Precursor solution for polyimide/silica composite material, its manufacture method, and polymide/silica composite material having low volume shrinkage

1. A process for preparing a precursor solution for polyimide/silica composite material, comprising:

(A) providing a poly(amic acid) solution;

(B) adding an amino coupling agent having formula H 2 N—R 1 —Si(R 2 ) 3 (in which R 1 is a C 1-6 -alkylene or an arylene, and R 2 may be the same or different, each representing a C 1-6 -alkoxy) to the solution of step (A);

(C) adding a monomer of a silane compound to the solution obtained from step (B) to allow the poly(amic acid) to carry a silica moiety;

(D) adding a monomer of formula (R 6 ) x Si(R 7 ) (4−x) (in which R 6 is a photo-polymerizable unsaturated group ended group, R 7 is halogen, C 1-6 -alkoxy, C 2-6 -alkenoxy or aryloxy, and x is an integer of 1 to 3) to the solution obtained from step (C) to allow the silica moiety to carry a photo-polymerizable unsaturated group; and

(E) adding a monomer of formula R 8 N(R 9 ) 2 (in which R 8 is a photo-polymerizable unsaturated group ended group and R 9 is a C 1-6 -alkyl) to the solution obtained from step (D) to allow the poly(amic acid) to carry a photo-polymerizable unsaturated group to produce a precursor solution for a photo-polymerizable polyimide/silica composite material.

2. The process of claim 1 , wherein step (E) is conducted in the presence of a photoinitiator.

3. The process of claim 2 , wherein said monomer of the silane compound is selected from the group consisting of tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane, tetrabutyloxysilane and mixtures thereof.

4. The process of claim 1 , further comprising, before step (D), adding a coupling agent of formula R 4 Si(R 5 ) 3 (in which R 4 is an epoxy ended group and R 5 is halogen, C 1-6 -alkyl, C 2-6 -alkenoxy, or aryloxy) to the solution obtained from step (C).

5. The process of claim 1 , wherein said monomer of the silane compound has formula Si(R 3 ) 4 , in which R 3 may be the same or different, each represents halogen, C 1-6 -alkoxy, C 2-6 -alkenoxy, or aryloxy, provided that not all the four R 3 are halogen at the same time.

6. The process of claim 1 , wherein said photo-polymerizable unsaturated group is an ethylenically unsaturated group, which is selected from the group consisting of vinyl, allyl, vinylphenyl, allylphenyl, propenyloxymethyl, propenyloxyethyl, propenyloxypropyl, propenyloxybutyl, propenyloxyamyl, propenyloxyhexyl, methylpropenyloxymethyl, methylpropenyloxyethyl, methylpropenyloxypropyl, methylpropenyloxybutyl, methylpropenyloxyamyl and methylpropenyloxyhexyl.

7. The process of claim 1 , wherein the monomer of formula (R 6 ) x Si(R 7 ) (4−x) is selected from the group consisting of:

3 -methylpropenyloxypropyltrimethoxysilane,

3-methylpropenyloxypropyltriethoxysilane,

2-methylpropenyloxyethyltrimethoxysilane,

2-methylpropenyloxyethyltriethoxysilane,

3-methylpropenyloxybutyltrimethoxysilane,

3-methylpropenyloxybutyltriethoxysilane,

3-propenyloxypropyltrimethoxysilane,

3-propenyloxypropyltriethoxysilane,

2-propenyloxyethyltrimethoxysilane,

2-propenyloxyethyltriethoxysilane,

3-propenyloxybutyltrimethoxysilane,

3-propenyloxybutyltriethoxysilane,

3-methylmethylpropenyloxypropyltrimethoxysilane,

3-methylmethylpropenyloxypropyltriethoxysilane,

3-methylmethylpropenyloxyethyltrimethoxysilane,

3-methylmethylpropenyloxyethyltriethoxysilane,

3-methylmethylpropenyloxybutyltrimethoxysilane,

3-methylmethylpropenyloxybutyltriethoxysilane,

3-methylpropenyloxypropyltrimethoxysilane,

3-methylpropenyloxypropyltriethoxysilane,

3-methylpropenyloxyethyltrimethoxysilane,

3-methylpropenyloxyethyltriethoxysilane,

3-methylpropenyloxybutyltrimethoxysilane,

3-methylpropenyloxybutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-vinylphenyltrimethoxysilane,

3-vinylphenyltriethoxysilane, 4-vinylphenyltrimethoxysilane,

4-vinylphenyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane,

4-allylphenyltrimethoxysilane, 4-allylphenyltriethoxysilane,

bis(3-methylpropenyloxypropyl)dimethoxysilane,

bis(3-methylpropenyloxypropyl)diethoxysilane,

bis(2-methylpropenyloxyethyl)dimethoxysilane,

bis(2-methylpropenyloxyethyl)diethoxysilane,

bis(3-methylpropenyloxybutyl)dimethoxysilane,

bis(3-methylpropenyloxybutyl)diethoxysilane,

bis(3-propenyloxypropyl)dimethoxysilane,

bis(3-propenyloxypropyl)diethoxysilane,

bis(2-propenyloxyethyl)dimethoxysilane,

bis(2-propenyloxyethyl)diethoxysilane,

bis(3-propenyloxybutyl)dimethoxysilane,

bis(3-propenyloxybutyl)diethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, diallyldimethoxysilane, diallyldiethoxysilane,

tri(3-methylpropenyloxypropyl)methoxysilane,

tri(3-methylpropenyloxypropyl)ethoxysilane,

tri(2-methylpropenyloxyethyl)methoxysilane,

tri(2-methylpropenyloxyethyl)ethoxysilane,

tri(3-methylpropenyloxybutyl)methoxysilane,

tri(3-methylpropenyloxybutyl)ethoxysilane,

tri(3-propenyloxypropyl)methoxysilane,

tri(3-propenyloxypropyl)ethoxysilane,

tri(2-propenyloxyethyl)methoxysilane,

tri(2-propenyloxyethyl)ethoxysilane,

tri(3-propenyloxybutyl)methoxysilane,

tri(3-propenyloxybutyl)ethoxysilane, trivinylmethoxysilane, trivinylethoxysilane, triallylmethoxysilane, and triallylethoxysilane and mixtures thereof.

8. The process of claim 7 , wherein the monomer of formula (R 6 ) x Si(R 7 ) (4−x) is selected from the group consisting of:

3-methylpropenyloxypropyltrimethoxysilane.

3-methylpropenyloxypropyltriethoxysilane,

2-methylpropenyloxyethyltrimethoxysilane, and

2-methylpropenyloxyethyltriethoxysilane and mixtures thereof.

9. The process of claim 1 , wherein the monomer of formula R 8 N(R 9 ) 2 is selected from the group consisting of

2-dimethylaminoethyl methacrylate,

2-diethylaminoethyl methacrylate,

2-dipropylaminoethyl methacrylate,

3-methylpropenyloxypropyldimethylamine,

3-methylpropenyloxypropyldiethylamine,

3-methylpropenyloxypropyldipropylamine,

3-propenyloxypropyldimethylamine,

3-propenyloxypropyldiethylamine,

3-propenyloxypropyldipropylamine,

3-methylmethylpropenyloxypropyldimethylamine,

3-methylmethylpropenyloxypropyldiethylamine,

3-methylmethylpropenyloxypropyldipropylamine,

4-(methylpropenyloxypropyl)phenyldimethylamine,

4-(methylpropenyloxypropyl)phenyldiethylamine,

4-(methylpropenyloxypropyl)phenyldipropylamine,

4-(methylpropenyloxyethyl)phenyldimethylamine,

4-(methylpropenyloxyethyl)phenyldiethylamine,

4-(methylpropenyloxyethyl)phenyldipropylamine,

4-(methylpropenyloxymethyl)phenyldimethylamine,

4-(methylpropenyloxymethyl)phenyldiethylamine,

4-(methylpropenyloxymethyl)phenyldipropylamine, allyldimethylamine, allyldiethylamine,allyldipropylamine, vinyldimethylamine, vinyldiethylamine, vinyldipropylamine and mixtures thereof.

10. The process of claim 9 , wherein the monomer of formula R 8 N(R 9 ) 2 is selected from 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dipropylaminoethyl methacrylate, and allyldimethylamine and mixtures thereof.

11. The process of claim 1 , wherein said monomer of the silane compound has formula Si(R 3 ) 4 , in which R 3 may be the same or different, each represents halogen or C 1-6 -alkoxy, provided that not all the four R 3 are halogen at the same time;

wherein the monomer of formula (R 6 ) x Si(R 7 ) (4−x) is selected from the group consisting of 3-methylpropenyloxypropyltrimethoxysilane, 3-methylpropenyloxypropyltriethoxysilane, 2-methylpropenyloxyethyltrimethoxysilane, 2-methylpropenyloxyethyltriethoxysilane, 3-methylpropenyloxybutyltrimethoxysilane, 3-methylpropenyloxybutyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, 2-propenyloxyethyltrimethoxysilane, 2-propenyloxyethyltriethoxysilane, 3-propenyloxybutyltrimethoxysilane, 3-propenyloxybutyltriethoxysilane, 3-methylmethylpropenyloxypropyltrimethoxysilane, 3-methylmethylpropenyloxypropyltriethoxysilane, 3-methylmethylpropenyloxyethyltrimethoxysilane, 3-methylmethylpropenyloxyethyltriethoxysilane, 3-methylmethylpropenyloxybutyltrimethoxysilane, 3-methylmethylpropenyloxybutyltriethoxysilane, 3-methylpropenyloxypropyltrimethoxysilane, 3-methylpropenyloxypropyltriethoxysilane, 3-methylpropenyloxyethyltrimethoxysilane, 3-methylpropenyloxyethyltriethoxysilane, 3-methylpropenyloxybutyltrimethoxysilane, and 3-methylpropenyloxybutyltriethoxysilane, and mixtures thereof; and

wherein the monomer of formula R 8 N(R 9 ) 2 is selected from the group consisting of 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, and 2-dipropylaminoethyl methacrylate, and mixtures thereof, and

wherein said photo-polymerizable unsaturated group is an ethylenically unsaturated group, which is selected from the group consisting of propenyloxymethyl, propenyloxyethyl, propenyloxypropyl, propenyloxybutyl, propenyloxyamyl, propenyloxyhexyl, methylpropenyloxymethyl, methylpropenyloxyethyl, methylpropenyloxypropyl, methylpropenyloxybutyl, methylpropenyloxyamyl, and methylpropenyloxyhexyl, and mixtures thereof.