Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1995-06-06
2001-02-27
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C526S112000, C526S124200, C526S124300, C526S125800, C526S125500
Reexamination Certificate
active
06194342
ABSTRACT:
BACKGROUND OF THE INVENTION
The supported highly active and highly stereospecific catalysts for the polymerization of propylene and higher olefins, known up to now are obtained by the reaction of an Al alkyl compound partially complexed with an electron donor compound (outside donor) with a solid component comprising a Ti compound and an electron-donor compound (inside donor) supported on a Mg halide in active form.
Examples of such catalysts have been described in British Patent No. 1,559,194 and Belgian Patent No. 868,682.
Outside donors consisting of silicon compounds containing Si—O—C bonds also have been described (published Japanese patent applications Sho 79/94590 and Sho 80/36203). Among the various and numerous inside donors such compounds as methyl methacrylate and ethyl pivalate also have been cited.
However, in all the prior art catalysts in which a silicon compound containing Si—O—C bonds is used as outside donor, esters of benzoic acid and derivatives thereof are used as inside donor.
The performance of the above catalysts, expressed in terms of activity and stereospecificity, is not different from the performance of the catalysts in which ethyl benzoate and similar esters of benzoic acid are used as outside donor.
THE PRESENT INVENTION
One object of this invention is to provide new catalyst-forming components comprising, as outside donor, a silicon compound containing Si—O—C bonds and an inside ester different from the esters of benzoic acid and derivatives, and which result in final catalysts of increased activity and stereospecificity as compared to the components heretofore known comprising, as inside donor, an ester of benzoic acid or derivative thereof; and the catalysts based on such components.
This and other objects are achieved by this invention in accordance with which, and unexpectedly, it has been found that it is possible to increase the activity and stereo-specificity of the prior art supported catalysts comprising, as outside donor, a silicon compound containing Si—O—C bonds, by using as inside donor an ester having a particular structure as described hereinafter.
The catalysts of this invention comprise the product of reaction between the following components:
(a) an Al trialkyl or an Al-alkyl compound containing 2 or more aluminum atoms linked to each other through oxygen or nitrogen atoms or through SO
4
or SO
3
groups;
(b) a silicon compound containing one or more S
i
—OR, Si—OCOR or Si—NR
2
bonds (R being a hydrocarbyl radical);
(c) a solid comprising, as essential support, an anhydrous Mg dihalide present in active form and, supported on said dihalide, a Ti halide or a Ti haloalcoholate and an electron-donor compound selected from the following groups of compounds:
(1) mono- and polyesters of saturated polycarboxylic acids wherein at least one of the esteric carbonyl groups is linked to a tertiary or quaternary carbon atom or to a linear or branched chain of at least 4 carbon atoms;
(2) mono- and polyesters of unsaturated polycarboxylic acids wherein two carboxy groups are linked to vicinal double bond-forming carbon atoms and in which at least one of the R hydrocarbyl radicals of the COOR groups is a branched saturated or unsaturated radical with 3 to 20 C atoms or is an aryl or arylalkyl radical with 6 to 20 C atoms;
(3) mono- and diesters of aromatic dicarboxylic acids having the COOH groups in ortho position wherein at least one of the R hydrocarbyl radicals of the COOR groups contains from 3 to 20 carbon atoms;
(4) mono- and polyesters of aromatic hydroxy compounds containing at least 2 hydroxyl groups in ortho position;
(5) esters of aromatic hydroxy acids wherein at least a hydroxyl group is in ortho position to the carboxy group;
(6) esters of saturated or unsaturated carboxylic acids wherein at least one of the hydrocarbyl R and R′ radicals of the R COOR′ group is a saturated or unsaturated branched radical containing from 3 to 20 C atoms, or is an arylalkyl radical with 7 to 20 C atoms or R is an aryl radical with 3 to 20 carbon atoms linked to the esteric carbonyl group directly or through a methylene group, and in which the R′ radical contains from 3 to 20 C when it is a linear hydrocarbyl radical; and
(7) esters of carbonic acid of formula
in which at least one of the R radicals which can be the same or different is a hydrocarbyl radical with 3 to 20 carbon atoms.
Representative esters which are suitable in preparing component (c) are the following:
Class 1
diethyl diisobutylmalonate, diethyl n-butylmalonate, diethyl-n-dibutylmalonate, diethylphenylmalonate, diethyl-1,2-cyclohexane-dicarboxylate, dioctylsebacate, diisobutyl adipate.
Class 2
di-2-ethyl-hexyl-maleate, diisobutylmaleate, diisobutyl-3,4-furan-dicarboxylate, di-2-ethylhexylfumarate, 2-ethylhexylmonomaleate.
Class 3
diisobutyl-2,3-naphthalen-dicarboxylate, di-n-propyl, di-n-butyl, diisobutyl, di-n-heptyl, di-2-ethyl-hexyl, di-noctyl, di-neopentil phthalates, monobutyl and monoisobutyl esters of phthalic acid, ethyl-isobutyl-phthalate, ethyl-n-butyl-phthalate.
Class 4
2,3-diacetoxynaphthalene, 1,2-diacetoxybenzene, 1-methyl-2,3-diacetoxybenzene.
Class 5
benzoyl-ethylsalicylate, acetyl-methylsalicylate.
Class 6
ethylene-glycol-pivalate, 1,4-butanediol-pivalate, benzyl and isobutylpivalate, n-propylpivalate, ethyl diphenylacetate, isobutylmethacrylate, isobutylacrylate, ethyl-benzoylacetate, isobutylpyruvate, isobutyl-trans-3-methoxy-2-butenoate.
Class 7
phenyl-ethylcarbonate, diphenyl carbonate.
Preferred compounds are the esters of maleic, pivalic, methacrylic, carbonic and phthalic acids.
As indicated, the esters of the polycarboxylic acids can contain, besides the ester groups, also unesterified COOH groups.
In preparing component (c) the esters are contacted with the active Mg dihalide or the precursors of said dihalides as preformed compounds or the esters can be formed in situ by means of known reactions as, for instance, by esterification between an alcohol or an alcoholate and an aryl halide or between an anhydride or a hemiester of a polycarboxylic acid with an alcohol or by transesterification. The esters can be used, also, in mixture with other known inside donors.
The active anhydrous Mg dihalides forming the essential support of component (c) are the Mg dihalides showing in the X-rays powder spectrum of component (c) a broadening of at least 30% of the most intense diffraction line which appears in the powder spectrum of the corresponding dihalide having 1 m
2
/g of surface area or are the Mg dihalides showing an X-rays powder spectrum in which said most intense diffraction line is replaced by a halo with the intensity peak shifted with respect to the interplanar distance of the most intense line and/or are the Mg dihalides having a surface area greater than 3 m
2
/g.
The measurement of the surface area of the Mg dihalides is made on component (c) after treatment with boiling TiCl
4
for 2 hours. The found value is considered as surface area of the Mg dihalide.
Very active forms of Mg dihalides are those showing an X-rays powder spectrum in which the most intense diffraction line appearing in the spectrum of the corresponding halide having 1 m
2
/g of surface area is decreased in relative intensity and broadened to form a halo or are those in which said most intense line is replaced by a halo having its intensity peak shifted with respect to the interplanar distance of the most intense line. Generally, the surface area of the above forms is higher than 30-40 m
2
/g and is comprised in particular between 100-300 m
2
/g.
Active forms are also those deriving from the above forms by heat-treatment of component (c) in inert hydrocarbon solvents and showing in the X-rays spectrum sharp diffraction lines in place of the halos.
The sharp, most intense line of these forms shows, in any case, a broadening of at least 30% with respect to the corresponding line of the Mg dihalide having 1 m
2
/g of surface area. Preferred Mg dihalides are Mg dichloride and Mg dibromide. The content in water of the dihalides is generally less than 1% by weig
Barbe′ Pier Camillo
Giannini Umberto
Nocci Roberto
Parodi Sandro
Scata′ Umberto
Choi Ling-Siu
Montell Technology Company BV
Wu David W.
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