Preparation of isocyanatosilanes
View Patent ↗There is provided herein a method of preparing an isocyanatosilane including reacting an olefinic isocyanate with a hydridosilane in the presence of a dinuclear rhodium complex under hydrosilylation conditions.
1. A method of preparing an isocyanatosilane having the general formula (I):
(R 1 O) 3-n (R 2 ) n Si—R—NCO (I)
wherein
R is a divalent hydrocarbyl group containing up to 12 carbon atoms and optionally containing at least one heteroatom,
R 1 and R 2 are each independently a linear or branched alkyl, cycloalkyl or aromatic group containing up to 12 carbon atoms, and
the subscript n is an integer of from 0 to 2 comprising reacting an olefinic isocyanate having the general formula (II):
R″—NCO (II)
wherein R″ is a linear, branched, cyclic or aromatic monovalent olefinic hydrocarbyl group containing up to about 12 carbon atoms, optionally having at least one heteroatom with a hydridosilane having the general formula (III):
(R 1 O) 3-n (R 2 ) n Si—H (III)
wherein R 1 and R 2 are each independently a linear or branched alkyl, cycloalkyl or aromatic group containing up to 12 carbon atoms, and where the subscript n is an integer of from 0 to 2 in the presence of at least one dinuclear rhodium complex having the general formula (IV):
Rh 2 (μ-X) 8 L 1 x L 2 y L 3 z (IV)
wherein L 1 , L 2 , L 3 and X are ligands selected from the group consisting of Cl, Br, I, OH, R^, OR^, OSiR^ 3 , H, CO, R^C(═O)O, O, SR^, S, Se, CO 3 , SO 3 , SO 4 , HPO 4 , R^PO 4 , CN, NCO, NCS, NO 2 , NO 3 , ClO 4 , R^SO 4 , phosphonate, phosphinate, phosphine, amine, imine, amide, ammine, nitrile, heterocycle, β-diketonate, β-diketiminate, amidinate, sulfonate, olefin, ether, thioether, isonitrile, R^NCO, R^NCS, R^OCN, sulfoxide, amineoxide, SO 2 , CO 2 , NO, wherein each R^ is independently a linear, branched, cyclic or aromatic hydrocarbon moiety which contains up to 16 carbon atoms and optionally at least one heteroatom, and combinations of two or more of the foregoing ligands which are incorporated into a single ligand, provided that X is a bridging ligand bridging the two rhodium atoms, and where the subscript a is an integer of from 1 to 8, and the subscripts x, v and z are each independently an integer of from 0 to 8 under hydrosilylation conditions.
2. The method of claim 1 wherein R is a divalent alkyl group contain up to 8 carbon and each R 1 and R 2 is independently a linear or branched alkyl group containing up to 6 atoms.
3. The method of claim 1 wherein the isocyanatosilane produced is selected from the group consisting of 3-isocyanatopropyltrimethoxysilane, 2-isocyanato-1-methylethyltrimethoxysilane, 2-isocyanatopropyltrimethoxysilane, 4-isocyanatobutyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-isocyanato-1-methylethyltriethoxysilane, 2-isocyanatopropyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 2-isocyanato-1-methylethylmethyldimethoxysilane, 2-isocyanatopropylmethyldimethoxysilane, 4-isocyanatobutylphenyldimethoxysilane, and combinations thereof.
4. The method of claim 1 wherein R″ is a linear or branched monovalent hydrocarbon containing up to 6 carbon atoms.
5. The method of claim 1 , wherein the olefinic isocyanate is selected from the group consisting of vinyl isocyanate, allyl isocyanate, 3-isocyanate-2-methyl-propene, vinylbenzylisocyanate, 1-isocyanate-2-butene, 1-isocyanate-3-methyl-2-butene, 3-isocyanate-1-butene, 3-isocyanate-3-methyl-1-butene, 3-isocyanate-2,3-dimethyl-1-butene, 4-isocyanate-2-methyl-1-butene, 4-isocyanate-3,3-dimethyl-1-butene, 3-isocyanate-3-methyl-1-pentene, 4-isocyanate-4-methyl-1-pentene, 5-isocyanate-1-pentene, 3-isocyanate-1-hexene, 3-isocyanate-5,5-dimethyl-1-hexene, 1-isocyanate-2-heptene and combinations thereof.
6. The method of claim 1 wherein n is 0 or 1.
7. The method of claim 1 wherein the hydridosilane is selected from the group consisting of trimethoxysilane, triethoxysilane, tripropoxysilane, tri-iso-propoxysilane, tributoxysilane, tri-iso-butoxysilane, methyldiethoxysilane, methyldimethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, cyclohexyldi-iso-propoxysilane, phenyldimethoxysilane, and combinations thereof.
8. The method of claim 1 wherein each L 1 , L 2 and L 3 is independently selected from the group consisting of CO and 1,5-cyclooctadiene.
9. The method of claim 1 wherein the hydrocarbon moiety is selected from the group consisting of an alkyl, an aryl, and combinations thereof.
10. The method of claim 1 wherein the L 1 , L 2 , L 3 and X ligands are selected from the group consisting of Cl, Br, I, CO, OH, H, 1,5-cyclooctadiene, ethylene, norbornadiene, 1,5-hexadiene, carboxylate, triphenylphosphine, benzonitrile, benzene, and combinations thereof.
11. The method of claim 1 wherein each of the bridging ligands X are independently selected from the group consisting of Cl, Br, I, OH, R^, OR, OSiR^ 3 , SR^, CO, O, H, carboxylate, and combinations thereof.
12. The method of claim 11 wherein each of the bridging ligands X are selected from Cl, Br, OSiR^ 3 , and combinations thereof.
13. The method of claim 1 where the subscript a is an integer of from 1 to 4.
14. The method of claim 1 wherein the dinuclear rhodium complex is of the general formula (V):
[Rh(μ-X)L 1 x L 2 y L 3 z ] 2 (V)
and where L 1 , L 2 L 3 , and X are as defined and subscripts x, y and z are each an integer from 0 to 4.
15. The method of claim 14 wherein X is selected from the group consisting of Cl, Br, I, OH, R^, OR^, OSiR^ 3 , SR^, CO, O, H, carboxylate, and combinations thereof.
16. The method of claim 14 wherein X is Cl and L 1 , L 2 and L 3 are each independently 1,5-cyclooctadiene, norbornadiene, ethylene, cyclooctene, 1,5-hexadiene or CO.
17. The method of claim 1 wherein the dinuclear rhodium complex is of the general formula (VI):
L 1 x L 2 y L 3 z Rh(μ-X) a RhL 4 y L 5 v L 6 w (VI)
wherein L 1 , L 2 , L 3 , and a, x, y and z are as defined, and each of L 4 , L 5 and L 6 are as defined for each of L 1 , L 2 , L 3 , and the subscripts u, v and w are each as defined for each of x, y and z.
18. The method of claim 1 wherein the dinuclear rhodium complex is selected from the group consisting of Rh 2 Cl 2 (CO) 4 , Rh 2 Cl 2 (cod) 2 , Rh 2 Br 2 (CO) 4 , Rh 2 I 2 (CO) 4 , Rh 2 Cl 2 (nbd) 2 , Rh 2 Cl 2 (C 2 H 4 ) 4 , Rh 2 Cl 2 (coe) 4 , Rh 2 Cl 2 (hde) 2 , Rh 2 Cl 2 (PPh 3 ) 4 , Rh 2 Cl 2 (CO) 2 (PPh 3 ) 2 , Rh 2 Cl 4 (Cp*) 2 , Rh 2 Br 2 (cod) 2 , Rh 2 I 2 (cod) 2 , Rh 2 (OH) 2 (cod) 2 , Rh 2 (OCH 3 ) 2 (cod) 2 , and Rh 2 (OSiCH 3 ) 2 (cod) 2 .
19. The method of claim 1 wherein the hydrosilylation conditions comprise a temperature of from 50 to about 150° C. and/or a period of time of from about 1 h to about 8 h.
20. The method of claim 1 wherein the isocyanatosilane is produced in a purity of at least 50% based on the weight of the reaction product.
21. The method of claim 1 wherein the product isocyanatosilane is produced having an amount of less than 10% isocyanurate byproduct, based on the weight of the reaction product.