Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-11-14
2003-04-01
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S348000, C526S216000, C526S124100, C526S124200, C526S127000, C526S128000, C526S158000, C502S103000, C502S127000, C502S133000
Reexamination Certificate
active
06541582
ABSTRACT:
The present invention relates to catalyst components for the polymerization of olefins, to the catalyst obtained therefrom and to the use of said catalysts in the polymerization of olefins CH
2
═CHR in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms. In particular the present invention relates to catalyst components, suitable for the stereospecific polymerization of olefins, comprising Ti, Mg, halogen and an electron donor compound selected from esters of &bgr;-substituted glutaric acids (&bgr;-substituted glutarates). Said catalyst components when used in the polymerization of olefins, and in particular of propylene, are capable to give polymers in high yields and with high isotactic index expressed in terms of high xylene insolubility.
&bgr;substituted glutarates are known in the art. However, they have never been used as internal electron donors in catalysts for the polymerization of olefins.
EP-A45977 mentions the use of &agr;-substituted glutarates as internal donors in catalyst components for the polymerization of olefins. The use of such compounds is not exemplified. &bgr;-substituted glutarates are not even mentioned.
In EP-A-86644 is disclosed the use of &agr;-substituted diesters, including glutarates, as internal electron donors in catalysts for the polymerization of olefins. Diisobutyl &agr;-methyl glutarate is specifically named but the use of such compounds is not exemplified. &bgr;-substituted glutarates are never mentioned.
The Japanese patent application Jp 11/060625 describes a catalyst component for the polymerization of olefins containing titanium, magnesium and a compound represented by the formula:
where R
1
and R
2
are hydrocarbon groups having from 1 to 20 carbon atoms, while n can be an integer from 1 to 10. In spite of this broad formula only malonates are mentioned and exemplified in the specification. Nothing is said about esters with n higher than 1.
The use of polycarboxylic acid esters, including glutarates, as internal donors in catalyst components for the polymerization of olefins, is also generically disclosed in EP 125911. Diisobutyl &agr;-methyl glutarate and diisopropyl &bgr;-methyl glutarate are mentioned in the description although they are not exemplified. The applicant has carried out some polymerization tests employing catalyst components containing the above compounds as internal donors. As shown in the experimental section, both the catalysts gave an unsatisfactory activity/stereospecificity balance. The same poor results have been obtained with catalysts containing other &agr;-substituted glutarates or unsubstituted glutarates.
It has been therefore very surprising to discover that, apart from diisopropyl &bgr;-methyl glutarate, the substitution in the &bgr;-position of the glutarates generates compounds that, when used as internal donors, give catalyst components having increased activity and stereospecificity with respect to the catalyst components containing &agr;-substituted or unsubstituted glutarates as internal donors.
It is therefore an object of the present invention to provide a solid catalyst component for the polymerization of olefins CH
2
═CHR in which R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms comprising Mg, Ti, halogen and an electron donor selected from &bgr;-substituted glutarates with the proviso that diisopropyl &bgr;-methyl glutarate is excluded.
In particular, the electron donor compounds can be selected from &bgr;-substituted glutarates of formula (I):
wherein the radicals R
1
to R
3
equal to or different from each other, are H or a C
1
-C
20
linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups, optionally containing heteroatoms, and two or more of said radicals can also be joined to form a cycle, with the provisions that R
1
and R
2
are not contemporaneously hydrogen, R
7
and R
8
are different from hydrogen and diisopropyl &bgr;-methyl glutarate is excluded.
An interesting class of &bgr;-substituted glutarates is that in which R
1
is H and R
2
is selected from linear or branched C
1
-C
10
alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups. Preferably, R
2
is selected from linear or branched C
1
-C
10
alkyls, cycloalkyl, and arylalkyl groups. Moreover, particularly good results have been obtained by using the compounds of formula (I) in which both R
1
and R
2
are different from hydrogen and are selected, in particular, from linear or branched C
1
-C
10
alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups.
R
7
and R
8
are preferably primary alkyl, arylalkyl or alkylaryl groups having from 1 to 10 carbon atoms. More preferably they are primary branched alkyl groups having from 1 to 8 carbon atoms. Examples of suitable R
7
and R
8
groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.
Specific examples of suitable &bgr;-monosubstituted glutarate compounds are diisobutyl 3-methylglutarate, diisobutyl 3-phenylglutarate, diethyl 3-ethylglutarate, diethyl 3-n-propylglutarate, diethyl 3-isopropylglutarate, diethyl 3-isobutylglutarate, diethyl 3-phenylglutarate, diisobutyl 3-ethylglutarate, diisobutyl 3-isopropylglutarate, diisobutyl 3-isobutylglutarate, diethyl 3-(3,3,3-trifluoropropyl)glutarate, diethyl 3-cyclohexylmethyl glutarate, diethyl 3-tertbutyl glutarate.
Specific examples of suitable &bgr;-disubstituted glutarates are: diethyl 3,3-dimethylglutarate, diisobutyl 3,3-dimethylglutarate, diethyl 3-methyl-3-isobutyl glutarate, diethyl 3-methyl-3-t-butyl glutarate, diisobutyl 3-methyl-3-isobutyl glutarate, diethyl 3-methyl-3-phenyl glutarate, diethyl 3,3-diisobutyl glutarate, diethyl 3-methyl-3-butyl glutarate, diethyl 3,3-diphenyl glutarate, diethyl 3-methyl-3-ethyl glutarate, diethyl 3,3-diethylglutarate, diethyl 3-methyl-3-isopropyl glutarate, diethyl 3-phenyl-3-n-butyl glutarate, diethyl 3-methyl-3-t-butyl glutarate, diethyl 3,3-diisopropyl glutarate diisobutyl 3-methyl-3-phenyl glutarate, diisobutyl 3,3-diisobutyl glutarate, diisobutyl 3-methyl-3-butyl glutarate, diisobutyl 3,3-diphenyl glutarate, diisobutyl 3-methyl-3-ethyl glutarate, diisobutyl 3,3-diethylglutarate, diisobutyl 3-methyl-3-isopropyl glutarate, diisobutyl 3-phenyl-3-n-butyl glutarate, diisobutyl 3-methyl-3-t-butyl glutarate, diisobutyl 3,3-diisopropyl glutarate, diethyl 3-ethyl-3 n butyl glutarate, diisobutyl 3-ethyl-3-n-butyl glutarate, diethyl 3-i-propyl-3-n-butyl glutarate, diisobutyl 3-i-propyl-3-n-butyl glutarate, diethyl 3-(2-methyl-butyl)-3-ethyl glutarate, diisobutyl 3-(2-methyl-butyl)-3-ethyl glutarate, diethyl 3-n-propyl-3-phenyl glutarate, diisobutyl 3-n-propyl-3-phenyl glutarate.
Specific examples of suitable &agr;,&bgr;-disusbstituted glutarates are: diethyl 2-methyl-3-phenyl glutarate, diethyl 2,2-dimethyl-3-phenyl glutarate, diethyl 2-methyl-3,3-diisobutyl glutarate, diethyl 2-ethyl-3-isopropylglutarate, diisobutyl 2-methyl-3-phenyl glutarate, diisobutyl 2,4-dimethyl-3-phenyl glutarate, diisobutyl 2-methyl-3,3-diisobutyl glutarate, diisobutyl 2-ethyl-3-isopropylglutarate.
Specific examples of suitable glutarates in which the substituents R
1
and R
2
are linked to form a cycle are 9,9-bis(ethoxyacetyl)fluorene, 1,1-bis(ethoxyacetyl)cyclopentane, 1,1-bis(ethoxyacetyl)cyclohexane, 1,3-bis(ethoxycarbonyl)-1,2,2-trimethylcyclopentane.
As explained above, the catalyst components of the invention comprise, in addition to the above electron donors, Ti, Mg and halogen. In particular, the catalyst components comprise a titanium compound having at least a Ti-halogen bond, the above mentioned electron donor compound and a Mg dihalide. The magnesium halide is preferably MgCl
2
in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts. U.S. Pat. No. 4,298,718 and U.S. Pat. No. 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that the magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerization of olefins are characterized by X-ray spect
Balbontin Giulio
Morini Giampiero
Basell Poliolefine Italia S.p.A.
Choi Ling-Siu
Wu David W.
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