Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2003-05-07
2004-06-01
Lu, Caixia (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S160000, C526S165000, C526S172000, C526S201000, C502S108000, C502S109000, C502S152000, C502S167000
Reexamination Certificate
active
06743873
ABSTRACT:
The present invention relates to: an olefin polymerization catalyst composition including an epoxy functional porous organic polymer, a catalytic component, and an activator component; a process of making the olefin polymerization catalyst composition; and a process for preparing a variety of polyolefin products using a range of olefin polymerization catalyst compositions.
Commercial catalytic processes for the production of polyolefins, such as polyethylene and polypropylene, have traditionally relied on the use of heterogeneous Ziegler-Natta catalyst systems. Typical catalyst systems for polyethylene are exemplified by chromium catalysts and titanium/MgCl
2
catalysts. Although the catalyst systems are quite active and can produce high molecular weight polymers, they tend to produce a broad molecular weight distribution of a particular polyolefin and are poor at incorporating alpha olefins such as 1-hexene and 1-octene. When making copolymers, these catalysts typically produce polyethylene resins of moderately broad to very broad molecular weight distribution, as characterized by molecular weight distribution polydispersities of 3 or more. Lack of a narrow molecular weight distribution in polyolefins produced using such catalyst systems is believed due to the presence of more than one type of catalytic site.
More recently, olefin polymerization catalyst systems containing well defined single reactive sites have been developed. Single-site catalysts allow for the production of polymers with varied molecular weights, narrow molecular weight distributions and the ability to incorporate large amounts of comonomers. Metallocene catalysts based on Group 4 metals of the Periodic Table (IUPAC nomenclature) containing cyclopentadienyl groups are examples of these active single-site catalysts. Such catalysts have been disclosed in U.S. Pat. Nos. 5,064,802, 5,198,401, and 5,324,800.
The mechanism of olefin polymerization has been the subject of much study and is believed to involve generation of an unsaturated, electron deficient metal species, which coordinates olefins to form intermediate alkyl olefin complexes, subsequently undergoing rapid alkyl migration to afford a growing polymer chain. Olefin coordination followed by migration (insertion) continues until a termination step occurs or the reaction is stopped.
Several methods are currently employed to generate and stabilize the unsaturated electron deficient metal catalysts of such systems. The activation of transition metal complexes to afford stabilized, unsaturated transition metal catalysts for the polymerization of olefins is a key part of this mechanism. Several methods are currently employed to generate and stabilize the unsaturated, electron deficient metal catalysts of such systems and include halide abstraction, protonation followed by reductive elimination of an alkane or hydrogen, or oxidation. A key element of the activation process is the stabilization of the resulting activated complex using non-coordinating anions. For example, halide containing metallocene complexes can be activated using an organoaluminoxane such as methylaluminoxane (MAO) or isopropylaluminoxane. MAO serves as both a methyl alkylating agent and a non-coordinating anion. Other activating components of utility containing boron include silver tetraphenyl borate, triphenylcarbenium tetrakis(pentafluorophenyl) borate, triaryl carbenium tetraarylborates, tris(pentafluorophenyl) boron, N,N-dimethylanilinium tetra(pentafluorophenyl) borate and sodium tetrakis[3,5-bis(trifluoromethyl)-phenyl] borate. Catalyst systems using such activators have been disclosed in U.S. Pat. Nos. 4,808,561; 4,897,455; 4,921,825; 5,191052; 5,198,401; 5,387,568; 5,455,214; 5,461,017; 5,362,824; 5,498,582; 5,561,092; 5,861,352 and publications WO 91/09882; EP0206794B1; EP0507876B1; WO 95/15815; WO 95/23816; EP0563917B1; EP0633272A1; EP0633272B1; EP0675907B1; JP96-113779; EP0677907B1; WO 98/55518; WO 00/04059.
The greatest utility of single-site catalyst systems to the polyolefin industry is realized when they are used in existing gas phase and slurry phase reactors. Inorganic oxides such as silica, alumina and magnesia currently have the greatest utility as support materials in the formulation of supported Ziegler-Natta polyolefin catalyst systems. The inorganic supports have also been used with varying degrees of success in supporting metallocene and other types of single-site metal catalysts. A significant limitation of such supports, however, is the presence of surface hydroxyl groups, which can render the metallocene catalysts less active. Large quantities of MAO are used to overcome this effect, with varying degrees of success coupled with the high costs associated with using excess MAO.
EP-0767184-B1 discloses porous organic polymers as supports for olefin polymerization catalysts and activators. The disclosed porous organic polymers are acrylic polymers having polar functional groups. Most of these polar functional groups have active hydrogens capable of reacting with activators such as aluminoxanes. The disclosed polar groups are amino, imino, amide, imide, hydroxyl, formyl, carboxyl, sulfone, and thiol. Although these polar groups afford varying degrees of reactivity with aluminoxanes, they are also capable of producing undesirable side reactions that can limit the efficiency, specificity, and activity characteristics of supported catalysts produced using them. A group that is reactive with activator components, yet is less prone to side reactions than, for example, hydroxyl and thiol groups would be expected to react with activator components and catalytic components (the organometallic catalyst) to produce catalyst compositions having the efficiency, specificity, and activity characteristics desired in catalysts for olefin polymerization.
We have surprisingly found that porous organic polymers, for example macroreticular resins, bearing pendant olefinic groups may be epoxidized to form pendant epoxy groups which combine with organometallic catalysts and activators to produce olefin polymerization catalyst compositions. In addition, epoxy functional catalyst compositions can be produced directly by polymerization of monomer mixtures containing epoxy functional monomers. These olefin polymerization catalyst compositions are highly active, providing high yields of spherical polyolefins with minimal reactor fouling.
An aspect of the present invention relates to an olefin polymerization catalyst composition, wherein said catalyst composition comprises:
(a) at least one catalytic component;
(b) at least one activator component; and
(c) at least one epoxy functional porous organic polymer,
wherein said epoxy polymer comprises a plurality of epoxy groups covalently bound to said epoxy polymer.
A second aspect of the present invention relates to a process of making an olefin polymerization catalyst composition, said process comprising:
(a) combining:
(i) at least one epoxy functional porous organic polymer;
(ii) at least one catalytic component; and
(iii) at least one activator;
(b) allowing said epoxy polymer, said catalytic component, and said activator component to react; and,
(c) optionally, isolating said catalyst composition.
A third aspect of the present invention relates to an olefin polymerization process, wherein said olefin polymerization process comprises:
(a) contacting at least one olefin monomer with at least one olefin polymerization catalyst composition;
(b) polymerizing said olefin monomer to produce a polyolefin;
(c) isolating said polyolefin, wherein said catalyst composition comprises:
(i) at least one catalytic component;
(ii) at least one activator component; and
(iii) at least one epoxy functional porous organic polymer, wherein said epoxy polymer comprises a plurality of epoxy groups covalently bound to said epoxy polymer.
Used herein, the following terms have these definitions:
A “catalytic component” is an organometallic catalyst based on a metal, wherein said metal is a metal selected from the group consisting of metals of Group 3-10, la
Kirk Thomas Cleveland
Lundquist Eric Gustave
Lynn Timothy Roger
Clikeman Richard R.
Lu Caixia
Rohm and Haas Company
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