Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-12-31
2002-07-16
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...
C526S151000, C526S158000, C526S123100, C502S103000, C502S172000, C502S115000, C502S132000
Reexamination Certificate
active
06420500
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a novel supported catalyst component useful for &agr;-olefin polymerization and a method of polymerizing an &agr;-olefin using the same. In more detail, the intention relates to a catalyst component with transition metal complex supported onto a carrier such as magnesium chloride and a method of efficiently and stereoselectively homo- or co-polymerizing an &agr;-olefin such as ethylene or propylene, using the same.
BACKGROUND TECHNOLOGIES
It is publicly known that, generally, as a catalyst for yielding stereoselective &agr;-olefin polymer, titanium catalyst component supported onto magnesium halide can be applied to the high-activity polymerization of olefin. For most of those catalyst components, not only magnesium halides, for example, magnesium dihalide and magnesium alkoxy halide, but also magnesium compounds containing no halogen can be used, if using a suitable halogenating agent. Exemplifying some of them, for example, in Japanese Unexamined Patent Publication No. 54-123594, a method of reacting a complex consisting of organomagnesium compound and organoaluminum compound with tertiary alkyl halide, and then treating the product with carboxylic ester and titanium tetrachloride is proposed. Also, in Japanese Unexamined Patent Publication No. Sho 54-133584, a method of treating solid product obtainable through the reaction between organomagnesium compound and organic halide compound with electron donor compound, and then supporting titanium tetrachloride thereonto is proposed and, in Japanese Unexamined Patent Publication No. Sho 55-133408, a method of treating solid organomagnesium compound with aromatic alcohol and electron donor compound, and then treating with titanium tetrachloride is proposed, and so on.
For the titanium catalyst component used in the publicly known methods as describe above, titanium tetrachloride is used in almost all cases, but it has a drawback that, when titanium compound is reduced with cocatalyst, it forms clusters, leading to nonuniform active species of catalyst. As the reports relating thereto, for example, Macromol. Chem., 189, 1531 (1988) and Macromol. Chem., Rapid Commun., 14, 85 (1993) can be mentioned.
Moreover, a catalyst system that uses no titanium tetrachloride as a metal source has also been developed and studied extensively. A typical example thereof is one generally called Kaminsky type catalyst, in which metallocene compound having cyclopentadienyl ring is combined with cocatalyst such as methylaluminoxane to perform the homo- or co-polymerization of ethylene or &agr;-olefin.
These catalyst systems are so-called homogeneous catalysts and said to have uniform polymerization active sites. In the case of aiming at the industrial application, however, high-temperature polymerization over 80° C. is required, for example, on polymerization of propylene, and decreased stability of complex and stereoregularity of polymer produced arise problems. For these, a method of introducing substituent into ligand, in particular, cyclopentadienyl ring, a method of crosslinking ligand each other, a method of introducing suitable substituent into crosslinked site, etc. are proposed. However, the modifications of metallocene complex as above accompany complicated organic reactions in general, causing increased cost for catalyst, if attempting to use industrially.
On the other hand, a method of using organometallic complex having no cyclopentadienyl ring, which is called non-metallocene type catalyst, for the homo or co-polymerization of ethylene or &agr;-olefin is also proposed.
For example, in U.S. Pat. No. 5,223,465, a method of using titanium, ziroconium and hafnium complex having a ligand like &bgr;-diketone and cocatalyst of organoaluminum such as methyl aluminoxane for the polymerization of ethylene, &agr;-olefin, styrene or the like is proposed. Also, in U.S. Pat. No. 3,393,245, oligomerization of diene using &bgr;-diketone complex of nickel is proposed. Also, in Macomol. Chem., Rapid Commun. 15, 655 (1994)), oligomerization of ethylene with &bgr;-diketone complex of ziroconium and halogen-containing alkyl aluminum is reported.
The purpose of the invention is to provide a novel catalyst having polymerization activity to &agr;-olefin equivalent to metallocene catalyst without using expensive catalyst component that causes a problem in the metallocene type catalyst and being useful also in the industry, and a method of polymerizing &agr;-olefin such as ethylene or propylene, using the same.
DISCLOSURE OF THE INVENTION
The invention relates to a catalyst component for the polymerization of &agr;-olefin characterized by contacting a complex represented by general formula (1)
(wherein R
1
and R
2
are the same or different and each represents a linear or branched lower alkyl group with C
1
-C
6
, alkyl halide with C
1
-C
3
or optionally substituted phenyl group, and X represents a halogen atom), with a magnesium compound. The invention is to provide a catalyst, wherein R
1
and R
2
are the same or different and preferably each represents methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, trifluorornethyl group or phenyl group, and X represents a chlorine atom.
Moreover, the invention concurrently provides a method of polymerizing &agr;-olefin using the inventive catalyst component. As a concrete method, the invention relates to a method of polymerizing &agr;-olefin using said catalyst and organoaluminum compound in the coexistence or non-coexistence of organic acid or organosilicon compound as a third component, and, as an organoaluminum compound to be used, organoaluminum compound represented by general formula (2)
R
3
R
4
R
5
Al (2)
(wherein R
3
, R
4
and R
5
are the same or different and each represents a linear or branched lower alkyl group with C
1
-C
8
or halogen atom),
or an organoaluminum compound obtainable by partially hydrolyzing one or a plurality of those organoaluminum compounds can be used. Also, as the organic acid of the third component, preferably, aromatic carboxylic ester can be used.
Moreover, as the organosilicon compound of the third component, an organosilicon compound represented by general formula (3)
R
6
R
6
R
8
R
9
Si (3)
(wherein R
6
, R
7
, R
8
and R
9
are the same or different and each represents a linear, branched or cyclic lower alkyl group with C
1
-C
8
, optionally substituted phenyl group or alkoxy group), can be use.
As a catalyst component in the homo- or co-polymerization of &agr;-olefin such as ethylene or propylene, the invention is to provide a catalyst characterized by contacting a complex represented by general formula (1)
(wherein R
1
and R
2
are the same or different and each represents a linear or branched lower alkyl group with C
1
-C
6
, alkyl halide with C
1
-C
3
or optionally substituted phenyl group, and X represents a halogen atom),
with a magnesium compound, and, at the same time, a method of homo- or co-polymerizing &agr;-olefin such as ethylene or propylene, using said catalyst and organoaluminum compound in the coexistence of or non-coexistence organic acid or organosilicon compound as a third component.
In the general formula (1), as R
1
and R
2
, lower alkyl groups with C
1
-C
6
such as m ethyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group, alkyl halides such as trifluoromethyl group, and phenyl groups which are not substituted or may be substituted with lower alkyl group with C
1
-C
3
such as phenyl group, tolyl group and ethylphenyl group can be mentioned. Preferable are methyl group, t-butyl group, trifluoromethyl group and phenyl group. As X, for example, chlorine atom, bromine atom, iodine atom, etc. can be mentioned. Preferable is chlorine atom.
As such titanium complexes, concretely, for example, bis-(2,4-pentanedionato)titanium dichloride, bis(1,1,1-trifluoro-2,4-pentanedionato)titanium dichloride, bis(2,2-dimethyl-3,5-hexanedionato)titanium dichloride, bis(1-phenyl-1,3-butanedionato)titaniu
Kaji Eiichi
Soga Kazuo
Uozumi Toshiya
Choi Ling-Siu
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Tosoh Akzo Corporation
Wu David W.
LandOfFree
Catalyst for &agr;-olefin polymerization does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Catalyst for &agr;-olefin polymerization, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Catalyst for &agr;-olefin polymerization will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2898122