Components and catalysts for the polymerization of olefins

Details Components and catalysts for the polymerization of olefins Components and catalysts for the polymerization of olefins

2001-10-01

2004-04-06

Choi, Ling-Siu (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S142000, C526S123100, C526S124100, C526S348000, C502S103000, C502S127000, C502S115000

Reexamination Certificate

active

06716939

ABSTRACT:

The present invention relates to catalyst components for the polymerization of olefins, to the catalysts 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 substituted succinic acids (substituted succinates). 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.
The chemical class of succinates is known in the art. However, the specific succinates of the present invention have never been used as internal electron donors in catalysts for the polymerization of olefins.
EP-A-86473 mentions the use of unsubstituted succinates as internal donors in catalyst components for the polymerization of olefins. The use of diisobutyl succinate and di-n-butyl succinate is also exemplified. The results obtained in terms of isotactic index and yields are however poor.
The use of polycarboxylic acid esters, including succinates, as internal donors in catalyst components for the polymerization of olefins, is also generically disclosed in EP 125911. Diethyl methylsuccinate and diallyl ethylsuccinate are mentioned in the description although they are not exemplified. Furthermore, E1P263718 mentions, but does not exemplify, the use of diethyl methylsuccinate and di-n-butyl ethylsuccinate as internal donors. In order to check the performances of these succinates according to the teaching of the art the applicant has carried out some polymerization tests employing catalyst components containing diethyl methylsuccinate and diethyl ethylsuccinate, respectively, as internal donors. As shown in the experimental section, the so obtained catalysts gave an unsatisfactory activity/stereospecificity balance very similar to that obtained with catalysts containing unsubstituted succinates.
It has been therefore very surprising to discover that the specific substitution in the succinates of the invention generates compounds that, when used as internal donors, give catalyst components having improved activity and stereo specificity. 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 succinates of formula (I):
wherein the radicals R
1
and R
2
, equal to or different from each other, are a C
1
-C
20
linear or branched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containing heteroatoms and the radical R
3
is a linear alkyl group having at least four carbon atoms optionally containing heteroatoms.
R
1
and R
2
are preferably C
1
-C
8
alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl groups. Particularly preferred are the compounds in which R
1
and R
2
are selected from primary alkyls and in particular branched primary alkyls. Examples of suitable R
1
and R
2
groups are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl, and neopentyl.
One of the preferred groups of compounds described by the formula (I) is that in which R
3
is a linear alkyl having from 4 to 20 carbon atoms. Particularly preferred are the compounds in which R
3
is a linear alkyl group having from 4 to 15 carbon atoms.
Specific examples of suitable monosubstituted succinate compounds are dimethyl n-butylsuccinate, dimethyl n-pentylsuccinate, dimethyl n-hexylsuccinate, dimethyl n-heptylsuccinate, dimethyl n-octylsuccinate, dimethyl n-nonylsuccinate, dimethyl n-decylsuccinate, dimethyl n-undecylsuccinate, dimethyl n-dodecylsuccinate, dimethyl tetradecylsuccinate, diethyl n-butylsuccinate, diethyl n-pentylsuccinate, diethyl n-hexylsuccinate, diethyl n-heptylsuccinate, diethyl n-octylsuccinate, diethyl n-nonylsuccinate, diethyl n-decylsuccinate, diethyl n-undecylsuccinate, diethyl n-dodecylsuccinate, diethyl tetradecylsuccinate, diisobutyl n-butylsuccinate, diisobutyl n-pentylsuccinate, diisobutyl n-hexylsuccinate, diisobutyl n-heptylsuccinate, diisobutyl n-octylsuccinate, diisobutyl n-nonylsuccinate, diisobutyl n-decylsuccinate, diisobutyl n-undecylsuccinate, diisobutyl n-dodecylsuccinate, diisobutyl tetradecylsuccinate, dineopentyl n-butylsuccinate, dineopentyl n-pentylsuccinate, dineopentyl n-hexylsuccinate, dineopentyl n-heptylsuccinate, dineopentyl n-octylsuccinate, dineopentyl n-nonylsuccinate, dineopentyl n-decylsuccinate, dineopentyl n-undecylsuccinate, dineopentyl n-dodecylsuccinate, dineopentyl tetradecylsuccinate, di-n-butyl n-butylsuccinate, di-n-butyl n-pentylsuccinate, di-n-butyl n-hexylsuccinate, di-n-butyl n-heptylsuccinate, di-n-butyl n-octylsuccinate, di-n-butyl n-nonylsuccinate, di-n-butyl n-decylsuccinate, di-n-butyl n-undecylsuccinate, di-n-butyl n-dodecylsuccinate, di-n-butyl tetradecylsuccinate, methyl ethyl n-butylsuccinate, methyl ethyl n-pentylsuccinate, methyl ethyl n-hexylsuccinate, methyl ethyl n-heptylsuccinate, methyl ethyl n-octylsuccinate, methyl ethyl n-nonylsuccinate, methyl ethyl n-decylsuccinate, methyl ethyl n-undecylsuccinate, methyl ethyl n-dodecylsuccinate, methyl ethyl tetradecylsuccinate, isobutyl ethyl n-butylsuccinate, isobutyl ethyl n-pentylsuccinate, isobutyl ethyl n-hexylsuccinate, isobutyl ethyl n-heptylsuccinate, isobutyl ethyl n-octylsuccinate, isobutyl ethyl n-nonylsuccinate, isobutyl ethyl n-decylsuccinate, isobutyl ethyl n-undecylsuccinate, isobutyl ethyl n-dodecylsuccinate, isobutyl ethyl tetradecylsuccinate.
It is easily derivable for the ones skilled in the art that all the above mentioned compounds can be used either in form of pure isomers or in the form of mixtures of enantiomers, or mixture of regioisomers and enantiomers. When a pure isomer is to be used it is normally isolated using the common techniques known in the art.
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 and the above mentioned electron donor compound supported on a Mg halide. According to the present invention with the term supported on a Mg halide are meant the Ti compound and the electron donor compounds which are not extractable to an extent higher than 50% when the extraction is carried out with heptane at 80° C. in 2 hours. 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. Patents 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 spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line. The preferred titanium compounds used in the catalyst component of the present invention are TiCl
4
and TiCl
3
; furthermore, also Ti-haloalcoholates of formula Ti(OR)
n-y
X
y
, where n is the valence of titanium and y is a number between 1 and n, can be used.
The preparation of the solid catalyst component can be carried out according to several methods. According to one of these methods, the magnesium dichloride in an anhydrous state and the succinate of formula (I) are milled together under conditions in which activation of the magnesium dichloride occurs. The so obtained product

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