Phillips Petroleum Company

Srm Chemical, Ltd. Co.

The United States of America As Represented by the Administrator of the

Paul D Smith

Max P McDaniel

Eric T Hsieh

Gil R Hawley

M Bruce Welch

Helmut G Alt

Syriac J Palackal

Rolf L Geerts

Konstantinos Patsidis

Stefan Kwiatkowski

Lowell J Lawrence

Donald D Norwood

Joel L Martin

Michael Schmid

Brian K Conroy

Max P Mcdaniel

Marvin M Johnson

Douglas D Klendworth

Clarence J Wesselski

William C Schneider

Kornel Nagy

Jay Janzen

Krzysztof Pupek

John A Schliesing

Terry L Johnson

Stephan Kwiatkowski

John Westerman

Steven G Mobley

Reginald B Berka

Miroslaw J Golinski

Herbert C Kavanaugh

Frederick J Stebbins

Miroslaw Golinski

Kryzsztof Pupek

Richard C Parish

Fluorenyl-containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.

Organometallic fluorenyl compounds, preparations, and use

Bridged and unbridged fluorenyl-containing metallocenes of the formula R&Prime; (FlR )(CpR )MQ wherein Fl is a fluorenyl radical, Cp is a cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl radical, each R is an organo radical, R&Prime; is a structural bridge linking (FlR ) and (CpR ), M is a metal selected from the group consisting of IVB, VB, and VIB metals, each Q is selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals and halogen, x is 1 or 0, k is an integer sufficient to fill out the remaining valences of M, n is in the range of 0 to 7, and m is 0 to 7, further characterized by the fact that if (CpR ) is unsubstituted fluorenyl and metallocene is an unbridged metallocene, then n is 1 to 7 and if R&Prime; is 1,1-dimethylmethylene and (CpR ) is unsubstituted cyclopentadienyl or 3-methylcyclopentadienyl, then n is 1 to 7.

Organometallic fluorenyl compounds, preparation, and use

Bridged fluorenyl-containing metallocenes of metals of Groups 4-6 and their use in forming homopolymers of alpha olefins or polymers of ethylene and optionally minor amounts of alpha olefins, wherein in each case at least one of the cyclic groups of the bridged ligand is a fluorenyl and the other is selected from indenyl, tetrahydroindenyl, fluorenyl, and in the case of the polymerization of ethylene optionally cyclopentadienyl.

The invention is a process to manufacture the intermediate secondary amine N-ethyl-2-chloro-6-fluoro-benzylamine, and then the process of reacting this intermediate to manufacture the herbicide flumetralin. Equimolar quantities of monoethylamine, sodium hydroxide, and 2-chloro-6-fluorobenzyl chloride are reacted at a temperature between about 70.degree. C. and about 100.degree. C. in a composition containing at least 2.5 times the required quantity of monoethylamine. The reagent monoethylamine functions as solvent and heat sink for the reaction, and also minimizes the formation of undesired byproducts. The excess monoethylamine is removed after formation of the intermediate. Then, equimolar quantities of sodium hydroxide in water and molten 4-chloro-3-5-dinitrobenzotrifluoride are added to the intermediate, and the temperature is controlled between about 90.degree. C. and about 115.degree. C. The product of this reaction is relatively pure, i.e., 98 percent by weight, molten flumetralin. It is advantageous to wash the product with boiling water to facilitate removal of salt and excess sodium hydroxide.

Method of manufacturing flumetralin

Disclosed is a process of nitrating or dinitrating an aromatic amine compound that involves reacting the aromatic amine and nitric acid in the presence of acetic acid such that the molar ratio of the aromatic amine compound to acetic acid is from about 1:2 to about 1:16, and the molar ratio of nitric acid to the aromatic amine is between about 1.0 to about 1.5 times the nitric acid needed to complete the reaction. More particularly, the invention is a process of forming Pendimethalin, N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine, from N-(1-ethylpropyl)-3,4-xylidine (4-NAX) that involves reacting 4-NAX and nitric acid in the presence of acetic acid such that the molar ratio of nitric to the 4-NAX is between about 2:1 and about 3:1, preferably between about 2:1 and about 2.6:1, and such that the molar ratio of 4-NAX to acetic acid is between about 1:2 to about 1:16, preferably between about 1:4 and about 1:8.

Process for nitrating aromatic amines

This invention relates to pendralin �2,6-dinitro-N-(1-ethylpropyl)-4-tert-butylaniline!, preemergence and postemergence herbicidal methods and herbicidal compositions employing pendralin.

A2,6-dinitroaniline herbicide

A process is provided for preparing 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzenamine from 4-chlorotrifluoromethylbenzene. The process includes a two stage nitration and an amination step. Ethylene dichloride is utilized as a diluent and solvent in the nitration steps. Spent acid from the first nitration is reconstituted with sulfur trioxide for use in the second nitration. Spent acid from the second nitration is used directly in the first nitration and evaporation is used to remove nitrosoamines from the final trifluralin product.

Process for preparing trifluralin

Unbridged fluorenyl containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.

Organometallic fluorenyl compounds and use thereof in olefin

9-substituted fluorenyl-containing metallocenes and their use in the polymerization of olefins is disclosed. In addition, novel 9-cyclohexylfluorenyl or 9-phenylfluorenyl compounds are disclosed. Also methods for preparing such 9-substituted fluorenyl compounds are presented.

Unbridged metallocenes of 9-substituted fluorenyl compounds and use

In one embodiment of this invention a surface silicated alumina composition, as opposed to conventional silica alumina, is provided. Such composition may also be fluorided and/or phosphated or phosphited. The resulting compositions are broadly useful but are of particular applicability as supports for chromium olefin polymerization catalysts. In another aspect alumina is fluorided and used with hexavalent chromium catalyst and a co-catalyst or in the alternative with an organochromium catalyst. If desired the support in this embodiment can also be phosphated or phosphited. In another embodiment, aluminum phosphate is formed in the pores of alumina. In contrast with alumina catalyst supports of the prior art, the supports of this invention allow for the production of olefin polymers at high rates of productivity. Also novel high density ultrahigh molecular weight polymers are produced.

Olefin polymers prepared by polymerization with treated alumina

A vanadium dichloride-ether complex is carried on a porous support. This complex can be produced by either forming VCl.sub.2 and thereafter complexing the material with an ether or forming an ether complex with VCl.sub.4 or VCl.sub.3 and thereafter reducing the vanadium compound to VCl.sub.2. It is also possible to carry out the complexing reaction and the reduction essentially simultaneously. The resulting catalyst in combination with a cocatalyst is capable of giving high activity in olefin polymerization and demonstrates good sensitivity to molecular weight control agents, thus allowing the production of a broad spectrum of polymers so far as molecular weight is concerned.

Supported vanadium dihalide-ether complex catalyst

Olefin polymerization catalysts, processes for preparing the catalysts and processes for producing polyolefins utilizing the catalysts are provided. The catalysts are basically comprised of a pentadienyl derivative-transition metal complex adsorbed on an activated inorganic refractory compound.

Olefin polymerization using supported pentadienyl derivative-transition

Olefin polymerization catalysts, processes for preparing the catalysts and processes for producing polyolefins utilizing the catalysts are provided. The catalysts are basically comprised of a trialkylsilylamide-chromium complex adsorbed on an activated inorganic compound.

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Seabrook, TX, United States of America

Paul D Smith