Additives to prevent degradation of alkyl-hydrogen siloxanes
View Patent ↗An organohydrosiloxane composition comprising: a) one or more organohydrosiloxane compounds, each having at least one [—HSiR—O—] unit, wherein R═C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl, and b) an antioxidant compound shown in Formula (1) wherein the antioxidant compound is a phenolic compound and is present in a concentration from about 1 ppm to about 5,000 ppm and wherein R 1 through R 5 can each independently be H, OH, C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy or substituted or unsubstituted aryl. The compositions of present invention exhibit stability and significantly extend the shelf life of organohydrosiloxane products and allow greater flexibility in handling these products in chemical processes or semiconductor manufacturing. The resulting stabilization of siloxanes prevents the possibility of complete polymerization (i.e., solidification) of product in chemical delivery lines or valves, which lowers equipment maintenance and costs and reduces time the machinery is out of production.
1. An organohydrosiloxane composition comprising:
a. one or more organohydrosiloxane compounds, each having at least one [—HSiR—O—] unit, wherein R=C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl;
b. an antioxidant compound of Formula (1),
wherein the antioxidant compound is a phenolic compound and is present in an amount between about 1 ppm to about 5000 ppm, and wherein R 1 through R 5 are each independently H, OH, C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy or substituted or unsubstituted aryl; and
c. an alkoxysilane of Formula (2),
wherein said alkoxysilane is present in an amount between about 1 ppm and about 5000 ppm; and wherein R 6 is a C 1 –C 18 linear, branched, or cyclic alkyl or substituted or unsubstituted aryl; and
R 7 , R 8 , and R 9 , are independently H, C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy or substituted or unsubstituted aryl.
2. The composition of claim 1 , wherein R 1 through R 5 are H, OH, methyl, ethyl, methoxy, ethoxy, or tert-butyl.
3. The composition of claim 1 , wherein said antioxidant compound of Formula (1) is selected from the group consisting of: phenol, hydroquinone, 4-methylphenol, 3-methylphenol, 2-methylphenol, 4-ethylphenol, 4-propylphenol, 4-iso-propylphenol, 4-butylphenol, 4-sec-butylphenol, 4-iso-butylphenol, 4-tert-butylphenol, 4-methoxyphenol, 3-methoxyphenol, 2-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol, 2,4-di-tert-butylphenol, 2-(1-methylbutyl)phenol, 2-(benzyloxy)phenol, 2-tert-butyl-6-methylphenol, 3,4,5-trimethoxyphenol, 3-ethoxy-4-methylphenol, 4-benzyloxyphenol, 4-benzyl-2,6-di-tert-butylphenol, 2-(2-butenyl)phenol, 2-(4-methylbenzyl)phenol, 2,6-di-tert-butyl-4-methylphenol (BHT), 1,2-dihydroxybenzene, 2,4,6-tris-benzyloxyphenol, 2,4-dicyclohexyl-5-methylphenol, 6-tert-butyl-1,2-dihydroxybenzene, and any combinations thereof.
4. The composition of claim 1 , wherein said antioxidant compound is present in an amount between about 1 ppm to about 1000 ppm.
5. The composition of claim 1 , wherein said antioxidant compound is present in an amount between about 25 ppm to about 200 ppm.
6. The composition of claim 1 , wherein R 6 is methyl, ethyl, or propyl; and R 7 , R 8 and R 9 are methyl, ethyl, propyl, methoxy, ethoxy or propoxy.
7. The composition of claim 1 , wherein said alkoxysilane of Formula (2) is selected from the group consisting of: trimethylmethoxysilane, triethylmethoxysilane, tripropylmethoxysilane, triphenylmethoxysilane, tri(4-methylphenyl)methoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diphenyldimethoxysilane, di(4-methylphenyl)dimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, trimethylethoxysilane, triethylethoxysilane, tripropylethoxysilane, triphenylethoxysilane, tri(4-methylphenyl)ethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diphenyldiethoxysilane, di(4-methylphenyl)diethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, 4-methylphenyltriethoxysilane, trimethylpropoxysilane, triethylpropoxysilane, tripropylpropoxysilane, triphenylpropoxysilane, tri(4-methylphenyl)propoxysilane, dimethyldipropoxysilane, diethyldipropoxysilane, dipropyldipropoxysilane, diphenyldipropoxysilane, di(4-methylphenyl)dipropoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltripropoxysilane, phenyltripropoxysilane, 4-methylphenyltripropoxysilane, trimethylbutoxysilane, triethylbutoxysilane, tripropylbutoxysilane, triphenylbutoxysilane, tri(4-methylphenyl)butoxysilane, dimethyldibutoxysilane, diethyldibutoxysilane, dipropyldibutoxysilane, diphenyldibutoxysilane, di(4-methylphenyl)dibutoxysilane, methyltributoxysilane, ethyltributoxysilane, propyltributoxysilane, phenyitributoxysilane, 4-methylphenyltributoxysilane, trimethylphenoxysilane, triethylphenoxysilane, tripropylphenoxysilane, triphenylphenoxysilane, tri(4-methylphenyl)phenoxysilane, dimethyldiphenoxysilane, diethyldiphenoxysilane, dipropyldiphenoxysilane, diphenyldiphenoxysilane, di(4-methylphenyl)diphenoxysilane, methyltriphenoxysilane, ethyltriphenoxysilane, propyltriphenoxysilane, phenyltriphenoxysilane, 4-methylphenyltriphenoxysilane, trimethyl(4-methylphenoxy)silane, triethyl(4-methylphenoxy)silane, tripropyl(4-methylphenoxy)silane, triphenyl(4-methylphenoxy)silane, tri(4-methylphenyl)(4-methylphenoxy)silane, dimethyldi(4-methylphenoxy)silane, diethyldi(4-methylphenoxy)silane, dipropyldi(4-methylphenoxy)silane, diphenyldi(4-methylphenoxy)silane, di(4-methylphenyl)di(4-methylphenoxy)silane, methyltri(4-methylphenoxy)silane, ethyltri(4-methylphenoxy)silane, propyltri(4-methylphenoxy)silane, phenyltri(4-methylphenoxy)silafle, 4-methylphenyltri(4-methylphenoxy)silane, and any combinations thereof.
8. The composition of claim 1 , wherein said alkoxysilane is present in an amount between about 10 ppm to about 2500 ppm.
9. The composition of claim 1 , wherein said alkoxysilane is present in an amount between about 100 ppm to about 1000 ppm.
10. The composition of claim 1 , wherein said one or more organohydrosiloxane compounds are one or more linear compounds, one or more cyclic compounds, and any combinations thereof.
11. The composition of claim 10 , wherein said one or more linear compounds have a formula according to Formula (3),
wherein R 10 is C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; R 11 through R 16 are each independently H, C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; x is about 1 to about 20; and x can equal 0 when at least one of R 11 through R 16 is H.
12. The composition of claim 11 , wherein R 10 is methyl, ethyl, propyl, butyl, or cyclohexyl; R 11 through R 16 is methyl, ethyl, propyl, butyl, cyclohexyl or H; and x is about 1 to about 8.
13. The composition of claim 11 , wherein said linear organohydrosiloxanes of Formula (3) are selected from the group consisting of: 1,1,1,3,3-pentamethyldisiloxane, 1,1,1,3,3-pentaethyldisiloxane, 1,1,1,3,3-pentaphenyldisiloxane, 1,1,1,3,3-penta(4-methylphenyl)disiloxane, 1,1,5,5-tetramethyl-3-ethyltrisiloxane, 1,1,5,5-tetraethyl-3-methyltrisiloxane, 1,1,3,5,5-pentamethyltrisiloxane, 1,1,3,5,5-pentaethyltrisiloxane, 1,1,3,5,5-pentaphenyltrisiloxane, 1,1,3,5,5-penta(4-methylphenyl)trisiloxane, 1,1,1,5,5,5-heptamethyl-3-ethyltrisiloxane, 1,1,1,5,5,5-heptaethyl-3-methyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,5,5-heptaethyltrisiloxane, 1,1,1,3,5,5,5-heptaphenyltrisiloxane, 1,1,1,3,5,5,5-hepta(4-methylphenyl)trisiloxane, 1,1,3,5,7,7-hexamethyltetrasiloxane, 1,1,3,5,7,7-hexaethyltetrasiloxane, 1,1,3,5,7,7-hexaphenyltetrasiloxane, 1,1,3,5,7,7-hexa(4-methylphenyl)tetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,1,1,3,5,7,7,7-octaethyltetrasiloxane, 1,1,1,3,5,7,7,7-octaphenyltetrasiloxane, 1,1,1,3,5,7,7,7-octa(4-methylphenyl)tetrasiloxane, 1,1,3,5,7,9,9-heptamethylpentasiloxane, 1,1,3,5,7,9,9-heptamethylpentasiloxane, 1,1,3,5,7,9,9-heptaethylpentasiloxane, 1,1,3,5,7,9,9-heptaphenylpentasiloxane, 1,1,3,5,7,9,9-hepta(4-methylphenyl)pentasiloxane, 1,1,1,3,5,7,9,9,9-nonamethylpentasiloxane, 1,1,1,3,5,7,9,9,9-nonaethylpentasiloxane, 1,1,1,3,5,7,9,9,9-nonaphenylpentasiloxane, 1,1,1,3,5,7,9,9,9-nona(4-methylphenyl)pentasiloxane, 1,1,3,5,7,9,11,11-octaamethylhexasiloxane, 1,1,3,5,7,9,11,11-octaethylhexasiloxane, 1,1,3,5,7,9,11,11-octaphenylhexasiloxane, 1,1,3,5,7,9,11,11-octa(4-methylphenyl)hexasiloxane, 1,1,1,3,5,7,9,11,11,11-decamethylhexasiloxane, 1,1,1,3,5,7,9,11,11,11-decaethylhexasiloxane, 1,1,1,3,5,7,9,11,11,11-decaphenylhexasiloxane, 1,1,1,3,5,7,9,11,11,11-deca(4-methylphenyl)hexasiloxane, and any combinations thereof.
14. The composition of claim 10 , wherein said one or more linear compounds have a formula according to Formula (4),
wherein R 10 is C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; R 11 through R 16 are each independently H, C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; and y is about 0 to about 20.
15. The composition of claim 14 , wherein R 10 is methyl, ethyl, propyl, butyl, or cyclohexyl; R 11 through R 16 is methyl, ethyl, propyl, butyl, cyclohexyl or H; and y is about 0 to about 8.
16. The composition of claim 14 , wherein said linear organohydrosiloxanes of Formula (4) are selected from the group consisting of: 1,1-diethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraethyltrisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,1,3,3-tetra(4-methylphenyl)disiloxane, 1,1,5,5-tetramethyl-3,3-diethyltrisiloxane, 1,1,5,5-tetraethyl-3,3-dimethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5-hexaethyltrisiloxane, 1,1,3,3,5,5-hexaphenyltrisiloxane, 1,1,3,3,5,5-hexa(4-methylphenyl)trisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,3,5,7,7-octaethyltetrasiloxane, 1,1,3,3,5,5,7,7-octaphenyltetrasiloxane, 1,1,3,3,5,5,7,7-octa(4-methylphenyl)tetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, 1,1,3,3,5,5,7,7,9,9-decaethylpentasiloxane, 1,1,3,3,5,5,7,7,9,9-decaphenylpentasiloxane, 1,1,3,3,5,5,7,7,9,9-deca(4-methylphenyl)pentasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecaamethylhexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecaethylhexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecaphenylhexasiloxane, and 1,1,3,3,5,5,7,7,9,9,11,11-dodeca(4-methylphenyl)hexasiloxane, and any combinations thereof.
17. The composition of claim 10 , wherein said one or more cyclic compounds have a formula according to Formula (5),
wherein R 17 is independently C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; and z is about 2 to about 21.
18. The composition of claim 17 , wherein R 17 is methyl, ethyl, propyl, butyl, or cyclohexyl; and z is about 2 to about 11.
19. The composition of claim 17 , wherein said cyclic organohydrosiloxanes of Formula (5) are selected from the group consisting of: 1,3,5-trimethylcyclotrisiloxane, 1,3,5-triethylcyclotrisiloxane, 1,3,5-triphenylcyclotrisiloxane, 1,3,5-tri(4-methylphenyl)cyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetra(4-methylphenyl)cyclotetrasiloxane, 1,5-dimethyl-3,7-diethylcyclotetrasiloxane, 1,3-dimethyl-5,7-diethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentaethylcyclopentasiloxane, 1,3,5,7,9-pentaphenylcyclopentasiloxane, 1,3,5,7,9-penta(4-methylphenyl)cyclopentasiloxane, 1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11-hexaethylcyclohexasiloxane, 1,3,5,7,9,11-hexaphenylcyclohexasiloxane, 1,3,5,7,9,11-hexa(4-methylphenyl)cyclohexasiloxane, 1,5,9-trimethyl-3,7,11-triethylcyclohexasiloxane, 1,3,5-trimethyl-7,9,11-triethylcyclohexasiloxane, and any combinations thereof.
20. The composition of claim 1 , wherein said composition comprises:
a. one or more organohydrosiloxane compounds of Formula (3),
wherein R 10 is C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl, and R 11 through R 16 are each independently H, C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; and x is about 1 to about 20; and x can equal 0 when at least one of R 11 through R 16 is H;
b. an antioxidant compound of said Formula (1), wherein R 1 through R 5 are H, OH, methyl, ethyl, methoxy, ethoxy, and tert-butyl; and
c. an alkoxysilane of said Formula (2), wherein R 6 is methyl, ethyl, or propyl; and R 7 , R 8 and R 9 are methyl, ethyl, propyl, methoxy, ethoxy or propoxy.
21. The composition of claim 1 , wherein said composition comprises:
a. one or more organohydrosiloxane compounds of Formula (4),
wherein R 10 is C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl, and R 11 through R 16 are each independently H, C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; and y is about 0 to about 20;
b. an antioxidant compound of said Formula (1), wherein R 1 through R 5 are H, OH, methyl, ethyl, methoxy, ethoxy, and tert-butyl; and
c. an alkoxysilane of said Formula (2), wherein R 6 is methyl, ethyl, or propyl; and R 7 , R 8 and R 9 are methyl, ethyl, propyl, methoxy, ethoxy or propoxy.
22. The composition of claim 1 , wherein said composition comprises:
a. one or more organohydrosiloxane compounds of Formula (5),
wherein R 17 is independently C 1 –C 18 linear, branched, or cyclic alkyl, C 1 –C 18 linear, branched, or cyclic alkoxy, or substituted or unsubstituted aryl; and z is about 2 to about 21;
b. an antioxidant compound of said Formula (1), wherein R 1 through R 5 are H, OH, methyl, ethyl, methoxy, ethoxy, and tert-butyl; and
c. an alkoxysilane of said Formula (2), wherein R 6 is methyl, ethyl, or propyl; and R 7 , R 8 and R 9 are methyl, ethyl, propyl, methoxy, ethoxy or propoxy.