KR-102963475-B1 - Catalyst composition for polyolefin polymers

KR102963475B1KR 102963475 B1KR102963475 B1KR 102963475B1KR-102963475-B1

Abstract

A Ziegler-Natta catalyst composition is disclosed. The catalyst composition is formed from a procatalyst containing a magnesium moiety and a titanium moiety. At least one internal electron donor is introduced into the procatalyst. During the titaniumation process, a titanium extractant is used in conjunction with the internal electron donor to remove or inactivate low-activity or atactic titanium active sites.

Inventors

엡스타인 로날드
밀러 마이클
엘더 마이클
마린 블라디미르
힌톨레이 아흐메드
보이어 티모시

Assignees

더블유.알. 그레이스 앤드 캄파니-콘.

Dates

Publication Date: 20260512
Application Date: 20200916
Priority Date: 20190918

Claims (20)

As a process for producing a Ziegler-Natta procatalyst composition, A precatalyst containing magnesium undergoes at least a first titaniumation step and a second titaniumation step; A step of introducing an internal electron donor into the above-mentioned precatalyst; and A step of contacting the above-mentioned precatalyst with a titanium extractant during or after the titaniumation steps, wherein the titanium extractant removes titanium on the above-mentioned precatalyst. Includes, A process in which the titanium extractant comprises an alkyl benzoate, and at least one of the internal electron donor and the titanium extractant is in contact with a precatalyst during the first titaniumation step and the second titaniumation step.
In claim 1, the titanium extractant comprises ethyl benzoate, in the process.
In claim 1, the process wherein the internal electron donor comprises an aryl diester.
In claim 1, the process comprises the internal electron donor comprising naphthyl dibenzoate having the following chemical formula: (In the above formula, each R is independently hydrogen, a halogen, an alkyl having 1 to 8 carbon atoms, a phenyl, an arylalkyl having 7 to 18 carbon atoms, or an alkylaryl having 7 to 18 carbon atoms, and in other embodiments, each R is independently hydrogen, an alkyl having 1 to 6 carbon atoms, a phenyl, an arylalkyl having 7 to 12 carbon atoms, or an alkylaryl having 7 to 12 carbon atoms).
In claim 1, the process wherein the precatalyst is in contact with the titanium extractant during the first titaniumation step.
In claim 1, the process wherein the precatalyst is in contact with the titanium extractant during the second titaniumation step.
A process according to claim 1, wherein during the first titanium step, the precatalyst is in contact with the internal electron donor in the absence of the titanium extractant, and during the second titanium step, the precatalyst is in contact with the titanium extractant in the absence of the internal electron donor.
A process according to claim 1, wherein during the first titaniumation step, the precatalyst is in contact with the internal electron donor and the titanium extractant, and during the second titaniumation step, the precatalyst is in contact with the internal electron donor, the titanium extractant, or both the internal electron donor and the titanium extractant.
In claim 1, the process comprises a pre-catalyst comprising a spray-crystallized magnesium halide compound.
In claim 9, the process comprises the spray-crystallized magnesium halide compound containing ethanol and magnesium chloride in a weight ratio of 1.5:1 to 3.1:1.
In claim 1, the internal electron donor comprises the following: a process (In the above formula, R1 and R4 are each hydrogen or a hydrocarbyl group having 1 to 20 carbon atoms, at least one of R2 and R3 is hydrogen, and at least one of R2 and R3 comprises a substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, E1 and E2 are the same or different and are selected from the group consisting of an alkyl having 1 to 20 carbon atoms, a substituted alkyl having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms, a substituted aryl having 6 to 20 carbon atoms, or an inert functional group having 1 to 20 carbon atoms and optionally containing a heteroatom, and X1 and X2 are each O, S, an alkyl group or NR5 , where R5 is a hydrocarbyl group having 1 to 20 carbon atoms or hydrogen).
A process according to claim 11, wherein at least one of R2 and R3 comprises a hydrocarbyl group having a branched or linear structure or a cycloalkyl group having 5 to 15 carbon atoms.
In claim 1, the precatalyst is a magnesium moiety having the following chemical formula: Mg(OR) n X 2-n L m (in the above formula, R comprises an alkyl or aryl group containing a halogen atom; n is 0 to 2; X is bromine, chlorine, or iodine; L comprises a coordination ligand group of an ether and/or alcohol; m is the number of coordination ligands, and is 0 to 10); and A process comprising a titanium moiety represented by the following chemical formula: Ti(OR) g X 4-g (In the above formula, each R is independently a C1 - C4 alkyl group; X is bromine, chlorine, or iodine; and g is 0, 1, 2, or 3).
A catalyst composition comprising a total catalyst composition as defined in any one of claims 1 to 13, combined with a co-catalyst and optionally a selectivity control agent.
In claim 14, the above co-catalyst is a catalyst composition comprising triethylaluminum.
A catalyst composition according to claim 14, wherein the above-mentioned selective control agent is present and comprises an alkoxysilane.
In claim 14, the selective control agent is dicyclopentyldimethoxysilane, di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldiethoxysilane, isobutylisopropyldimethoxysilane, di-n-butyldimethoxysilane, cyclopentyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, A catalyst composition comprising diethylaminotriethoxysilane, cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, dimethyldimethoxysilane, or a mixture thereof.
In claim 14, the catalyst composition further comprises an activity limiting agent.
In paragraph 18, the above-mentioned active limiter is a catalyst composition comprising a carboxylic acid ester.
In claim 14, the above-mentioned precatalyst is a magnesium moiety having the following chemical formula: Mg(OR) n X 2-n L m (in the above formula, R comprises an alkyl or aryl group containing a halogen atom; n is 0 to 2; X is bromine, chlorine, or iodine; L comprises a coordination ligand group of an ether and/or alcohol; m is the number of coordination ligands, and is 0 to 10); and Catalytic composition comprising a titanium moiety having the following chemical formula: Ti(OR) g X 4-g (In the above formula, each R is independently a C1-C4 alkyl group; X is bromine, chlorine, or iodine; and g is 0, 1, 2, or 3).

Description

Catalyst composition for polyolefin polymers Related applications This application is based on and claims priority to U.S. provisional patent application No. 62/902,118, filed on September 18, 2019, which is incorporated herein by reference. Polyolefin polymers are used in a wide variety of applications and fields. Polyolefin polymers are, for example, thermoplastic polymers that can be easily processed. Polyolefin polymers can also be recycled and reused. Polyolefin polymers are formed from hydrocarbons, such as ethylene and alpha-olefins, which are obtained from petrochemicals and are abundantly available. Polypropylene polymers, a type of polyolefin polymer, generally have a linear structure based on propylene monomers. Polypropylene polymers can have various stereospecific configurations. For example, polypropylene polymers can be isotactic, syndiotactic, and atactic. Isotactic polypropylene is perhaps the most common form and can be highly crystalline. Polypropylene polymers that can be produced include homopolymers, modified polypropylene polymers, and polypropylene copolymers—including polypropylene terpolymers. By modifying polypropylene or copolymerizing propylene with other monomers, various polymers with desired properties for specific applications can be produced. For example, polypropylene copolymers with elastomeric properties can be produced, which significantly improve the impact strength of the polymer. The global demand for olefin-based polymers continues to increase as applications for these polymers become more diverse and sophisticated. Ziegler-Natta catalyst compositions are known for the production of olefin-based polymers. Ziegler-Natta catalyst compositions typically include a procatalyst containing transition metal halides (i.e., titanium, chromium, vanadium) and a cocatalyst, such as an organoaluminum compound. Ziegler-Natta catalyst compositions are prepared using organic electron donors. These electron donors are typically referred to as internal electron donors to indicate that they are bound to the pre-catalyst and to distinguish them from other electron donors used during the polymerization process—which are typically referred to as external electron donors. Internal electron donors can largely determine the performance characteristics of the overall catalyst composition, such as catalytic activity. Internal electron donors can also influence the properties of the polymer produced from the catalyst composition. For example, internal electron donors can affect the polymer melt flow rate, xylene soluble content, etc. In addition to internal electron donors introduced into the precatalyst, the manner in which the precatalyst is generated can also influence various performance characteristics. For example, varying the stoichiometry of the raw materials used to generate the precatalyst, as well as the conditions and number of steps used during synthesis, can affect various properties of the catalyst composition and the characteristics of the resulting polymer. Recently, significant efforts have been made to improve the performance of catalyst compositions through the use of internal electron donors with relatively complex structures. Although great progress has been made in this technical field, various improvements are still needed. For example, there is a need for catalyst compositions capable of producing polyolefin polymers with a wide range of xylene-soluble content, such as polymers with relatively high xylene-soluble content and polymers with relatively low xylene-soluble content. In addition to the above, there is also a need for a process to produce a catalyst composition that can not only improve the properties of the catalyst composition but also minimize the amount of internal electron donors required to produce the catalyst composition. Generally, the present invention relates to a catalyst system for producing polyolefin polymers. The present invention also relates to an improved catalyst composition and a process for producing said catalyst composition. The catalyst composition of the present invention can have many benefits and can be designed and formulated for specific applications. For example, a Ziegler-Natta catalyst composition prepared according to the present invention can have increased stereoselectivity and/or can produce polyolefin polymers over a very wide range of xylene-soluble content. Accordingly, the catalyst composition of the present invention is highly suitable for use in many different types of polymerization processes for producing a wide range of polyolefin products. The catalyst composition can produce polymers, such as propylene polymers, that have a reduced amorphous or atactic phase and a reduced xylene-soluble content. As a particular advantage, a catalyst composition can be prepared according to the present invention that has the above benefits and also requires a smaller amount of internal electron donor to produce the catalyst composi