Titanium was introduced into the montmorillonite structure by cation exchange with polymeric Ti cations, formed by partial hydrolysis of TiCl4 in HCl. On further hydrolysis and heating, TiO2 pillars in the form of anastase were formed between the montmorillonite layers. The resulting TiO2-cross-linked montmorillonites possessed surface areas in the range 200–350 m2/g and pore volumes of about 0.2 cm3/g and were thermally and hydrothermally stable to 700°C. The basal spacing of products heated at temperatures > 200°C was about 28A, as determined by X-ray powder diffraction and by N2-desorption pore-size analysis. The surface area increased and the pore volume decreased with increasing HCl-concentration in the Ti-solution. The uptake of TiO2 by the montmorillonite, the surface area, and the pore volume increased with increasing amount of Ti added in the preparation, to about 10 mmoles of Ti/g of montmorillonite. A further increase in the amount of Ti added resulted in a decrease in surface area, but the pore volume and the uptake of TiO2 remained almost constant. The high porosity and the interlayer spacing of the product are consistent with a structure similar to that previously proposed for smectites, cross-linked with hydroxy-Al oligocations.

Synthesis and Properties of Titanium Oxide Cross-Linked Montmorillonite

Solutions containing hydroxy-SiA1 (HSA) oligocations were prepared by two procedures: (1) treatment of a mixture of orthosilicic acid and A1C13 with aqueous NaOH, followed by aging of the product; and (2) preliminary preparation and aging of hydroxy-Al~3 oligocations followed by reaction of the latter with orthosilicic acid. Ion exchange of Na,Ca-montmorillonite with HSA oligocations yielded pillared, crossqinked montmorillonites (designated as HSA-CLM) showing a maximum d(001) value of 19.5 ,~ for air-dried samples, and maximum surface areas of -500 m2/g after outgassing at 250~ -3 tort. Corresponding ion exchange of Li-fluorhectorite yielded HSA fluorhectorites (HSA-CLFH) showing a maximum d(001) value of 19.0/~ and a surface area of 355 mVg. Calculated structural formulae for the HSA-CLM and HSA-CLFH products, based on elemental analysis, showed a gradual increase in the Si/A1 ratio in the intercalated HSA oligocations with increasing Si/A1 ratio in the pillaring solution. Optimum d(001) values and surface areas of HSA-CLM and HSA-CLFH products were obtained using method 2 and applying a ratio of 1.6-2.5 mmole (Si)A1/g smectite. The thermal stabilities of HSA-CLM and HSA-CLFH products were determined by heat treatment between 250 ~ and 700~ and subsequent measurement of the d(001) values and surface areas. HSA-CLFH products showed the unusual behavior of increase of d(001) with increase in temperature from 400 ~ to 500~ and essential constancy of d(001) from 500 ~ to 600~ The HSA-CLM products showed a gradual decrease in surface area, whereas the HSA-CLFH products prepared with a Si/A1 ratio of 1.04-2.18 in the pillaring solution showed constant surface areas with increasing temperature from 250 ~ to 600~ HSA-CLM and HSA-CLFH show sharply higher acidities compared with those of reference A1-CLM and A1-CLFH samples obtained by pillaring with hydroxy-Al~3 oligocations. This increased acidity is probably due to the presence of acidic, surface silanol groups in the HSA oligocations.

Cross-linked smectites: V. Synthesis and properties of hydroxy- silicoaluminum montmorillonites and fluorhectorites

The present invention is directed to a coordinating catalyst system comprising at least one metallocene or constrained geometry pre-catalyst transition metal compound, (e.g., di-(n-butylcyclopentadienyl) zirconium dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology.

Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation

Layered chalcogenide materials of high thermal stability and surface area which contain interspathic polymeric chalcogenides such as polymeric silica are prepared by ion exchanging a layered metal oxide, such as layered titanium oxide, with organic cation, to spread the layers apart. A compound such as tetraethylorthosilicate, capable of forming a polymeric oxide, is thereafter introduced between the layers. The resulting product is treated to form polymeric oxide, e.g. by hydrolysis, to produce the layered oxide material. The resulting product may be employed as catalyst material in the conversion of organic compounds.

Layered metal chalcogenides containing interspathic polymeric chalcogenides

The present invention provides new high resolution resists applicable to next generation lithographies, methods of making these novel resists, and methods of using these new resists in lithographic processes to effect state-of-the-art lithographies. New nanocomposite resists comprising nanoparticles in a polymer matrix are provided in this invention. New chemically amplified resists that incorporate inorganic moieties as part of the polymer are presented herein, as are new chemically amplified resists that incorporate photoacid generating groups within the polymeric chain. Novel non-chemically amplified yet photosensitive resists, and new organic-inorganic hybrid resists are also provided herein. This invention and the embodiments described herein constitute fundamentally new architectures for high resolution resists.

High resolution resists for next generation lithographies

The present invention relates to intercalated clay compositions wherein the interlayers of said clay have been intercalated with three-dimensional silicon oxide pillars whereby the pillars comprise at least two silicon atom layers parallel to the clay interlayers. These materials have useful catalytic and adsorbent properties.

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Silica-clay complexes

This invention relates to clay compositions intercalated with inorganic oxide particles and the process from preparing them.

Intercalated clay compositions

The present invention relates to intercalated crystalline zirconium phosphate-types compositions wherein the interlayers of said composition have been intercalated with three-dimensional silicon oxide pillars whereby the pillars comprise at least two silicon atom layers parallel to the clay interlayers.

Silica intercalated crystalline zirconium phosphate-type materials

A copper-alkali metal-ruthenium supported on silica catalyst is utilized in syngas reactions to produce linear alpha-olefins in high yield.

Copper-alkali metal-ruthenium/silica catalyst for converting syngas to linear alpha-olefins

A process is disclosed for oxidizing dimethyl ether to formaldehyde using a catlyst comprising a mixture of oxides of bismuth, molybdenum and copper.

Robert M. Lewis

Papers

Silica-clay complexes

Intercalated clay compositions

Silica intercalated crystalline zirconium phosphate-type materials

Copper-alkali metal-ruthenium/silica catalyst for converting syngas to linear alpha-olefins

Conversion of dimethyl ether to formaldehyde using Bi-Mo-Cu catalyst