conducted in the presence of a solvent and optionally one or more catalysts.

20. The method of claim 17 , wherein the one or more catalysts are selected from the group consisting of: aliphatic amines, trialkylamine; and phase transfer catalyst of the formula (A 3 )4L+B, wherein each A is independently a C1-10 alkyl group; L is a nitrogen or phosphorus atom; and B is a halogen atom or a C1-8 alkoxy group or C6-18 aryloxy group.

Assignments (10)