Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Patent
1998-03-16
1999-09-28
Geist, Gary
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
502151, 502217, 556428, 560231, 568 32, B01J 3140, B01J 2753, C07F 704, C07C31504
Patent
active
059588225
DESCRIPTION:
BRIEF SUMMARY
This invention concerns compounds possessing a sulfonic acid fluoride, chloride or ester group wherein said group is adjacent to a substantially fluorinated bidentate hydrocarbylene group which is in turn adjacent to a hydrocarbylene group linked to a hydrolyzable silane group, and compounds possessing a sulfonic acid or a salt of a sulfonic acid group wherein said group is adjacent to a substantially fluorinated bidentate hydrocarbylene group which is in turn adjacent to a hydrocarbylene group linked to a hydrolyzed silane group. Siloxane derivatives, which may be oligomeric or polysiloxanes, of these latter compounds are also provided via self-condensation. Optionally, condensation can be carried out in the presence of other network forming materials to yield a network composite with hydrolyzed fluorosulfonic acid derivatives incorporated therein.
This invention further concerns novel compositions comprising a solid material bearing a reactive surface to which surface has been attached via a hydrolyzed silane group a compound possessing a sulfonic acid or a salt of a sulfonic acid group which group is adjacent to a substantially fluorinated bidentate hydrocarbylene group which is in turn adjacent to a hydrocarbylene group linked to said silane group.
BACKGROUND OF THE INVENTION
Canadian Patent Application A1 2,084,967 describes solid acid catalysts wherein a hydrocarbon chain with a pendant sulfonic acid group is bonded to a silicon. These catalysts are not of a high acid strength and at high temperatures have stability problems.
Perfluorosulfonic acid catalysts, for example perfluoropolymers containing pendant sulfonic acid groups (e.g., NAFIONO.RTM. catalyst sold by E. I. du Pont de Nemours and Company) are excellent catalysts for a wide variety of reactions. Perfluoropolymers containing pendant sulfonic acid groups are very strong acids and are used in reactions such as acylations, carbonylations, condensations, alkylations, esterifications, etherifications, hydrations, nitration, isomerizations and oligomerizations. These reactions have been reviewed extensively in "Catalysis with Nafion.RTM.", F. J. Waller, R. W. van Scoyac, Chem. Tech., 1987, 17, 438-441 and in "Perfluorinated resin sulfonic acid (Nafion.RTM. -H.sup.+) Catalysis" in Synthesis, G. A. Olah, P. S. Iyer and G. K. Surya Prakasch, 1986, 513-531. A drawback to the commercial use of perfluorocarbon sulfonic acid catalysts has been their high cost and relatively low catalytic activity, for some reactions, such as alkylations in non-polar solvents.
WO95/19222 describes a solid acid microcomposite catalyst which comprises a perfluorinated ion-exchange polymer containing pendant sulfonic and/or carboxylic acid groups entrapped within and highly dispersed throughout a network of metal oxide.
EP 582879 describes shaped organosiloxane condensates, processes for their preparation and use. These organosilanes, however, are not based on perfluorosulfonic acids which are known to have higher acid strength.
The present invention provides the benefits of increased stability, reduced costs, and in some cases higher catalytic activity and improved reaction selectivity over catalysts mentioned above.
SUMMARY OF THE INVENTION
The present invention provides a compound of formula I alkoxy, and acyloxy; group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl and aralkyl; n+m=3; between Si and R.sub.f,
The present invention also provides a compound of formula II Q.sub.x+II group consisting of: alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl and aralkyl; +m=3; between Si and R.sub.f,
The present invention further provides a siloxane or a polysiloxane comprising at least two groups, said groups being the same or different, having the formula --O).sub.q Si(OH).sub.nq R.sup.1.sub.m R.sup.2 R.sub.f SO.sub.3 Q, wherein R.sup.1, m, n, R.sup.2, R.sub.f and Q are as defined for formula II and q is l to n.
The present invention also provides a composite comprising a metal oxide network with at least one group having the formula q is l to n, incorporated
REFERENCES:
patent: 5093451 (1992-03-01), Panster et al.
patent: 5130396 (1992-07-01), Panster et al.
patent: 5239033 (1993-08-01), Panster et al.
patent: 5380791 (1995-01-01), Panster et al.
F.J. Waller et al., "Catalysis with Nafion.RTM.", Chem. Tech., 1987, 17, 438-441.
G.A. Clark et al., "Perfluorinated resin sulfonic acid (Nation.RTM., H.sup.T) Catalysis", Synthesis, 1986, 513-531.
J.S. Beck et al., "A New Family of Mesoporous Molecular Sieves Prepared with Liquid Crystal Templates", J. Am Chem. Soc., 1992, 14, 10834-10843.
G. A. Bargigia et al., "Perfluoro-w-iodo-3-oxaalkanesulfonyl fluorides as Intermediates for Surfactants and Vinyl Compounds", J. Of Fluorine Chem., 19, 403-410, 1982.
Degussa publication, "Polymers and Cataysis--The DELOXAN.RTM. Product Family", pp. 1-6.
Beckerbauer Richard
Harmer Mark Andrew
Sun Qun
Davis Brian J.
E. I. Du Pont de Nemours and Company
Geist Gary
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