Granted Patent B1

US 8,822,615 · App. 13/762,749 · Granted Sep 2, 2014

Abstract

Claims (38)

1. A copolymer composition, comprising:

a block copolymer having a poly(acrylate) block and a poly(silyl acrylate) block; and,

an antioxidant;

wherein the block copolymer exhibits a number average molecular weight, M N , of 1 to 1,000 kg/mol; wherein the copolymer composition contains ≧2 wt % antioxidant (based on the weight of the block copolymer) and,

wherein the block copolymer exhibits a polydispersity, PD, of 1 to 2.

2. The copolymer composition of claim 1 , wherein the copolymer composition contains 5 to 30 wt % antioxidant (based on the weight of the block copolymer).

3. The copolymer composition of claim 1 , wherein the antioxidant is selected from the group consisting of:

an antioxidant containing at least one 2,6-di-tert-butylphenol moiety;

an antioxidant containing at least one moiety according to the formula

an antioxidant containing at least one moiety according to the formula

an antioxidants containing at least one moiety according to the formula

mixtures thereof.

4. The copolymer composition of claim 1 , wherein the antioxidant is selected from the group consisting of

mixtures thereof.

5. The copolymer composition of claim 1 ,

wherein the poly(acrylate) block includes residues from at least one of an acrylate monomer, a deuterated acrylate monomer, an acrylate block modifying monomer and a deuterated acrylate block modifying monomer; wherein the poly(acrylate) block includes >75 wt % of acrylate monomer derived units; wherein the acrylate monomer is selected from the group consisting of C 6-14 aryl (C 1-5 alkyl)acrylate; C 1-5 alkyl (C 1-5 alkyl)acrylate; wherein the deuterated acrylate monomer is selected from the group consisting of deuterated C 6-14 aryl (C 1-5 alkyl)acrylate; deuterated C 1-5 alkyl (C 1-5 alkyl)acrylate; wherein the acrylate block modifying monomer is selected from the group consisting of a C 1-5 alkene and a C 3-7 cycloalkene; wherein the deuterated acrylate block modifying monomer is selected from a deuterated C 1-5 alkene and deuterated a C 3-7 cycloalkene; and,

wherein the poly(silyl acrylate) block includes residues from at least one of a silyl acrylate monomer, a deuterated silyl acrylate monomer, a silyl acrylate block modifying monomer and a deuterated silyl acrylate block modifying monomer; wherein the poly(silyl acrylate) block includes >75 wt % silyl acrylate monomer derived units; wherein the silyl acrylate monomer is according to the following formula

(R 1 )(R 2 )(R 3 )Si) r R 4 x OOCC(R 5 )═CR 6 2

wherein each R 1 , R 2 and R 3 is independently selected from the group consisting of a C 1-6 alkyl group, a silylated C 1-6 alkyl group, an oxy C 1-6 alkyl group, an oxy silylated C 1-6 alkyl group, a C 6-10 aryl group, an oxy C 6-10 aryl group, a silylated C 6-10 aryl group, an oxy silylated C 6-10 aryl group, a C 1-10 arylalkyl group, an oxy C 1-10 arylalkyl group, a silylated C 1-10 arylalkyl group, an oxy silylated C 1-10 arylalkyl group, a C 6-10 alkylaryl group, an oxy C 6-10 alkylaryl group, a silylated C 6-10 alkylaryl group, an oxy silylated C 6-10 alkylaryl group; wherein r is selected from the group consisting of 0, 1, 2 and 3; wherein R 4 is selected from the group consisting of a C 1-3 alkyl; wherein x is selected from the group consisting of 0 and 1; wherein R 5 is selected from the group consisting of a hydrogen and a methyl group; wherein each R 6 is a hydrogen; wherein the silyl acrylate monomer includes at least one Si atom; wherein the deuterated silyl acrylate monomer is according to the following formula

(R 7 (R 8 )(R 9 )Si) t R 10 y OOCC(R 11 )═CR 12 2

wherein each R 7 , R 8 and R 9 is independently selected from a C 1-6 alkyl group, a silylated C 1-6 alkyl group, an oxy C 1-6 alkyl group, an oxy silylated C 1-6 alkyl group, a C 6-10 aryl group, an oxy C 6-10 aryl group, a silylated C 6-10 aryl group, an oxy silylated C 6-10 aryl group, a C 1-10 arylalkyl group, an oxy C 1-10 arylalkyl group, a silylated C 1-10 arylalkyl group, an oxy silylated C 1-10 arylalkyl group, a C 6-10 alkylaryl group, an oxy C 6-10 alkylaryl group, a silylated C 6-10 alkylaryl group, an oxy silylated C 6-10 alkylaryl group, a deuterated C 1-6 alkyl group, a deuterated silylated C 1-6 alkyl group, a deuterated oxy C 1-6 alkyl group, a deuterated oxy silylated C 1-6 alkyl group, a deuterated C 6-10 aryl group, a deuterated oxy C 6-10 aryl group, a deuterated silylated C 6-10 aryl group, a deuterated oxy silylated C 6-10 aryl group, a deuterated C 1-10 arylalkyl group, a deuterated oxy C 1-10 arylalkyl group, a deuterated silylated C 1-10 arylalkyl group, a deuterated oxy silylated C 1-10 arylalkyl group, a deuterated C 6-10 alkylaryl group, a deuterated oxy C 6-10 alkylaryl group, a deuterated silylated C 6-10 alkylaryl group and a deuterated oxy silylated C 6-10 alkylaryl group; wherein t is selected from the group consisting of 0, 1, 2 and 3; wherein R 10 is selected from the group consisting of a C 1-3 alkyl group, and a deuterated C 1-3 alkyl; wherein y is 0 or 1; wherein R 11 is selected from the group consisting of a hydrogen, a deuterium, a methyl group and a deuterated methyl group; wherein each R 12 is selected from a hydrogen and a deuterium; wherein the deuterated silyl acrylate monomer contains at least one Si atom; and, wherein the deuterated silyl acrylate monomer contains at least one deuterium; wherein the silyl acrylate block modifying monomer is selected from the group consisting of an alkene and a cycloalkene; and, wherein the deuterated silyl acrylate block modifying monomer is selected from the group consisting of a deuterated alkene and a deuterated cycloalkene.

6. The copolymer composition of claim 5 , wherein the copolymer composition contains 5 to 30 wt % antioxidant (based on the weight of the block copolymer).

7. The copolymer composition of claim 5 ,

wherein the acrylate monomer is selected from the group consisting of butyl (meth)acrylate, propyl (meth)acrylate), ethyl (meth)acrylate, methyl (meth)acrylate; wherein the deuterated acrylate monomer is selected from the group consisting of deuterated butyl (meth)acrylate, deuterated propyl (meth)acrylate), deuterated ethyl (meth)acrylate, deuterated methyl (meth)acrylate; wherein the acrylate block modifying monomer is ethylene; and, wherein the deuterated acrylate block modifying monomer is deuterated ethylene; and,

wherein the silyl acrylate monomer is selected from the group consisting of (trimethylsilyl)methyl (meth)acrylate, (triethylsilyl)methyl (meth)acrylate, (tripropylsilyl)methyl (meth)acrylate, (triisopropylsilyl)methyl (meth)acrylate, (tributylsilyl)methyl (meth)acrylate, (tri-sec-butylsilyl)methyl (meth)acrylate, (triisobutylsilyl)methyl (meth)acrylate, (sec-butylmethylsilyl)methyl (meth)acrylate, (sec-butyldimethylsilyl)methyl (meth)acrylate, (dimethylpropylsilyl)methyl (meth)acrylate, (monomethyldipropylsilyl)methyl (meth)acrylate, (methylethylpropylsilyl)methyl (meth)acrylate, bis(trimethylsilyl)methyl (meth)acrylate, tris(trimethylsilyl)methyl (meth)acrylate, (pentamethyldisilyl)methyl (meth)acrylate, tris(trimethylsiloxy)methyl (meth)acrylate, tris(trimethylsiloxy)propyl (meth)acrylate), (pentamethyldisiloxy)methyl (meth)acrylate, (pentamethyldisiloxy)propyl (meth)acrylate, (trimethoxysilyl)propyl (meth)acrylate and (triethoxysilyl)propyl (meth)acrylate; wherein the deuterated silyl acrylate monomer is selected from the group consisting of deuterated (trimethylsilyl)methyl (meth)acrylate, deuterated (triethylsilyl)methyl (meth)acrylate, deuterated (tripropylsilyl)methyl (meth)acrylate, deuterated (triisopropylsilyl)methyl (meth)acrylate, deuterated (tributylsilyl)methyl (meth)acrylate, deuterated (tri-sec-butylsilyl)methyl (meth)acrylate, deuterated (triisobutylsilyl)methyl (meth)acrylate, deuterated (sec-butylmethylsilyl)methyl (meth)acrylate, deuterated (sec-butyldimethylsilyl)methyl (meth)acrylate, deuterated (dimethylpropylsilyl)methyl (meth)acrylate, deuterated (monomethyldipropylsilyl)methyl (meth)acrylate, deuterated (methylethylpropylsilyl)methyl (meth)acrylate, deuterated bis(trimethylsilyl)methyl (meth)acrylate, deuterated tris(trimethylsilyl)methyl (meth)acrylate, deuterated (pentamethyldisilyl)methyl (meth)acrylate, deuterated tris(trimethylsiloxy)methyl (meth)acrylate, deuterated tris(trimethylsiloxy)propyl (meth)acrylate), deuterated (pentamethyldisiloxy)methyl (meth)acrylate, deuterated (pentamethyldisoloxy)propyl (meth)acrylate, deuterated (trimethoxysilyl)propyl (meth)acrylate and deuterated (triethoxysilyl)propyl (meth)acrylate; wherein silyl acrylate block modifying monomer is ethylene; and, wherein the deuterated silyl acrylate block modifying monomer is selected from a deuterated ethylene.

8. The copolymer composition of claim 7 ,

wherein the poly(acrylate) block includes >95 wt % of acrylate monomer derived units, wherein the acrylate monomer is methyl (meth)acrylate; and,

wherein the poly(silyl acrylate) block includes >95 wt % of silyl acrylate monomer derived units, wherein the silyl acrylate monomer is (trimethylsilyl)methyl methacrylate.

9. The copolymer composition of claim 8 , wherein the copolymer composition contains 5 to 30 wt % antioxidant (based on the weight of the block copolymer).

10. A method comprising:

providing a substrate;

providing a copolymer composition according to claim 1 ;

applying a film of the copolymer composition to the substrate;

optionally, baking the film;

annealing the film, leaving a pattern of poly(acrylate) domains and poly(silyl acrylate) domains;

treating the annealed film to remove the poly(acrylate) domains from the annealed film and to convert the poly(silyl acrylate) domains in the annealed film to SiO x .

11. A copolymer composition, comprising: a block copolymer having a poly(acrylate) block and a poly(silyl acrylate) block; wherein the block copolymer exhibits a number average molecular weight, M N , of 1 to 1,000 kg/mol; wherein the block copolymer exhibits a polydispersity, PD, of 1 to 2; and, wherein the block copolymer contains ≦75 wt % of a poly(methyl methacrylate)-block-poly((trimethylsilyl)methyl methacrylate) diblock copolymer.

12. The copolymer composition of claim 11 , wherein the block copolymer contains <0.001 wt % of a poly(methyl methacrylate)-block-poly((trimethylsilyl)methyl methacrylate) diblock copolymer.

Assignments (6)