METAL OXIDE NANOPARTICLES, METHODS OF MAKING, AND METHODS OF USE

1 . A polymerizable composition, comprising:

a polymerizable compound, wherein the polymerizable compound is a monomer or oligomer comprising a functional group capable of undergoing radical, cationic, anionic, thermal, or photochemical polymerization; and

treated titanium oxide nanoparticles;

wherein the treated titanium oxide nanoparticles are prepared by hydrolyzing metal alkoxide with an acidic alcohol solution to form a first sol, wherein the acidic alcohol solution comprises an alkyl alcohol, water, and an acid;

treating the first sol with an organosilane to form a second sol; and

treating the second sol with an organic base in an amount of about 0.1:1 to about 0.9:1 molar ratio of organic base to acid to form a third sol comprising treated titanium oxide nanoparticles; and

wherein the polymerizable composition is prepared by combining the polymerizable compound with the third sol to form a mixture; and removing solvent from the mixture to form a polymerizable composition.

2 . The polymerizable composition of claim 1 , wherein the metal is titanium, cerium, zirconium, or tin; and the alkoxide is a linear or branched C 1 -C 12 alkoxide.

3 . The polymerizable composition of claim 1 , wherein the acid is present in an amount of about 0.1:1 to about 2:1 molar ratio of acid to metal alkoxide.

4 . The polymerizable composition of claim 1 , wherein the water is present in an amount of about 0.1:1 to about 5:1 molar ratio of water to metal alkoxide.

5 . The polymerizable composition of claim 1 , wherein the organosilane is an alkoxyorganosilane, an aryloxyorganosilane, an arylalkoxyorganosilane, an arlyalkylalkoxyorganosilane, an alkylaminoorganosilane, or a combination comprising at least one of the foregoing organosilanes.

6 . The polymerizable composition of claim 1 , wherein the organosilane lacks groups reactive with a polymerizable compound.

7 . The polymerizable composition of claim 1 , wherein the organosilane is in an amount of about 1:1 to about 1:10 molar ratio of metal alkoxide to organosilane.

8 . The polymerizable composition of claim 1 , the organic base is a linear or branched chain C 1 -C 12 alkylamine.

9 . The polymerizable composition of claim 1 , wherein the second sol is formed at a temperature of about 25° C. to about 100° C. for about 8 hours.

10 . The polymerizable composition of claim 1 , wherein the polymerizable composition further comprises an initiator.

11 . The polymerizable composition of claim 1 , wherein the polymerizable compound is a mono or polyfunctional (meth)acrylate.

12 . The polymerizable composition of claim 1 , wherein the polymerizable compound is a (meth)acrylate according to general structure (I)

wherein

R 1 is substituted or unsubstituted C 1 -C 12 alkyl, cycloalkyl, alkenyl, cycloalkenyl, or alkynyl; or substituted or unsubstituted C 6 -C 16 aryl, including phenyl, wherein the substitution independently includes fluorine, chlorine, bromine, iodine, C 1 -C 6 alkyl, C 1 -C 3 perhalogenated allyl, C 1 -C 6 alkoxy, hydroxy, C 1 -C 6 ketone, C 1 -C 6 ester, N,N—(C 1 -C 3 ) alkyl substituted amide, or a combination comprising at least one of the forgoing substituents, and wherein the C 6 -C 16 aryl group, when substituted, may be mono-, di-, tri-, tetra- or penta-substituted;

R 2 is substituted or unsubstituted C 1 -C 12 alkylene, cycloalkylene, alkenylene, cycloalkenylene, or alkynylene; or substituted or unsubstituted C 6 -C 16 arylene, including phenylene, wherein the substitution independently includes fluorine, chlorine, bromine, iodine, C 1 -C 6 alkyl, C 1 -C 3 perhalogenated allyl, C 1 -C 6 alkoxy, hydroxy, C 1 -C 6 ketone, C 1 -C 6 ester, N,N—(C 1 -C 3 ) allyl substituted amide, or a combination comprising at least one of the forgoing substituents, and wherein the C 6 -C 6 aryl group, when substituted, may be mono-, di-, tri-, or tetra-substituted;

R 3 is hydrogen, methyl, or ethyl;

X 1 and X 2 are each independently O, S, or NR 4 , wherein R 4 is hydrogen or R 1 ;

X 3 is O or S;

m is 0 or 1;

n is 0, 1, 2, or 3; and

p is 1, 2, 3, or 4.

13 . The polymerizable composition of claim 1 , wherein the polymerizable compound is a (meth)acrylate according to general structure (II)

wherein

R 5 is hydrogen or methyl;

X 4 is O, S, or NR 7 , wherein R 7 is hydrogen or C 1 -C 6 alkyl;

R 6 is substituted or unsubstituted C 1 -C 300 alkyl, aryl, alkaryl, arylalkyl, or heteroaryl, wherein the substitution independently includes fluorine, chlorine, bromine, iodine, C 1 -C 6 alkyl, C 1 -C 3 perhalogenated alkyl, hydroxy, C 1 -C 6 ketone, C 1 -C 6 ester, N,N—(C 1 -C 3 ) alkyl substituted amide, or a combination comprising at least one of the forgoing substituents; and

b is 2, 3, or 4.

14 . The polymerizable composition of claim 13 , wherein R 6 is a group according to according to general structure (III)

wherein

Q is —C(CH 3 ) 2 —, —CH 2 —, —C(O)—, —S(O)—, or —S(O) 2 —;

Y is C 1 -C 6 alkyl or hydroxy substituted C 1 -C 6 alkyl;

i is 1 to 10;

t is 0, 1, 2, 3, or 4; and

d is about 1 to about 3.

15 . The polymerizable composition of claim 1 , wherein the polymerizable compound is

a urethane (meth)acrylate or

a (meth)acrylate produced by the reaction of an acrylic or methacrylic acid with bisphenol-A diglycidyl ether; bisphenol-F diglycidyl ether; tetrabromo bisphenol-A diglycidyl ether; tetrabromo bisphenol-F diglycidyl ether; 1,3-bis-{4-[1-methyl-1-(4-oxiranylmethoxy-phenyl)-ethyl]-phenoxy}-propan-2-ol; 1,3-bis-{2,6-dibromo-4-[1-(3,5-dibromo-4-oxiranylmethoxy-phenyl)-1-methyl-ethyl]-phenoxy}-propan-2-ol; or a combination comprising at least one of the foregoing di-epoxides.

16 . An article prepared from curing the polymerizable composition of claim 1 .

17 . An optical article or light management film prepared from curing the polymerizable composition of claim 1 .

18 . The polymerizable composition of claim 1 , wherein the polymerizable composition exhibits a yellowness index of less than about 30 as measured by ASTM D1925 using a path length of 1 mm.

19 . A polymerizable composition, comprising:

a polymerizable compound; and

treated titanium oxide nanoparticles, wherein the treated titanium oxide nanoparticles are prepared by hydrolyzing titanium tetraalkoxide with an acidic alcohol solution to form a first sol, wherein the acidic alcohol solution comprises

an alkyl alcohol,

water in an amount of about 0.1:1 to about 5:1 molar ratio of water to titanium tetraalkoxide, and

an acid in an amount of about 0.1:1 to about 2:1 molar ratio of acid to titanium tetraalkoxide;

treating the first sol with an organosilane to form a second sol; and

treating the second sol with an organic base in an amount of about 0.1:1 to about 0.9:1 molar ratio of organic base to acid to form a third sol comprising treated titanium oxide nanoparticles.

20 . An article prepared from curing the polymerizable composition of claim 19 .