Continuous manufacture of silicone copolymers via multi-stage blade-mixed plug flow tubular reactor
View Patent ↗A process is disclosed for producing silicone copolymers, wherein the process comprises the steps of: (a) providing at least one multi-stage blade-mixed plug flow reactor having an entry and an exit; (b) continuously feeding (i) hydrogen siloxane, (ii) olefinically substituted polyether or olefin capable of reacting with said hydrogen siloxane, and (iii) catalyst for the reaction to the entry of the multi-stage blade-mixed plug flow reactor, and (c) continuously withdrawing from the exit of the multi-stage blade-mixed plug flow reactor a stream that comprises silicone copolymer and is substantially free of unreacted hydrogen siloxane, provided that said hydrogen siloxane and said polyether or olefin have a residence time at reaction temperature in the multi-stage blade-mixed plug flow reactor sufficient to effect substantially complete hydrosilation.
1. A process for producing silicone copolymers, comprising the steps of:
(a) providing at least one multi-stage blade-mixed plug flow reactor having an entry and an exit;
(b) continuously feeding (i) hydrogen siloxane, (ii) olefinically substituted polyether or olefin capable of reacting with said hydrogen siloxane, and (iii) catalyst for the reaction to the entry of the multi-stage blade-mixed plug flow reactor; and
(c) continuously withdrawing from the exit of the multi-stage blade-mixed plug flow reactor a stream that comprises silicone copolymer and is substantially free of unreacted hydrogen sioxane, provided that said hydrogen sioxane and said polyether or olefin have a residence time at reaction temperature in the multi-stage blade-mixed plug flow reactor sufficient to effect substantially complete hydrosilation.
2. The method of claim 1 wherein the hydrogen sioxane is an organohydrogen siloxane comprising any combination of siloxane units selected from the group consisting of R 3 SiO 1/2 , R 2 HSiO 1/2 , R 2 SiO 2/2 , RHSiO 2/2 , RSiO 3/2 , and HSiO 3/2 , wherein each R group is an independently selected hydrocarbon moiety; provided that the hydrogen siloxane comprises sufficient R-containing sioxane units to provide an average of from 1 to 3 R radicals per silicon atom and sufficient H-containing siloxane units to provide from 0.01 to 1 silicon-bonded hydrogen atoms per silicon atom and a total of R radicals and silicon-bonded hydrogen atoms of from 1.5 to 3.0 per silicon atom.
3. The method of claim 2 wherein the hydrocarbon moiety is an alkyl moiety of from 1 to 12 carbon atoms, a cycloaliphatic moiety of from from 5 to 12 carbon atoms, or an aryl moiety, optionally substituted with from 1 to 6 alkyl groups, each of from 1 to 6 carbon atoms.
4. The method of claim 3 wherein all the R groups are the same.
5. The method of claim 4 wherein all the R groups are methyl.
6. The method of claim 1 wherein the olefin reactant is selected from the group consisting of allyl chloride, methallyl chloride, 1-octene, 1-hexene, amylene, 1-octadecene, allyl glycidyl ether, vinylcyclohexene monoxide, allyl (meth)acrylate, perfluorooctylethylene, and terminally unsaturated poly(alkylene oxides).
7. The method of claim 6 wherein the olefin reactant is a terminally unsaturated poly(alkylene oxide) of the formula R 1 (OCH 2 CH 2 ) v (OCH 2 CH(CH 3 )) w - 0 R 2 , wherein R 1 is an alkenyl group containing from 2 to 10 carbon atoms and R 2 is selected from the group consisting of hydrogen, alkyl of from 1 to 5 carbon atoms, acyl of from 2 to 5 carbon atoms, vinyl, allyl, methallyl, and trialkylsilyl; v has a value of from 0 to about 50; and w has a value of from 0 to about 50, provided that the sum of v+w is greater than 0.
8. The method of claim 1 wherein the catalyst is a noble metal-containing catalyst.
9. The method of claim 8 wherein the noble metal is selected from the group consisting of platinum, palladium, and rhodium.
10. The method of claim 9 wherein the noble metal is platinum.
11. The method of claim 10 wherein the catalyst is selected from the group consisting of chloroplatinic acid and the platinum complexes of 1,3-divinyltetramethyldisiloxane.