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US 5,969,073 AGranted
Group 4 metal-containing organosilicon dendrimers and method for synthesizing organosilicon denrimers
AssigneeMassachusetts Institute of Technology
InventorsDietmar Seyferth, Ralf Wyrwa
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Abstract
Group 4 metal-containing organosilicon dendrimers are described. Also described are methods for synthesizing the dendrimers. The dendrimers can be useful in several applications including as olefin polymerization and copolymerization catalysts and as silane polymerization catalysts.
Claims76
An organosilicon dendrimer comprising a dendrimer arm including a metal-containing unit, wherein a metal in the metal-containing unit is a Group 4 metal selected from the group consisting of Ti, Zr, and Hf.
A method for synthesizing an organosilicon dendrimer comprising steps of:
- (a) providing a core molecule further including a reactive functional group;
- (b) providing a silicon hydride;
- (c) providing a hydrosilylation catalyst;
- (d) reacting said silicon hydride with said core molecule in the presence of said hydrosilylation catalyst to produce an intermediate organosilicon dendrimer;
- (e) reacting said intermediate organosilicon dendrimer to introduce an unsaturated organic functional group;
- (f) repeating steps (b), (c), (d), and (e) n times using said intermediate organosilicon dendrimer as formed in step (e) as said core molecule to produce a G.sub.n generation organosilicon dendrimer wherein n is an integer in the range of from about 1 to about 10 and G.sub.n is the generation number;
- and
- (g) reacting said G.sub.n generation organosilicon dendrimer with a Group 4 metal-containing reagent to form an organosilicon dendrimer including a Group 4 metal.
5 more elements
A method for synthesizing a Group 4 transition metal-containing organosilicon dendrimer comprising steps of:
- (a) providing starting monomers including at least one Si--H bond and at least two functional groups each further including a terminal .dbd.CH.sub.2 bond;
- (b) inducing a hydrosilylation reaction so that said monomers are consumed to produce an intermediate organosilicon dendrimer;
- and
- (c) reacting said intermediate organosilicon dendrimer with a Group 4 metal-containing reagent to form an organosilicon dendrimer including a Group 4 metal.
1 more element
A method for synthesizing a Group 4 transition metal-containing organosilicon dendrimer comprising steps of:
- (a) providing a core molecule selected from the group consisting of Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 wherein n is an integer in the range of from about 0 to 20;
- RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and R is selected from the group consisting of alkyl, aryl, halogen, alkoxy and aryloxy;
- Si[C.sub.6 H.sub.4 (CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and C.sub.6 H.sub.4 is selected from the group consisting of para-phenylene and meta-phenylene;
- and RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and R is selected from the group consisting of alkyl, aryl, halogen, alkoxy and aryloxy;
- and C.sub.6 H.sub.4 is selected from the group consisting of para-phenylene and meta-phenylene;
- (b) adding a first reagent selected from the group consisting of HSi(CH.dbd.CH.sub.2).sub.3 ;
- HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ;
- HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3, wherein n is an integer in the range of from about 2 to about 20;
- R(H)Si(CH.dbd.CH.sub.2).sub.2 ;
- R(H)Si(CH.sub.2 CH.dbd.CH.sub.2).sub.2 ;
- and R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2, wherein n is an integer in the range of from about 2 to about 20, R is selected from the group consisting of methyl and higher alkyl, phenyl and substituted phenyl, halogen, alkoxy, aryloxy and dialkylamino groups to said core to form an intermediate product;
- (c) adding additional reagent selected from the group consisting of HSi(CH.dbd.CH.sub.3).sub.2 ;
- HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ;
- HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3, wherein n is an integer in the range of from about 2 to about 20;
- R(H)Si(CH.dbd.CH.sub.2).sub.2 ;
- R(H)Si(CH.sub.2 CH.dbd.CH.sub.2).sub.2 ;
- and R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2, wherein n is an integer in the range of from about 2 to about 20, R is selected from the group consisting of methyl and higher alkyl, phenyl and substituted phenyl, halogen, alkoxy, aryloxy and dialkylamino groups to said intermediate product to form an intermediate organosilicon dendrimer;
- and
- (d) reacting said intermediate organosilicon dendrimer with a Group 4 metal-containing reagent to form an organosilicon dendrimer including a Group 4 metal.
16 more elements
A method for synthesizing a Group 4 transition metal-containing organosilicon dendrimer comprising steps of:
- (a) providing a core molecule selected from the group consisting of Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 wherein n is an integer in the range of from about 0 to 20;
- and RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and R is selected from the group consisting of alkyl, aryl, halogen, alkoxy and aryloxy;
- (b) reacting said core molecule with a first reagent characterized by the formula [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.2 C.sub.6 H.sub.5 SiH, wherein n is an integer in the range of from about 0 to 20 to form an intermediate product;
- (c) reacting said intermediate product with a second reagent selected from the group consisting of [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.3 SiH;
- and [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.2 SiRH, wherein R is alkyl and n is integer in the range of from about 0 to 20 to form an intermediate dendrimer including reactive dendrimer arm ends;
- (d) adding a third reagent characterized by the formula R.sub.2 SiHX wherein X is selected from the group consisting of F, Cl, Br and I, and R is an alkyl group to react with said reactive dendrimer arm ends to form peripheral Si--X dendrimer arm ends wherein X is selected from the group consisting of F, Cl, Br, and I;
- (e) reducing said peripheral Si--X dendrimer arm ends to form Si--H peripheral dendrimer arm ends;
- (f) reacting said Si--H peripheral dendrimer arm ends with a reagent including a terminal olefin group to form a second intermediate dendrimer;
- (g) reacting said second intermediate dendrimer with HX, wherein X is selected from the group consisting of O.sub.3 SCF.sub.3 and Br, to form a dendrimer having a Si--X internal functionality;
- (h) reacting said dendrimer having a Si--X internal functionality with a reducing agent to form a dendrimer having a Si--H internal functionality;
- (i) reacting said dendrimer having a Si--H internal functionality with a Group 4 metal-containing reagent to form an organosilicon dendrimer including a Group 4 metal.
8 more elements
A method for synthesizing a Group 4 transition metal-containing organosilicon dendrimer comprising steps of:
- (a) providing a core molecule selected from the group consisting of Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 wherein n is an integer in the range of from about 0 to 20;
- and RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and R is selected from the group consisting of alkyl, aryl, halogen, alkoxy and aryloxy;
- (b) reacting said core molecule with [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ]R.sub.2 SiH wherein R is selected from the group consisting of methyl and alkyl groups to form an intermediate product and n is an integer in the range of from about 0 to about 20;
- (c) reacting said intermediate product with [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.2 C.sub.6 H.sub.5 SiH wherein n is an integer in the range of from about 0 to about 20 to form a second intermediate product;
- (d) reacting said second intermediate product with a reagent selected from the group consisting of [CH.sub.2 .dbd.CH(CH.sub.2)n].sub.3 SiH and [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.2 RSiH wherein R is alkyl and n is an integer in the range of from about 0 to 20 to form an intermediate dendrimer including reactive dendrimer arm ends;
- (e) adding a second reagent characterized by the formula R.sub.2 SiHX wherein R is an alkyl group and X is selected from the group consisting of F, Cl, Br and I to react with said reactive dendrimer arm ends to form peripheral Si--X dendrimer arm ends wherein X is selected from the group consisting of F, Cl, Br, and I;
- (f) reducing said peripheral Si--X dendrimer arm ends to form Si--H peripheral dendrimer arm ends;
- (g) reacting said Si--H peripheral dendrimer arm ends with a reagent including a terminal olefin group to form a second intermediate dendrimer;
- (h) reacting said second intermediate dendrimer with HX, wherein X is selected from the group consisting of O.sub.3 SCF.sub.3 and Br, to form a dendrimer having a Si--X internal functionality;
- (i) reacting said dendrimer having a Si--X internal functionality with a reducing agent to form a dendrimer having a Si--H internal functionality;
- (j) reacting said dendrimer having a Si--H internal functionality with a Group 4 metal-containing reagent to form an organosilicon dendrimer including a Group 4 metal.
8 more elements
A method for synthesizing a Group 4 transition metal-containing organosilicon dendrimer comprising steps of:
- (a) providing a core molecule selected from the group consisting of Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 wherein n is an integer in the range of from about 0 to 20;
- and RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and R is selected from the group consisting of alkyl, aryl, halogen, alkoxy and aryloxy;
- (b) reacting said core molecule with a first reagent characterized by the formula [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.2 C.sub.6 H.sub.5 SiH, wherein n is an integer in the range of from about 0 to 20 to form an intermediate product;
- (c) reacting said intermediate product with a second reagent selected from the group consisting of [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.3 SiH;
- and [CH.sub.2 .dbd.CH(CH.sub.2).sub.n ].sub.2 SiRH, wherein R is alkyl and n is an integer in the range of from about 0 to 20 to form an intermediate dendrimer including reactive dendrimer arm ends;
- (d) adding a third reagent characterized by the formula R.sub.2 SiHX where R is an alkyl group and X is selected from consisting of F, Cl, Br, and I to react with said reactive dendrimer arm ends to form peripheral Si--X dendrimer arm ends wherein X is selected from the group consisting of F, Cl, Br, and I;
- (e) alkylating said peripheral Si--X dendrimer arm ends to form a second intermediate dendrimer;
- (f) reacting said second intermediate dendrimer with HX, wherein X is selected from the group consisting of O.sub.3 SCF.sub.3 and Br, to form a dendrimer having a Si--X internal functionality;
- (g) reacting said dendrimer having a Si--X internal functionality with a reducing agent to form a dendrimer having a Si--H internal functionality;
- (h) reacting said dendrimer having a Si--H internal functionality with a Group 4 metal-containing reagent to form an organosilicon dendrimer including a Group 4 metal.
7 more elements
A method for synthesizing a carbosilane dendrimer comprising steps of:
- (a) providing starting monomers including at least one Si--H bond and at least two functional groups each further including a terminal .dbd.CH.sub.2 bond;
- (b) inducing a hydrosilylation reaction so that said monomers are consumed to produce an intermediate organosilicon dendrimer including a reactive CH.dbd.CH.sub.2 group;
- (c) adding a reagent characterized by the general formula R.sub.2 SiHX wherein R is selected from the group consisting of Me, Et, higher alkyl, and aryl and X is selected from the group consisting of F, Cl, Br, I and alkoxy;
- reducing said Si--X bond to produce a reactive Si--H bond;
- and
- (d) reacting said reactive Si--H bond with an organic compound including an unsaturated carbon-carbon bond selected from the group consisting of olefinic and acetylenic bonds to form said carbosilane dendrimer.
3 more elements
A method for synthesizing a carbosilane dendrimer comprising steps of:
- (a) providing a core molecule selected from the group consisting of Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 wherein n is an integer in the range of from about 0 to 20;
- and RSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and R is selected from the group consisting of alkyl, aryl, halogen, alkoxy and aryloxy;
- Si[C.sub.6 H.sub.4 (CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.4 wherein n is an integer in the range of from about 0 to 20 and C.sub.6 H.sub.4 is selected from the group consisting of para-phenylene and meta-phenylene;
- and RSi[C.sub.6 H.sub.4 (CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3 wherein n is an integer in the range of from about 0 to 20 and R is selected from the group consisting of alkyl, aryl, halogen, alkoxy and aryloxy;
- and C.sub.6 H.sub.4 is selected from the group consisting of para-phenylene and meta-phenylene;
- (b) adding a first reagent selected from the group consisting of HSi(CH.dbd.CH.sub.2).sub.3 ;
- HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ;
- HSi(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3, wherein n is an integer in the range of from about 2 to about 20;
- R(H)Si(CH.dbd.CH.sub.2).sub.2 ;
- R(H)Si(CH.sub.2 CH.dbd.CH.sub.2).sub.2 ;
- and R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2, wherein n is an integer in the range of from about 2 to about 20, R is selected from the group consisting of methyl and higher alkyl, phenyl and substituted phenyl, halogen, alkoxy, aryloxy and dialkylamino groups to said core molecule to form an intermediate product;
- (c) adding additional reagent selected from the group consisting of HSi(CH.dbd.CH.sub.2).sub.3 ;
- HSi(CH.sub.2 CH.dbd.CH.sub.2).sub.3 ;
- HSi[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.3, wherein n is an integer in the range of from about 2 to about 20;
- R(H)Si(CH.dbd.CH.sub.2).sub.2 ;
- R(H)Si(CH.sub.2 CH.dbd.CH.sub.2).sub.2 ;
- and R(H)Si[(CH.sub.2).sub.n CH.dbd.CH.sub.2 ].sub.2, wherein n is an integer in the range of from about 2 to about 20, R is selected from the group consisting of methyl and higher Alkyl, phenyl and substituted phenyl, halogen, alkoxy, aryloxy and dialkylamino groups and (CH.sub.2 .dbd.CHCH.sub.2).sub.2 (CH.sub.3)SiH to said intermediate product to form an intermediate organosilicon dendrimer including a terminal CH.dbd.CH.sub.2 ;
- (d) adding a reagent characterized by the general formula R.sub.2 SiHX wherein R is selected from the group consisting of Me, Et, higher alkyl, and aryl and X is selected from the group consisting of F, Cl, Br, I and alkoxy and including a Si--X bond;
- reducing said Si--X bond to produce a reactive Si--H bond;
- and
- (e) reacting said reactive Si--H bond with an organic compound including an unsaturated carbon-carbon bond selected from the group consisting of olefinic and acetylenic bonds to form said carbosilane dendrimer.
18 more elements
Dependencies are inferred from the claim text.