Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1995-06-07
2002-12-03
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...
C526S129000, C526S098000, C526S099000, C526S100000
Reexamination Certificate
active
06489410
ABSTRACT:
BACKGROUND OF INVENTION
This invention relates to a method of producing a supported catalyst component, the catalyst component produced according to the method, to an olefin polymerization supported catalyst composition, and to an olefin polymerization process using such a supported catalyst.
Supported catalysts of the Ziegler or Ziegler-Natta type can be used in the polymerization of olefins in various types of polymerization reaction systems, including high pressure, solution, slurry, and gas phase processes. Different techniques are known for producing supported catalysts. In each of the known techniques the reactive catalytic metal (e.g., titanium) is typically added after preparation of the support. This support is typically a magnesium halide or alkoxide species, or a silica support onto which a magnesium halide or alkoxide is deposited.
For example, U.S. Pat. No. 4,526,943 discloses an olefin polymerization catalyst prepared by the reaction of a hydrocarbon soluble organomagnesium compound with a trialkylaluminum reagent and an aliphatic alcohol to generate a soluble magnesium alkoxide precursor to which a transition metal compound (typically a titanium compound) is added. U.S. Pat. No. 4,560,733 teaches the use of a catalyst system having a titanium coating component made from a milled blend of two different supports, each support being treated with a dihyrocarboxylmagnesium compound, and a halogenated tetravalent titanium compound.
U.S. Pat. Nos. 4,672,096 and 4,670,413 disclose contacting a magnesium compound and the carrier with a transition metal (e.g., titanium or vanadium) compound to produce a supported solid catalyst composition.
With each of these methods the support treated with the organomagnesium halide compound is subsequently treated by the addition of the polymerization active transition metal. These procedures can lead to a less than uniform distribution of polymerization active metal on the catalytic support and can involve difficult handling procedures such as refluxing the catalyst precursors in neat or concentrated solutions of the transition metal reagent until sufficient metal absorption has been achieved. Furthermore, by adding the active metal to the precursor after the precursor is formed, in order to obtain a sufficient quantity of catalytic metal, the active metal salt must often be added in excess requiring the additional step of eliminating the excess afterwards. Failure to remove the excess metal salt can produce soluble polymerization active metal centers that adversely affect slurry and gas phase polymerization processes, i.e., formation of skins or agglomerates.
Accordingly, it is the object of the present invention to overcome these problems and disadvantages by providing an active polymerization catalyst and one that does not require the subsequent addition of the polymerization active transition metal. Moreover, the additional object of the present invention is to eliminate handling and excessive transition metal reagent usage associated with the preparation of the typical Ziegler-Natta catalysts. Furthermore, the present invention converts normally inactive transition metal centers into centers capable of preparing narrow molecular weight distribution olefins such as ethylene or other &agr;-olefins. The present invention also achieves a catalyst that is displays excellent hydrogen response and is capable of producing a range of moleular weight polymers from ultra high molecular weight (zero melt flow) polyethylene to low molecular weight (high melt flow) polyethylene.
SUMMARY OF INVENTION
In accordance with one aspect of the present invention, there is provided novel compositions of matter which are useful for polymerization of olefins by providing a catalyst composition that does not require the additional treatment with the polymerization active transition metal.
Also provided in accordance with this invention are methods for making the novel compositions and methods of using the compositions for polymerization of olefins. In its broadest form, the method of producing the supported catalytic composition of the present invention comprises treating an inorganic support (e.g., gels, co-gel, tergels) which has incorporated therein a Groups 3-10 transition metal from the Periodic Table with a metal alkylating reagent wherein the reaction product is then treated with a halogenating reagent. The resultant reaction product is, optionally, recovered and available for use in conjunction with the activating co-catalyst (a.k.a an activator) for the polymerization of polyolefins.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a novel method of making active polymerization catalyst compositions and the novel composition provided therefrom. The method of the present invention provides that a supported catalyst component is obtained by:
1) treating a support, preferably calcined and preferably a gel, co-gel or tergel and mixtures thereof, containing at least one Group 3-10 transition metal, preferably an oxide, with an alkylating reagent;
2) treating the reaction product from step one with a halogenating reagent; and, optionally,
3) recovering the reaction product from step 2.
The resulting catalyst is suitable for homo-polymerizing and copolymerizing olefinic monomers and co-monomers, particularly, ethylene and other &agr;-olefins, e.g., propylene, 1-butene, 1-hexene.
The catalysts produced according to the present invention are described below in terms of the manner in which they are made.
The Metal Containing Support Material
The metal containing support can be purchased from suppliers or prepared using known techniques wherein the metal is uniformly distributed throughout the support's structure. For example, U.S. Pat. No. 3,887,494 teaches one method of preparing a SiO
2
—TiO
2
cogel. Any inorganic or inorganic oxide support material containing a metal from the Group 3-10 transitional metals from the Periodic Table can be used in this invention upon mixing with suitable alkylating and halogenating reagents.
Suitable inorganic oxides in the support include talcs, clays SiO
2
, Al
2
O
3
, MgO, ZrO
2
, TiO
2
, Fe
2
O
3
, B
2
O
3
, CaO, ZnO, BaO, ThO
2
and mixtures thereof such as silica alumina, silica alumina titania, zeolite, ferrite and glass fibers. Such mixtures include physical and gelled mixtures. In addition, the above-mentioned inorganic oxide carriers may contain a small amount of carbonates, nitrates, sulfates or the like. Additional suitable inorganic oxide materials include aluminum phosphate gel materials and mixtures of two or more of the foregoing.
The transition metal combined with the inorganic or inorganic oxide material describe above, is selected from metals in Groups 3 to 10 of the Periodic Table and preferably in an oxide form of these metals. Most preferred transition metals are oxides from the Groups 3-6 of the Periodic Table. Most preferably are vanadia, zirconia, chromia, and titania and mixtures thereof. The transition metal is from about 0.1 wt. % of the total weight of the support to 100 wt. % of the total weight of the support.
The degree of porosity in the carrier may be any level that is achievable in the starting material. Preferably, the carrier particles of the present invention have a pore volume of at least 0.1 cc/g; preferably from 0.25 to 5 cm
3
/g; most preferably from about 0.7 to 3.0 cm
3
/g.
Preferably, the particles have a surface area of about 1-1000 m
2
/g; preferably from about 25-600 m
2
/g; more preferably from about 100 to 450 m
2
/g. The typical median particle size for a suitable co-gel for this invention is from 1 to 300 microns; preferably from 5 to 200 microns; and more preferably from 180 microns.
Pore volume and surface area can be, for example, measured from volume of nitrogen gas adsorbed in accordance with BET method. (Refer to J. Am. chem. Soc., Vol. 60, p. 309 (1983)).
The metal containing support is preferably calcined prior to treatment with the alkylating and halogenating reagents at a temperature in the range of from about 150° C. to 1000° C.,
Carney Michael John
Ward David George
Cheung William K.
Maggio Robert A.
W. R. Grace & Co.,-Conn.
Wu David W.
LandOfFree
Supported catalyst composition for polymerization of olefins does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Supported catalyst composition for polymerization of olefins, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Supported catalyst composition for polymerization of olefins will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2997336