Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-03-19
2001-09-11
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...
C526S124300, C526S124500, C526S126000, C526S125300, C526S351000, C526S348600, C502S116000, C502S125000
Reexamination Certificate
active
06288180
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to a process for the polymerization of C
3
-C
12
-&agr;-olefins, wherein
A) a catalyst system is prepared by bringing a support which comprises magnesium chloride, a derivative thereof or a reagent forming it into contact with at least titanium tetrachloride or a reagent forming it, in order to produce a titanated support, by bringing the titanated support into contact with at least a compound of a metal of group 1, 2 or 13 of the Periodic Table of the Elements (IUPAC 1990), which compound contains a C
1
-C
10
-alkyl and activates titanium tetrachloride to a catalytically active titanium group, in order to produce an activated support, and by bringing a substance selected from among the said support, titanated support and activated support into contact with at least one donor or a reagent forming it, in order to produce a catalyst system;
B) polymerization is carried out by using the catalyst system by contacting it with at least a C
3
-C
12
-&agr;-olefin, whereupon poly-C
3
-C
12
-&agr;-olefin chains are formed in the catalytically active titanium groups, and preferably by contacting the said catalyst system, the said C
3
-C
12
-&agr;-olefin and the said poly-C
3
-C
12
-&agr;-olefin chains with hydrogen or some other similar chain transfer agent, whereby a poly-C
3
-C
12
-&agr;-olefin terminated with hydrogen or suchlike is formed.
The invention also relates to a method for the preparation of a catalyst system intended for the polymerization of C
3
-C
12
-&agr;-olefins, in which process a support which comprises magnesium chloride, a derivative thereof or a reagent forming it is contacted with at least titanium tetrachloride or a reagent forming it, in order to form a titanated support; the titanated support is contacted with at least a compound of the said group 1, 2, or 13 metal, which compound contains a C
1
-C
10
-alkyl and activates titanium tetrachloride to a catalytically active titanium group, in order to produce an activated support; and a substance selected from among the said support, titanated support and activated support is contacted with at least one donor or a reagent forming it, whereby the said catalyst system is formed.
By titanated support is meant a contact product of a support and titanium tetrachloride or a reagent forming it. By activated support is meant a support which has first been contacted with titanium tetrachloride or a reagent forming it, and thereafter with a metal compound which contains a C
1
-C
10
-alkyl and activates titanium tetrachloride.
Finally the invention relates to a catalyst system intended for the polymerization of C
3
-C
12
-&agr;-olefins, the catalyst system being prepared by the above method for the preparation of a catalyst system.
1. Discussion of Related Art
The conventional process for the polymerization of poly-C
3
-C
12
-&agr;-olefins has the disadvantage that all of the donors used therein participate in a random equilibrium system. Thus the quantity and quality of the poly-C
3
-C
12
-&agr;-olefin fractions depending on equilibrium cannot be regulated. This has resulted, for example, in that, when the isotacticity of the product is raised by using a larger donor quantity, the hydrogen sensitivity of the catalyst system has decreased and its activity has dropped.
2. Summary of the Invention
In the said step A) of the polymerization process, when a support comprising magnesium chloride, a derivative thereof or a reagent forming is contacted with titanium tetrachloride or a reagent forming it, there is formed a titanated support having at least titanium tetrachloride coordinated to its magnesium chloride.
Thus, when the said titanated support is contacted with a metal compound containing a C
1
-C
10
-alkyl, there is formed an activated support having catalytically active titanium groups coordinated to its magnesium chloride.
Finally, when a substance selected from among the said support, titanated support and activated support is contacted with at least one donor or a reagent forming it, a catalyst system is formed the activated support of which has, coordinated in its magnesium chloride, catalytically active titanium groups and at least one type of donor.
An object of the present invention is to provide a poly-C
3
-C
12
-&agr;-olefin as isotactic as possible, without reducing the hydrogen sensitivity or activity of the catalyst system.
The above-mentioned objects of the invention have now been achieved by a novel process for the polymerization of C
3
-C
12
-&agr;-olefins, the process being primarily characterized in that in step A):
i) on the surface of the said support, titanated support or activated support there is provided a first controlled amount of a less soluble internal donor and a second controlled amount of a more soluble internal donor to produce an internal donoration product, and
ii) the internal donoration product is contacted with at least one eluant eluting the more soluble internal donor and with at least one external donor or a reagent forming it, in order to produce an external donoration product,
the catalyst system thereby formed containing at least catalytically active titanium groups, the said first controlled amount of the less soluble internal donor, and the said second controlled amount comprising the external donor.
REFERENCES:
patent: 5541260 (1996-07-01), Pelliconi et al.
patent: 5684173 (1997-11-01), Hosaka et al.
patent: 0409492 (1991-01-01), None
patent: 0 489 536 A2 (1992-06-01), None
patent: 0489536 (1992-06-01), None
patent: 0627449 (1994-12-01), None
patent: 0665243 (1995-08-01), None
patent: 0683175 (1995-11-01), None
patent: 0728769 (1996-08-01), None
patent: 0728770 (1996-08-01), None
Ala-Huikku Sirpa
Garoff Thomas
Leinonen Timo
Birch & Stewart Kolasch & Birch, LLP
Borealis Polymers OY
Harlan R.
Wu David W.
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