Patent US5068383A successfully refreshed from Google Patents.
US5068383A
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Catalyzed redistribution of polyorganosiloxanes
Assignee: Dow Silicones Corp
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Filing: 1990-11-09
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Granted: 1991-11-26
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Expires: 2010-11-09
Abstract
Abstract The instant invention is a catalyzed process for the redistribution of linear, chloride or hydroxy end-terminated polyorganosiloxanes or cyclic polyorganosiloxanes. Effective catalysts for the described process are alumina, silica-alumina, activated carbon, zeolite, and acid clay. The catalyzed redistribution process can be incorporated as an element of a three-stage process. The three-stage process allows control of the yield of cyclic polyorganosiloxanes.
Inventors
- 👤 Jodi A. Bourgoin
- 👤 Steven K. Freeburne
- 👤 Roland L. Halm
- 👤 Brian M. Naasz
- 👤 David S. Niswonger
- 👤 Dennis G. VanKoevering
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 13:21
CPC Classifications
C; C07; C07F; C07F7/00; C07F7/02; C07F7/21; C07F7/08; C07F7/0834; C07F7/0838; C07F7/0872; C07F7/0874; C08; C08G; C08G77/00; C08G77/04; C08G77/06; C08G77/08; C08G77/10
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
111 words
A process for the redistribution of chlorosiloxanes, the process comprising: (A) contacting a monodispersed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.m SiR.sub.2 Cl where each R is independently selected from a group consisting of hydrogen, and alkyl and substituted alkyl radicals of one to six carbon atoms, and m is an integer from one to 100; with a catalyst which facilitates redistribution of the chlorosiloxane, the catalyst selected from a group consisting of alumina, silica-alumina, activated carbon, zeolite, and acid clay; and (B) forming a polydispersed redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.m' SiR.sub.2 Cl, where R is as previously described and m' is a mean value equivalent to m.
Claim 2
Dependent Claim
111 words
A process for the redistribution of chlorosiloxanes, the process comprising: (A) contacting a monodispersed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.m SiR.sub.2 Cl where each R is independently selected from a group consisting of hydrogen, and alkyl and substituted alkyl radicals of one to six carbon atoms, and m is an integer from one to 100; with a catalyst which facilitates redistribution of the chlorosiloxane, the catalyst selected from a group consisting of alumina, silica-alumina, activated carbon, zeolite, and acid clay; and (B) forming a polydispersed redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.m' SiR.sub.2 Cl, where R is as previously described and m' is a mean value equivalent to m.
Claim 3
Dependent Claim
11 words
A process according to claim 1, where the catalyst is alumina.
Claim 4
Dependent Claim
10 words
A process according to claim 1, where R is methyl.
Claim 5
Dependent Claim
22 words
A process according to claim 1, where each R is a radical independently selected from a group consisting of methyl and 3,3,3-trifluoropropyl.
Claim 6
Dependent Claim
21 words
A process according to claim 1, where each R is independently selected from a group consisting of hydrogen atoms and methyl.
Claim 7
Dependent Claim
15 words
A process according to claim 1, where m is an integer from four to 25.
Claim 8
Dependent Claim
21 words
A process according to claim 1, where the process is conducted at a temperature of about 25° C. to 60° C.
Claim 9
Dependent Claim
15 words
A process according to claim 1, where R is methyl and the catalyst is alumina.
Claim 10
Dependent Claim
149 words
A process for the redistribution of chlorosiloxanes, the process comprising: (A) contacting a first polydispersed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.x SiR.sub.2 Cl, where each R is independently selected from a group consisting of hydrogen, alkyl and substituted alkyl radicals of one to six carbon atoms, and x is a mean value of one to 5000, with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.y SiR.sub.2 Cl, where R is as previously described and y is a mean value of zero to less than x; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes, the catalyst selected from a group consisting of alumina, silica-alumina, activated carbon, zeolite, and acid clay; and (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.z SiR.sub.2 Cl, where R is as previously described and z is a mean value greater than y and less than x.
Claim 11
Dependent Claim
149 words
A process for the redistribution of chlorosiloxanes, the process comprising: (A) contacting a first polydispersed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.x SiR.sub.2 Cl, where each R is independently selected from a group consisting of hydrogen, alkyl and substituted alkyl radicals of one to six carbon atoms, and x is a mean value of one to 5000, with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.y SiR.sub.2 Cl, where R is as previously described and y is a mean value of zero to less than x; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes, the catalyst selected from a group consisting of alumina, silica-alumina, activated carbon, zeolite, and acid clay; and (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.z SiR.sub.2 Cl, where R is as previously described and z is a mean value greater than y and less than x.
Claim 12
Dependent Claim
11 words
A process according to claim 9, where the catalyst is alumina.
Claim 13
Dependent Claim
10 words
A process according to claim 9, where R is methyl.
Claim 14
Dependent Claim
21 words
A process according to claim 9, where each R is independently selected from a group consisting of methyl and 3,3,3-trifluoropropyl radicals.
Claim 15
Dependent Claim
21 words
A process according to claim 9, where each R is independently selected from a group consisting of hydrogen atoms and methyl.
Claim 16
Dependent Claim
16 words
A process according to claim 9, where x is seven to 1000 and y is zero.
Claim 17
Dependent Claim
21 words
A process according to claim 9, where the process is conducted at a temperature of about 25° C. to 60° C.
Claim 18
Dependent Claim
15 words
A process according to claim 9, where the catalyst is alumina and R is methyl.
Claim 19
Dependent Claim
23 words
A process according to claim 9, where the catalyst is alumina, R is methyl, x is seven to 1000, and y is zero.
Claim 20
Dependent Claim
149 words
A process for the redistribution of hydroxysiloxanes, the process comprising: (A) contacting a first polydispersed mixture comprising hydroxysiloxanes of formula HO(SiR.sub.2 O).sub.x SiR.sub.2 OH, where each R is independently selected from a group consisting of hydrogen, alkyl and substituted alkyl radicals of one to six carbon atoms, and x is a mean value of one to 5000, with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.y SiR.sub.2 Cl, where R is as previously described and y is a mean value of zero to less than x; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes, the catalyst selected from a group consisting of alumina, silica-alumina, activated carbon, zeolite, and acid clay; and (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.z SiR.sub.2 Cl, where R is as previously described and z is a mean value greater than y and less than x+2y.
Claim 21
Dependent Claim
149 words
A process for the redistribution of hydroxysiloxanes, the process comprising: (A) contacting a first polydispersed mixture comprising hydroxysiloxanes of formula HO(SiR.sub.2 O).sub.x SiR.sub.2 OH, where each R is independently selected from a group consisting of hydrogen, alkyl and substituted alkyl radicals of one to six carbon atoms, and x is a mean value of one to 5000, with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.y SiR.sub.2 Cl, where R is as previously described and y is a mean value of zero to less than x; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes, the catalyst selected from a group consisting of alumina, silica-alumina, activated carbon, zeolite, and acid clay; and (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.z SiR.sub.2 Cl, where R is as previously described and z is a mean value greater than y and less than x+2y.
Claim 22
Dependent Claim
11 words
A process according to claim 18, where the catalyst is alumina.
Claim 23
Dependent Claim
10 words
A process according to claim 18, where R is methyl.
Claim 24
Dependent Claim
21 words
A process according to claim 18, where each R is independently selected from a group consisting of methyl and 3,3,3-trifluoropropyl radicals.
Claim 25
Dependent Claim
21 words
A process according to claim 18, where each R is independently selected from a group consisting of hydrogen atoms and methyl.
Claim 26
Dependent Claim
16 words
A process according to claim 18, where x is seven to 1000 and y is zero.
Claim 27
Dependent Claim
21 words
A process according to claim 18, where the process is conducted at a temperature of about 25° C. to 60° C.
Claim 28
Dependent Claim
15 words
A process according to claim 18, where the catalyst is alumina and R is methyl.
Claim 29
Dependent Claim
23 words
A process according to claim 18, where the catalyst is alumina, R is methyl, x is seven to 1000, and y is zero.
Claim 30
Dependent Claim
147 words
A process for the redistribution of cyclic siloxanes, the process comprising: (A) contacting a first polydispersed mixture comprising cyclic siloxanes of formula (SiR.sub.2 O).sub.j, where each R is independently selected from a group consisting of hydrogen, alkyl and substituted alkyl radicals of one to six carbon atoms, and j is a mean value of three to 50, with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.y SiR.sub.2 Cl, where R is as previously described and y is a mean value of zero to less than j; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes, the catalyst selected from a group consisting of alumina, silica-alumina, zeolite, and acid clay; and (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.z SiR.sub.2 Cl, where R is as previously described and z is a mean value greater than y and less than j.
Claim 31
Dependent Claim
147 words
A process for the redistribution of cyclic siloxanes, the process comprising: (A) contacting a first polydispersed mixture comprising cyclic siloxanes of formula (SiR.sub.2 O).sub.j, where each R is independently selected from a group consisting of hydrogen, alkyl and substituted alkyl radicals of one to six carbon atoms, and j is a mean value of three to 50, with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.y SiR.sub.2 Cl, where R is as previously described and y is a mean value of zero to less than j; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes, the catalyst selected from a group consisting of alumina, silica-alumina, zeolite, and acid clay; and (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.z SiR.sub.2 Cl, where R is as previously described and z is a mean value greater than y and less than j.
Claim 32
Dependent Claim
11 words
A process according to claim 27, where the catalyst is alumina.
Claim 33
Dependent Claim
10 words
A process according to claim 27, where R is methyl.
Claim 34
Dependent Claim
21 words
A process according to claim 27, where each R is independently selected from a group consisting of hydrogen atoms and methyl.
Claim 35
Dependent Claim
16 words
A process according to claim 27, where j is 3 to 10 and y is zero.
Claim 36
Dependent Claim
21 words
A process according to claim 27, where the process is conducted at a temperature of about 25° C. to 60° C.
Claim 37
Dependent Claim
15 words
A process according to claim 27, where the catalyst is alumina and R is methyl.
Claim 38
Dependent Claim
23 words
A process according to claim 27, where the catalyst is alumina, R is methyl, j is 3 to 10, and y is zero.
Claim 39
Dependent Claim
190 words
A three-stage process for preparing cyclic siloxanes, the process comprising: (A) contacting a first mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.x SiR.sub.2 Cl, where each R is independently selected from a group consisting of hydrogen atoms, and alkyl and substituted alkyl radicals of one to six carbon atoms and x is a mean value of one to 5000; with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.p SiR.sub.2 Cl, where R is as previously described and p is a mean value of zero to 7; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes; (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.o SiR.sub.2 Cl where R is as previously described and o is a mean value within a range of greater than zero and less than seven; (C) hydrolyzing the redistributed mixture of chlorosiloxanes to form a hydrolysate comprising cyclic siloxanes of formula (R.sub.2 SiO).sub.q, where R is as previously described and q is a mean value of three to 25, and chlorosiloxanes; (D) separating the cyclic siloxanes from the chlorosiloxanes; and (E) recycling the chlorosiloxanes as a feed to step (A).
Claim 40
Dependent Claim
190 words
A three-stage process for preparing cyclic siloxanes, the process comprising: (A) contacting a first mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.x SiR.sub.2 Cl, where each R is independently selected from a group consisting of hydrogen atoms, and alkyl and substituted alkyl radicals of one to six carbon atoms and x is a mean value of one to 5000; with a second mixture comprising chlorosilanes and chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.p SiR.sub.2 Cl, where R is as previously described and p is a mean value of zero to 7; in the presence of a catalyst which facilitates redistribution of chlorosiloxanes; (B) forming a redistributed mixture comprising chlorosiloxanes of formula Cl(SiR.sub.2 O).sub.o SiR.sub.2 Cl where R is as previously described and o is a mean value within a range of greater than zero and less than seven; (C) hydrolyzing the redistributed mixture of chlorosiloxanes to form a hydrolysate comprising cyclic siloxanes of formula (R.sub.2 SiO).sub.q, where R is as previously described and q is a mean value of three to 25, and chlorosiloxanes; (D) separating the cyclic siloxanes from the chlorosiloxanes; and (E) recycling the chlorosiloxanes as a feed to step (A).
Claim 41
Dependent Claim
24 words
A process according to claim 35, where the catalyst is selected from a group consisting of alumina, silicaalumina, zeolite, activated carbon, and acid clay.
Claim 42
Dependent Claim
11 words
A process according to claim 35, where the catalyst is alumina.
Claim 43
Dependent Claim
10 words
A process according to claim 35, where R is methyl.
Claim 44
Dependent Claim
21 words
A process according to claim 35, where each R is independently selected from a group consisting of hydrogen atoms and methyl.
Claim 45
Dependent Claim
15 words
A process according to claim 35, where the catalyst is alumina and R is methyl.
Claim 46
Dependent Claim
31 words
A process according to claim 35, where the contacting of the first mixture and the second mixture with the catalyst occurs at a temperature of about 25° C. to 60° C.
Claim 47
Dependent Claim
18 words
A process according to claim 35, where hydrolysis of the redistributed mixture is conducted in a fixed-bed reactor.
Claim 48
Dependent Claim
36 words
A process according to claim 35, where separating the cyclic siloxanes from the chlorosiloxanes is effected by gravitational separation into a siloxane phase and an aqueous hydrogen chloride phase and the siloxane phase is flash distilled.
Claim 49
Dependent Claim
22 words
A process according to claim 35, where the catalyst is selected from a group consisting of alumina, silica-alumina, zeolite, and acid clay.
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