Silsesquioxane derivatives and process for production thereof
The present inventors have obtained a PSQ derivative of a completely condensed type into which a functional group is readily introduced by using a novel PSQ derivative of an incompletely condensed type in which four alkaline metal atoms are bonded to silsesquioxane of a cage type having eight Si's. The above silsesquioxane derivative is represented by Formula (1). A silsesquioxane derivative to which alkaline metal atoms are bonded is represented by Formula (2). In Formula (1) and Formula (2), R is a group selected from alkyl, aryl and arylalkyl; Y is a group represented by Formula (a) or Formula (b); and M is a monovalent alkaline metal atom. X in Formula (a) and Formula (b) is hydrogen, halogen, a hydroxyl group or a monovalent organic group, and Z is —O—, —CH 2 — or a single bond. The preferred organic group is a functional group or a group having a functional group.
1. A silsesquioxane derivative represented by Formula (1):
wherein each R is alkyl having 1 to 45 carbon atoms, a substituted or non-substituted aryl, or a substituted or non-substituted arylalkyl; Y is a group represented by Formula (a) or Formula (b); in the alkyl having 1 to 45 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in alkylene of the substituted or non-substituted arylalkyl, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene:
wherein in Formula (a), each X is independently alkyl having 1 to 45 carbon atoms, a substituted or non-substituted phenyl, or a group having a functional group, and at least one X is a group having a functional group; in Formula (b), each X is independently hydrogen, alkyl having 1 to 45 carbon atoms, a substituted or non-substituted phenyl, or a group having a functional group, Z is —O—, —CH 2 — or a single bond, and at least one X is hydrogen or a group having a functional group; in the alkyl having 1 to 45 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; the group having a functional group in Formula (a) is cyanoalkyl, carboxyalkyl, mercaptoalkyl, acryloyloxyalkyl, methacryloyloxyalkyl, glycidyloxyalkyl, 2,4-dioxo-3-oxa-cyclopentylalkyl, or oxetanyloxyalkyl, and the carbon number of alkylene in these groups is 2 to 4; the group having a functional group in Formula (b) is chloroalkyl, cyanoalkyl, aminoalkyl, hydroxyalkyl, carboxyalkyl, mercaptoalkyl, ethenyl, 2-propenyl, acryloyloxyalkyl, methacryloyloxyalkyl, acetoxyalkyl, glycidyloxyalkyl, 2,4-dioxo-3-oxa-cyclopentylalkyl, or oxetanyloxyalkyl, and the carbon number of alkylene in these groups is 2 to 4; and, when two Xs in Formula (a) are same groups, they may be chlorines.
2. The silsesquioxane derivative according to claim 1 , wherein each R is independently a substituted or non-substituted phenyl; in the substituted phenyl, at least one hydrogen of phenyl is replaced by halogen or alkyl having 1 to 10 carbon atoms; in the above alkyl having 1 to 10 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or phenylene; and, when the phenyl has plural substituents, the substituents may be the same group or different groups.
3. The silsesquioxane derivative according to claim 1 , wherein each R is independently a substituted or non-substituted phenylalkyl; in the substituted phenylalkyl, at least one hydrogen of phenyl is replaced by halogen or alkyl having 1 to 12 carbon atoms; in the above alkyl having 1 to 12 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or phenylene; in alkylene of the substituted or non-substituted phenylalkyl, the number of carbon atoms is 1 to 12, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O— or cycloalkylene; and, when the phenyl has plural substituents, the substituents may be the same group or different groups.
4. The silsesquioxane derivative according to claim 1 , wherein each R is independently alkyl having 1 to 8 carbon atoms, a substituted or non-substituted phenyl, or a substituted or non-substituted phenylalkyl; in the alkyl having 1 to 8 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 —may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in the substituted phenyl, at least one hydrogen of phenyl is replaced by halogen, methyl or methoxy; in the substituted phenylalkyl, at least one hydrogen of phenyl is replaced by fluorine, alkyl having 1 to 4 carbon atoms, ethenyl or methoxy; in alkylene of the substituted or non-substituted phenylalkyl, the number of carbon atoms is 1 to 8, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, when the phenyl has plural substituents, the substituents may be the same group or different groups.
5. The silsesquioxane derivative according to claim 1 , wherein all of R's are the same group selected from alkyl having 1 to 8 carbon atoms, a substituted or non-substituted phenyl, or a substituted or non-substituted phenylalkyl; in the alkyl having 1 to 8 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in the substituted phenyl, at least one hydrogen of phenyl is replaced by halogen, methyl or methoxy; in the substituted phenylalkyl, at least one hydrogen of phenyl is replaced by fluorine, alkyl having 1 to 4 carbon atoms, ethenyl or methoxy; in alkylene of the substituted or non-substituted phenylalkyl, the number of carbon atoms is 1 to 8, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, when the phenyl has plural substituents, the substituents may be the same group or different groups.
6. The silsesquioxane derivative according to claim 1 , wherein all of R's are the same group selected from a substituted or non-substituted phenyl and a substituted or non-substituted phenylalkyl; in the substituted phenyl, at least one hydrogen of phenyl is replaced by halogen, methyl or methoxy; in the substituted phenylalkyl, at least one hydrogen of phenyl is replaced by fluorine, alkyl having 1 to 4 carbon atoms, ethenyl or methoxy; in alkylene of the substituted or non-substituted phenylalkyl, the number of carbon atoms is 1 to 8, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, when the phenyl has plural substituents, the substituents may be the same group or different groups.
7. The silsesquioxane derivative according to claim 1 , wherein all of R's are non-substituted phenyls.
8. The silsesquioxane derivative according to claim 1 , wherein at least one X in each of Formula (a) and Formula (b) is a polymerizable group.
9. The silsesquioxane derivative according to claim 1 , wherein at least one X in Formula (a) acryloyloxyalkyl, methacryloyloxyalkyl, glycidyloxyalkyl, or oxetanyloxyalkyl, and at least one X in Formula (b) is ethenyl, 2-propenyl, acryloyloxyalkyl, methacryloyloxyalkyl, glycidyloxyalkyl or oxetanyloxyalkyl.
10. The silsesquioxane derivative according to claim 1 , wherein at least one X in each of Formula (a) and Formula (b) is 2,4-dioxo-3-oxa-cyclopentylalkyl.
11. A polymer having the silsesquioxane derivative defined in claim 8 as a structural unit, obtained by polymerizing the silsesquioxane derivative defined in claim 8 as a monomer, a comonomer, or a raw material for a polycondensed matter.
12. A polymer having the silsesquioxane derivative defined in claim 9 as a structural unit, obtained by polymerizing the silsesquioxane derivative defined in claim 9 as a monomer or comonomer.
13. A polymer having the silsesquioxane derivative defined in claim 10 as a structural unit, obtained by polymerizing the silsesquioxane derivative defined in claim 10 as a raw material for a polycondensed matter.
14. A production process for the silsesquioxane derivative represented by Formula (1), characterized by reacting a silsesquioxane derivative represented by Formula (2) with a silicon compound having at least two chlorines:
wherein each R is a group independently selected from hydrogen, the group of alkyls having 1 to 45 carbon atoms, the group of substituted or non-substituted aryls and the group of substituted or non-substituted arylalkyls; Y is a group represented by Formula (a) or Formula (b); in the alkyl having 1 to 45 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in alkylene of the substituted or non-substituted arylalkyl, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene:
wherein each X is independently hydrogen, halogen, a hydroxyl group, alkyl having 1 to 45 carbon atoms, a substituted or non-substituted aryl, a substituted or non-substituted arylalkyl, a functional group or a group having a functional group; in the alkyl having 1 to 45 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 —may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in alkylene of the substituted or non-substituted arylalkyl, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, Z is —O—, —CH 2 — or a single bond:
wherein R is the same as R in Formula (1); and, M is a monovalent alkaline metal atom.
15. The production process according to claim 14 , wherein the silicon compound having at least two chlorines is a compound represented by Formula (3):
wherein n is 0 or 1; Z and X 1 are defined in the same manner as Z and X in Formula (b) respectively.
16. The production process according to claim 14 , wherein the silicon compound having at least two chlorines is a compound represented by Formula (4):
wherein X 1 is defined in the same manner as X in Formula (a).
17. The production process according to claim 14 , wherein the silicon compound having at least two chlorines is a compound represented by Formula (5):
wherein Z and X 1 are defined in the same manner as Z and X in Formula (b) respectively.
18. A silsesquioxane derivative represented by Formula (2):
wherein each R is a group independently selected from hydrogen, the group of alkyls having 1 to 45 carbon atoms, the group of substituted or non-substituted aryls and the group of substituted or non-substituted arylalkyls; in the alkyl having 1 to 45 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in alkylene of the substituted or non-substituted arylalkyl, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, M is a monovalent alkaline metal atom.
19. The silsesquioxane derivative according to claim 18 , wherein all of R's are the same group selected from alkyl having 1 to 8 carbon atoms, a substituted or non-substituted phenyl, a substituted or non-substituted phenylalkyl, and naphthyl; in the alkyl having 1 to 8 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in the substituted or non-substituted phenyl, optional hydrogen on the benzene ring may be replaced by halogen, methyl or methoxy; in phenyl of the substituted or non-substituted phenylalkyl, optional hydrogen on the benzene ring may be replaced by fluorine, alkyl having 1 to 4 carbon atoms, ethenyl or methoxy; in alkylene of the substituted or non-substituted phenylalkyl, the number of carbon atoms is 1 to 8, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, when the phenyl has plural substituents, the substituents may be the same group or different groups.
20. A production process for the silsesquioxane derivative represented by Formula (2), which comprises hydrolyzing and condensing a silicon compound represented by Formula (6) in the presence of a monovalent alkaline metal hydroxide, water and an alcohol:
wherein each R is a group independently selected from hydrogen, the group of alkyls having 1 to 45 carbon atoms, the group of substituted or non-substituted aryls and the group of substituted or non-substituted arylalkyls; in the alkyl having 1 to 45 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in alkylene of the substituted or non-substituted arylalkyl, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, M is a monovalent alkaline metal atom:
wherein R is the same as R in Formula (2); and, A is a hydrolyzable group.
21. The production process according to claim 20 , wherein the monovalent alkaline metal hydroxide is sodium hydroxide or potassium hydroxide.
22. The production process according to claim 20 , wherein A is chlorine or alkyloxy having 1 to 4 carbon atoms.
23. The production process according to claim 20 , wherein all of R's in formula (2) are the same group selected from alkyl having 1 to 8 carbon atoms, a substituted or non-substituted phenyl, a substituted or non-substituted phenylalkyl, and naphthyl; in the alkyl having 1 to 8 carbon atoms, optional hydrogen may be replaced by fluorine, and optional —CH 2 — may be replaced by —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in the substituted or non-substituted phenyl, optional hydrogen on the benzene ring may be replaced by halogen, methyl or methoxy; in phenyl of the substituted or non-substituted phenylalkyl, optional hydrogen on the benzene ring may be replaced by fluorine, alkyl having 1 to 4 carbon atoms, ethenyl or methoxy; in alkylene of the substituted or non-substituted phenylalkyl, the number of carbon atoms is 1 to 8, and optional —CH 2 — may be replaced by —O—, —CH═CH— or cycloalkylene; and, when the phenyl has plural substituents, the substituents may be the same group or different groups; and, A is chlorine or alkyloxy having 1 to 4 carbon atoms.