2-cyanoethyl-containing organoxysilane compound, silsesquioxane, and making methods

Abstract

A 2-cyanoethyl-containing organoxysilane compound having the formula: NC—CH 2 —CH 2 —X—Si(OR 1 ) 3 is heat resistant and compatible with organic solvents. R 1 is a C 1 -C 20 monovalent hydrocarbon group, and X is a C 2 -C 20 divalent hydrocarbon group which contains a methylene and/or methine moiety, at least one of the methylene and methine moieties being substituted with a divalent heteroatom linking moiety NR (wherein R is hydrogen, C 1 -C 20 monovalent hydrocarbon group or 2-cyanoethyl), a trivalent heteroatom linking moiety N, or a combination thereof.

1 . A method for preparing a 2-cyanoethyl-containing organoxysilane compound of formula (1):
   NC—CH 2 —CH 2 —X—Si(OR 1 ) 3   (1)
   
       wherein
 each R 1  is independently a C 1 -C 20  straight chain, branched, or cyclic monovalent hydrocarbon group, and 
 X is a C 2 -C 20  straight chain, branched, or cyclic divalent hydrocarbon group which contains a methylene and/or methine moiety, at least one of the methylene and methine moieties being substituted by a divalent heteroatom linking moiety NR wherein R is hydrogen, a C 1 -C 20  monovalent hydrocarbon group, or 2-cyanoethyl, a trivalent heteroatom linking moiety N, or a combination thereof, 
 with the proviso that the heteroatom linking moieties do not adjoin each other, the heteroatom linking moiety does not adjoin a silicon atom, and the NC—CH 2 —CH 2 — linkage is bonded to the heteroatom linking moiety included in X,
 said method comprising 
 
 conducting a Michael addition reaction of an organoxysilane compound of formula (2):
   HX—Si(OR 1 ) 3   (2)
 
 
 
       wherein R 1  and X are as defined above, and the hydrogen atom H in the formula is bonded to the heteroatom linking moiety included in X
 with acrylonitrile. 
 
     
     
         2 . The method of  claim 1 , wherein R is a C 1 -C 6  straight chain monovalent hydrocarbon group or 2-cyanoethyl. 
     
     
         3 . A silsesquioxane of formula (3):
   [NC—CH 2 —CH 2 —X—SiO 3/2 ] p [Z—SiO 3/2 ] q   (3)
   
       wherein
 X is a C 2 -C 20  straight chain, branched, or cyclic divalent hydrocarbon group which contains a methylene and/or methine moiety, at least one of the methylene and methine moieties being substituted by a divalent heteroatom linking moiety NR wherein R is hydrogen, a C 1 -C 20  monovalent hydrocarbon group, or 2-cyanoethyl, a trivalent heteroatom linking moiety N, or a combination thereof, with the proviso that the heteroatom linking moieties do not adjoin each other, the heteroatom linking moiety does not adjoin a silicon atom, and the NC—CH 2 —CH 2 — linkage is bonded to the heteroatom linking moiety included in X, 
 Z is a substituted or unsubstituted, C 1 -C 20  straight, branched or cyclic monovalent hydrocarbon group, 
 p is an integer of 1 to 150, 
 q is an integer of 0 to 100, and 
 p+q is 4 to 150. 
 
     
     
         4 . A method for preparing a silsesquioxane, said method comprising
 effecting hydrolysis and condensation of a 2-cyanoethyl-containing organoxysilane compound of formula (1):
   NC—CH 2 —CH 2 —X—Si(OR 1 ) 3   (1)
 
   
       wherein
 each R 1  is independently a C 1 -C 20  straight chain, branched, or cyclic monovalent hydrocarbon group, and 
 X is a C 2 -C 20  straight chain, branched, or cyclic divalent hydrocarbon group which contains a methylene and/or methine moiety, at least one of the methylene and methine moieties being substituted by a divalent heteroatom linking moiety NR wherein R is hydrogen, a C 1 -C 20  monovalent hydrocarbon group, or 2-cyanoethyl, a trivalent heteroatom linking moiety N, or a combination thereof, 
 with the proviso that the heteroatom linking moieties do not adjoin each other, the heteroatom linking moiety does not adjoin a silicon atom, and the NC—CH 2 —CH 2 — linkage is bonded to the heteroatom linking moiety included in X, 
 the silsesquioxane having the formula (3):
   [NC—CH 2 —CH 2 —X—SiO 3/2 ] p [Z—SiO 3/2 ] q   (3)
 
 
 
       wherein
 X is as defined above, 
 Z is a substituted or unsubstituted C 1 -C 20  straight chain, branched, or cyclic monovalent hydrocarbon group, 
 p is an integer of 4 to 150, and 
 q is 0. 
 
     
     
         5 . A method for preparing a silsesquioxane, said method comprising
 effecting co-hydrolysis and condensation of a 2-cyanoethyl-containing organoxysilane compound of formula (1):
   NC—CH 2 —CH 2 —X—Si(OR 1 ) 3   (1)
 
   
       wherein
 each R 1  is independently a C 1 -C 20  straight chain, branched, or cyclic monovalent hydrocarbon group, and 
 X is a C 2 -C 20  straight chain, branched, or cyclic divalent hydrocarbon group which contains a methylene and/or methine moiety, at least one of the methylene and methine moieties being substituted by a divalent heteroatom linking moiety NR wherein R is hydrogen, a C 1 -C 20  monovalent hydrocarbon group, or 2-cyanoethyl, a trivalent heteroatom linking moiety N, or a combination thereof, 
 with the proviso that the heteroatom linking moieties do not adjoin each other, the heteroatom linking moiety does not adjoin a silicon atom, and the NC—CH 2 —CH 2 — linkage is bonded to the heteroatom linking moiety included in X,
 with 
 
 at least one trifunctional organoxysilane compound of formula (4):
   Z—SiR 2   3   (4)
 
 
 
       wherein R 2  is a group which becomes hydrolytic upon bonding with a silicon atom and Z is a substituted or unsubstituted C 1 -C 20  straight chain, branched, or cyclic monovalent hydrocarbon group,
 the silsesquioxane having the formula (3):
   [NC—CH 2 —CH 2 —X—SiO 3/2 ] p [Z—SiO 3/2 ] q   (3)
 
 
 
       wherein X and Z are as defined above, p is an integer of 1 to 150, q is an integer of 1 to 100, and p+q is 4 to 150. 
     
     
         6 . The method of  claim 5 , wherein R 2  is a C 1 -C 6  organoxy group, a C 1 -C 3  acyloxy group, or a halogen atom.