RU2236417C2 - Catalyst modifier and its employment in olefin polymerization - Google Patents

Abstract

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to methods of increasing olefin polymerization process effectiveness and, more particularly, to a method of controlling olefin polymerization catalysis kinetics. Invention provides catalytic composition including polymerization catalyst and a solid compound, which at temperature exceeding polymerization temperature undergoes phase transfer and deactivates catalyst, and catalytic composition including metallocene-type catalyst compound with a bulky ligand, activator, support, and solid acid compound. Methods for preparation of such compositions and olefin polymerization methods utilizing such compositions are also described.

EFFECT: increased stable productivity of catalytic composition with low tendency to pollution (formation of depositions) and increased duration of continuous polymerization process.

33 cl, 4 tbl, 24 ex

Description

FIELD OF THE INVENTION

The present invention relates to a method for increasing the efficiency of the polymerization process of olefin (s). Specifically, the invention relates to a method for controlling the kinetics of catalysis in the polymerization of olefins.

BACKGROUND OF THE INVENTION

Advances in polymerization and catalysis techniques have made it possible to produce many new polymers having improved physical and chemical properties that can be used in a wide variety of excellent products and applications. The development of new catalysts allowed to significantly expand the choice of types of polymerization (in solution, suspension, under high pressure or in the gas phase) upon receipt of a specific polymer. Advances in polymerization technology have also allowed the development of more efficient, high-performance and economically improved methods.

An illustration of these achievements, in particular, is the development of technology using catalytic metallocene-type systems with a bulky ligand. Despite these technological advances in the polyolefin industry, common problems still exist, as well as new challenges associated with the effectiveness of the technology. For example, during the processes in the gas phase or in the suspension phase, the problem of using any olefin polymerization catalyst remains, due to the tendency to contamination and / or formation of deposits.

So, for example, in a continuous suspension process, contamination of the surface of the walls of the reactor, which provide heat transfer, can lead to many health problems. Poor heat transfer during polymerization can result in polymer particles sticking to the walls of the reactor. Such polymer particles may continue to polymerize on the walls, which may lead to premature shutdown of the reactor. In addition, depending on the conditions in the reactor, some of the polymer may be dissolved in the reactor diluent and reprecipitated, for example, on the surfaces of metal heat exchangers.

In typical continuous gas-phase processes, for many reasons, including the removal of heat generated during the polymerization, a recirculation system is used. Pollution, scale formation and / or generation of static electricity during a continuous gas phase process can lead to inefficient operation of various reactor systems. In the case of influence, for example, on the cooling mechanism of the recirculation system, temperature sensors used for technological control, and on the distribution plate, this can lead to premature shutdown of the reactor.

Taking into account the evidence of this, the efforts of many specialists in this field of technology have been aimed at solving many problems of technological efficiency. Thus, for example, all US patents Nos. 4792592, 4803251, 4855370 and 5391657 discuss technical means of reducing the generation of static electricity during the polymerization process by introducing into the process, in particular, water, alcohols, ketones and / or inorganic chemical additives. In order to reduce pollution, EP B1-0634421 discusses the introduction of water, alcohol and ketones directly into the polymerization process. PCT publication WO 97/14721 of April 24, 1997 discusses the suppression of fines, which can cause deposits to form by adding an inert hydrocarbon to the reactor. US Pat. No. 5,627,243 discusses a new type of distribution plate for use in gas phase fluidized bed reactors. PCT publication WO 96/08520 discusses the possibility of eliminating the addition of a cleaning agent to the reactor. US 5,461,123 discusses the use of sound waves to reduce scale formation. US 5066736 and EP A1-0549252 discuss the introduction of a moderator into the reactor to reduce the formation of agglomerates. US No. 5610244 is devoted to the supply of fresh raw material monomer to the reactor directly above the bed in order to avoid contamination and improve polymer quality. US 5,126,414 discusses the implementation of an oligomer removal system in order to reduce the contamination of the distribution plate and to provide gels free of polymers. EP A1-0453116, published October 23, 1991, discusses the introduction of antistatic agents into the reactor to reduce the amount of deposits and agglomerates formed. US 4,012,574 discusses the addition of a perfluorocarbon series to the reactor to reduce contamination. No. 5026795 discusses the addition of an antistatic agent to a polymerization zone of a reactor together with a liquid carrier. US 5,441,0002 discusses the use of a conventional supported Ziegler-Natta titanium / magnesium catalyst system where, in order to reduce contamination, selected antistatic agents are added directly to the reactor. US 5034480 and 5034481 discuss the reaction product using a conventional Ziegler-Natta titanium catalyst with an antistatic agent to produce ultrahigh molecular weight ethylene polymers. US No. 3082198 discusses the introduction of a carboxylic acid, the amount of which depends on the amount of water, into the polymerization of ethylene using titanium / aluminum organometallic catalysts in a hydrocarbon liquid medium, and US No. 3919185 describes a suspension method using a non-polar hydrocarbon diluent and using a conventional catalyst a Ziegler-Natta type catalyst or a Phillips type catalyst and a polyvalent metal salt of an organic acid.

There are many other known ways to increase the efficiency of the process, including coating the polymerization equipment, for example processing the walls of the reactor using chromium compounds, as described in US No. 4532311 and 4876320; the introduction of various additives into the process, such as, for example, in PCT publication WO 97/46599 dated December 11, 1997, which discusses the introduction of a carrier-free metallocene type catalytic system into the lean zone of a polymerization reactor and the introduction of anti-pollution or antistatic additives into the reactor; regulation of the rate of polymerization, in particular at the initial stage; and structural rearrangement of the reactor.

In the description of other attempts made in the art to improve the efficiency of the process, the modification of the catalyst system using various ways of preparing the catalyst system is discussed. So, for example, methods developed in the art include introducing components of the catalyst system into the composition in a specific order; manipulation with the ratio of various components of the catalytic system; varying the duration and / or temperature of the contact with the introduction of the components of the catalyst system into the composition and simply adding various compounds to the catalyst system. These technical solutions and their combinations are discussed in the literature. Specific illustrations thereof in the art are methods for preparing catalytic metallocene type systems with a bulky ligand, more particularly supported on carriers of metallocene type catalytic systems with a bulky ligand with a reduced tendency to contamination and improved efficiency. Examples thereof include WO 96/11961, published April 26, 1996, in which an antistatic agent is discussed as a component of a supported catalyst system to reduce fouling and scale formation during the polymerization process in a gas, suspension or liquid medium; US patent No. 5283218, dedicated to prepolymerization using a metallocene catalyst; US patent No. 5332706 and 5473028, in accordance with which resort to a special technology for the preparation of the catalyst by impregnation at the initial stage; US patents No. 5427991 and 5643847, which describes the chemical binding of non-coordinating anionic activators with carriers; US patent No. 5492975, which discusses polymer-bonded metallocene-type catalyst systems; US patent No. 5661095, which discusses the deposition of a metallocene type catalyst on a copolymer of olefin and unsaturated silane; PCT application WO 97/06186, published February 20, 1997, which deals with the removal of inorganic and organic impurities after the preparation of the metallocene type catalyst itself; PCT application WO 97/15602, published May 1, 1997, which discusses metal complexes that are easily applied to carriers; PCT application WO 97/27224, published July 31, 1997, relating to the preparation of a transition metal compound supported on a carrier in the presence of an unsaturated organic compound with at least one double bond at the end of the molecule; and EP A2-811638, which discusses the use of a metallocene catalyst and activating cocatalyst in the polymerization process in the presence of a nitrogen-containing antistatic agent.

In US No. 4942147 and 5362823 discusses the addition of inhibitors of self-acceleration in order to prevent the formation of deposits.

PCT publication WO 98/20045 dated May 14, 1998 discusses a method for suppressing the formation of polymer deposits in the presence of a non-supported liquid polymerization catalyst system, which comprises introducing an anti-contaminant additive, preferably 1,2-dimethyloxybenzene or propylene glycol, into the system.

EP A1-0630910 proposes the use of Lewis bases to control the rate of polymerization of olefins, which reduce the rate or stop the reaction, which is reversible when an additional amount of cocatalyst is introduced into the system.

Although the application of all these possible solutions to the problem could to some extent reduce the degree of pollution or the formation of deposits, some of them are expensive to implement and / or may not lead to a decrease in pollution and the formation of deposits to such a level that is sufficient for a successful continuous process, Features of an industrial or large-scale process.

Thus, there is a need to develop a polymerization process that could be carried out during a continuous process with improved reactor performance and at the same time producing new and improved polymers. There is also a great need to develop a process for carrying out a continuous polymerization process with a more stable catalyst productivity, reduced tendency to fouling / formation of deposits, and an extended process time.

Summary of the invention

The present invention provides a method for preparing a new and improved catalytic composition, a catalytic composition and its use in the polymerization process. The invention also relates to the use of a practically solid, preferably solid, compound which undergoes a phase transition during the polymerization in the presence of a polymerization catalyst at a predetermined temperature, as a result of which this solid compound turns into a liquid or gas, preferably into a liquid, and this liquid or gas makes the polymerization catalyst practically inactive, preferably inactive, in the polymerization of olefin (s). A preferred compound is a polar compound having low volatility, preferably an acidic compound, and in particular Bronsted acid.

The method includes the step of combining, contacting, combining and / or mixing any catalyst system, preferably a supported catalyst system, with a compound, preferably an acidic compound, so that, at a given temperature, this compound, preferably an acidic compound, changes its physical state and passed from a solid state to a liquid state and in this liquid state deactivated the catalytic system. In the most preferred embodiment, this acidic compound becomes liquid at a temperature higher than the polymerization temperature or the temperature of the reactor. In one embodiment, the catalyst system comprises a conventional type transition metal catalyst compound. In a most preferred embodiment, the catalyst system comprises a metallocene-type catalyst compound with a bulky ligand. Such a combination or use of an olefin polymerization catalyst and this compound, preferably an acidic compound, is effective in any olefin polymerization process. Preferred polymerization processes are processes in the gas phase and the suspension phase, the most preferred gas phase process.

In another preferred embodiment, the invention provides a method for the polymerization of olefin (s) in the presence of a polymerization catalyst and a compound, preferably an acidic compound, in a reactor at a working temperature, where this compound, preferably an acidic compound, is converted from a solid compound to a temperature above the working temperature. liquid compound, reducing the effectiveness of the polymerization catalyst in the polymerization of olefin (olefins). Most preferably, this liquid compound deactivates the polymerization catalyst.

In a further preferred embodiment, the invention provides a process for the polymerization of olefin (s) in the presence of a polymerization catalyst in a reactor under polymerization conditions, comprising the step of introducing a solid compound, preferably a solid acid compound, where this solid compound, preferably a solid acid compound, becomes substantially liquid, preferably a liquid acidic compound that reduces the effectiveness of the polymerization catalyst with respect to polymerization o lefin (olefins).

DETAILED DESCRIPTION OF THE INVENTION

Introduction

An object of the invention is a method for preparing a catalyst composition and the catalyst composition itself. The invention also provides a polymerization process characterized by enhanced potency using a catalyst composition. Not based on any theory, it is believed that one possible reason for the reduced potency, especially the formation of deposits and / or contamination, is a consequence of the tendency of the catalyst to actively continue polymerization after its initial activation. It has been found that the use of a solid compound, preferably an acid compound, which undergoes a phase transition to an almost liquid state, preferably a liquid state, in combination with a polymerization catalyst makes it possible to control the tendency of the catalyst to efficiently continue the polymerization of olefin (olefins). It was also found that this phase transformation can be controlled by the choice of the compound used. In the most preferred embodiment, the temperature at which the phase transition occurs is controlled by replacing the acidic compound. The present invention is applicable to all types of polymerization processes, especially processes in the suspension and gas phases.

Catalytic components and catalyst systems

All polymerization catalysts are acceptable for use in the polymerization method of the invention, including conventional transition metal catalysts and bulky ligand metallocene type catalysts. The following is a non-limiting discussion of the various polymerization catalysts that can be used in carrying out the invention.

Conventional transition metal catalysts

Conventional transition metal catalysts are those conventional Ziegler-Natta catalysts and Phillips-type catalysts that are well known in the art. Examples of conventional transition metal catalysts are discussed in US Pat. Catalytic compounds of the usual type with transition metals that can be used according to the present invention include compounds of transition metals of groups 3 to 17, preferably 4 to 12, more preferably 4 to 6, of the Periodic Table of the Elements.

These conventional transition metal catalysts can be represented by the formula MR _x , wherein M is a metal atom from groups 3 to 17, preferably from groups 4 to 6, more preferably group 4, and most preferably titanium; R represents a halogen atom or a hydrocarbyloxy group; and x denotes the valency of metal M. Non-limiting examples of R values include alkoxy, phenoxy, bromide, chloride, and fluoride. Non-limiting examples of conventional transition metal catalysts in which M represents a titanium atom include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OS ₂ H ₅ ) Cl ₃ , Ti (OS ₄ H ₉ ) ₃ Cl, Ti (OS ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , TiCl ₃ · 1 / 3AlCl ₃ and Ti (OS ₁₂ H ₂₅ ) Cl ₃ .

Catalytic compounds of transition metals of the usual type based on magnesium / titanium electron-donor complexes that can be used according to the invention are presented, for example, in US patents Nos. 4302565 and 4302566, which are fully incorporated into this description by reference. Particularly preferred is a derivative of MgTiCl ₆ (ethyl acetate) ₄ .

In the application UK 2105355 and US patent No. 5317036, incorporated into this description by reference, various catalytic vanadium compounds of the usual type are presented. Non-limiting examples of typical vanadium catalytic compounds include vanadyl trihalide, α-alkoxy halides and α-alkoxides such as VOCl ₃ , VQCl ₂ (OBu), where Bu is butyl and VO (OC ₂ H ₅ ) ₃ ; vanadium tetrahalide and vanadium alkoxy halides such as VCl ₄ and VCl ₃ (OBu); vanadium and vanadyl acetylacetonates and chloroacetylacetonates, such as V (AcAc) ₃ and VOCl ₂ (AcAc), where (AcAc) is acetylacetonate. Preferred conventional vanadium catalytic compounds are VOCl ₃ , VCl ₄ and VOCl ₂ -OR, where R is a hydrocarbon radical, preferably an aliphatic or aromatic hydrocarbon C ₁ -C ₁₀ radical, such as ethyl, phenyl, isopropyl, butyl, propyl, n- butyl, isobutyl, tertiary butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

Conventional type chromium catalyst compounds, often referred to as Phillips catalyst type compounds, suitable for use in the practice of the present invention include CrO ₃ , chromocene, silyl chromate, chromyl chloride (CrO ₂ Cl ₂ ), chrom-2-ethylhexanoate, chromoacetylacetonate [Cr ( AsAc) ₃ ], etc. Non-limiting examples are presented in US patents No. 3709853, 3709954, 3231550, 3242099 and 4077904, which are fully incorporated into this description by reference.

Another common type of transition metal catalyst compounds and catalyst systems suitable for use in the present invention are disclosed in US Pat. -0416815 and EP A1-0420436, all of which are incorporated herein by reference.

Other catalysts may include cationic catalysts, such as AlCl ₃ , and others, cobalt, iron, nickel and palladium catalysts, well known in the art (see, for example, US patents No. 3487112, 4472559, 4182814 and 4689437, which are all included in the present description by reference).

These conventional transition metal catalyst compounds, with the exception of certain conventional chromium-containing catalyst compounds, are typically activated by one or more of the conventional type cocatalysts described below.

Conventional type cocatalysts

Conventional type cocatalyst compounds for the aforementioned conventional type transition metal catalyst compounds can be represented by the formula M ³ M $\genfrac{}{}{0ex}{}{\text{4}}{\text{v}}$ X $\genfrac{}{}{0ex}{}{\text{2}}{\text{c}}$ R $\genfrac{}{}{0ex}{}{\text{3}}{\text{bc}}$ in which M ³ denotes a metal atom from groups 1 to 3 and 12 and 13 of the Periodic table of the elements; M ⁴ denotes a metal atom of group 1 of the Periodic table of the elements; v denotes a number from 0 to 1; each X ² represents an atom of any halogen; c is a number from 0 to 3; each R ³ is a monovalent hydrocarbon radical or a hydrogen atom; b denotes a number from 1 to 4, and in which the difference b minus c is at least 1. Other conventional organometallic cocatalytic compounds for the aforementioned conventional transition metal catalysts correspond to the formula M ³ R ³ k, where M ³ denotes a metal atom of a group IA, IIA, IIB or IIIA, such as lithium, sodium, beryllium, barium, boron, aluminum, zinc, cadmium and gallium; k in accordance with the valency of M ³ , which in turn usually depends on the particular group to which M ³ belongs, denotes 1, 2 or 3; and each of R ³ may denote any of the monovalent radicals, which include hydrocarbon radicals, as well as hydrocarbon radicals containing elements of groups 13 to 16, similar to fluorine, aluminum and oxygen, and combinations thereof.

Non-limiting examples of conventional type organometallic co-catalytic compounds that can be used in conjunction with the conventional type of catalyst compounds described above include methyl lithium, butyllithium, dihexyl mercury, butyl magnesium, diethyl cadmium, benzyl potassium, diethyl zinc, tri-n-butyl aluminum, diisobutyl ethyl di diethyl butylzinc and tri-n-amylboron, in particular aluminum alkyls such as trihexylaluminum, triethylaluminum, trimethylaluminum and triisobutylaluminum. Other conventional type co-catalytic compounds include group 2 metal organohalogen halides and hydrides and group 3 and 13 metal mono- and diorgano halides and metal hydrides. Non-limiting examples of such conventional type co-catalytic compounds include diisobutylaluminium bromide, isobutyl boride dichloride, hydromyldihydride dihydride, ethyl beryl chloride dihydride, , dipropyl borohydride, octyl magnesium hydride, butyl zinc hydride, dichloroborohydride, dibromoaluminum hydride and bromkadmiygidrid. Organometallic cocatalytic compounds of the usual type are known to those skilled in the art, a more complete discussion of these compounds can be found in US patents 3232002 and 5093415, which are fully incorporated into this description by reference.

Catalytic compounds of the metallodene type with a bulky ligand

Typically, bulky ligand metallocene type catalyst compounds include semi- and full-sandwich compounds containing one or more bulky ligands linked to at least one metal atom. Typical bulky ligand metallocene-type compounds are typically described as containing one or more bulky ligands and one or more leaving groups bonded to at least one metal atom. In one preferred embodiment, at least one of the bulky ligands is η-linked to a metal atom, most preferably η ^5- linked to a metal atom.

Bulk ligands are usually presented in the form of one or more open, acyclic or fused rings or ring systems, or combinations thereof. These bulky ligands, preferably rings or ring systems, typically consist of atoms selected from groups 13 to 16 of the Periodic Table of the Elements, the preferred atoms being selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorus, germanium, boron and aluminum and their combination. The most preferred rings and ring systems are composed of carbon atoms and are, in particular, although not limited to, cyclopentadienyl ligands, cyclopentadienyl type ligand structures or other ligand structures with a similar function, such as pentadiene, cyclooctatetraendienyl and imide ligands. The preferred metal atom is selected from groups 3 to 15 and from the rows of lanthanides and actinides of the Periodic Table of the Elements. A preferred metal atom is a transition metal atom of groups 4 to 12, more preferably groups 4, 5 and 6, and most preferably group 4.

In one embodiment, catalytic compounds of the metallocene type with a bulky ligand correspond to the formula

where M denotes a metal atom, which may refer to metals of groups 3 to 12 of the Periodic table of elements or to a number of lanthanides or actinides of the Periodic table of elements, with the preferred value of M being a transition metal atom of groups 4, 5 or 6, the more preferred value of M is an atom a transition metal of group 4, and an even more preferred value of M is a zirconium, hafnium or titanium atom. Bulk ligands L ^A and L ^B are open, acyclic or fused rings or ring systems, such as unsubstituted and substituted cyclopentadienyl ligands or cyclopentadienyl type ligands, heteroatom substituted and / or heteroatom containing cyclopentadienyl type ligands. Non-limiting examples of bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthrenyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendienyl ligands, azolenyl ligands, pyrene ligands, pyrene ligands, pyrene ligands etc., including hydrogenated variants thereof, for example tetrahydroindenyl ligands. In one embodiment, L ^A and L ^B may denote ligands of any other structures capable of forming η bonds with M, preferably η ³ bonds with M, and most preferably η ⁵ bonds. However, in another embodiment, the atomic molecular weight (Mw) L ^A or L ^B exceeds 60 at. mass, preferably greater than 65 at.ed, mass. In yet another embodiment, L ^A and L ^B may include one or more heteroatoms, in particular nitrogen, silicon, boron, germanium, sulfur, oxygen and phosphorus in combination with carbon atoms to form an open, acyclic or, preferably, fused ring or a ring system, for example a heterocyclopentadienyl auxiliary ligand. Other bulky ligands L ^A and L ^B include, although not limited to, bulky residues of amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles. Each of L ^A and L ^B can independently denote a bulky ligand of the same or another type that is associated with M. In one embodiment, in formula (I) contains only one of L ^A and L ^B.

Each of L ^A and L ^B may be independently unsubstituted or substituted with a combination of R substituent groups. Non-limiting examples of R substituent groups include groups selected from a hydrogen atom and linear and branched alkyl radicals and alkenyl radicals, alkynyl radicals, cycloalkyl radicals and aryl radicals, acyl radicals radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbamoyl radicals radicals, alkyl and dialkyl carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight chain, branched and cyclic alkylene radicals, and combinations thereof. In a preferred embodiment, the substituent group R contains up to 50 non-hydrogen atoms, preferably 1-30 carbon atoms, which may also be substituted by halogen atoms, heteroatoms or the like. Non-limiting examples of R alkyl substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like. Other hydrocarbyl radicals include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromhexyl, chlorobenzyl and hydrocarbyl substituted organometallic radicals, including trimethylsilyl, trimethylgermyl, methyldiethylsilyl, and the like; halocarbyl substituted organometallic radicals, including tris (trifluoromethyl) silyl, methylbis (difluoromethyl) silyl, bromomethyldimethylgermyl and the like; disubstituted boric radicals, including, for example, dimethylboron; disubstituted pnictogen radicals, including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; chalcogen radicals, including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide and ethyl sulfide. Non-hydrogen substituents of R include carbon, silicon, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, germanium and the like atoms, including olefins, such as, although not limited to, olefinically unsaturated substituents, including terminal vinyl ligands, for example, but-3-enyl, prop-2-enyl, hex-5-enyl and the like. In addition, at least two R groups, preferably two adjacent R groups, are associated with the formation of a ring structure containing 3-30 atoms selected from carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminum, boron and their ochetaniya. A substituted R group, such as 1-butanyl, with the metal atom M can also form a sigma bond.

Other ligands may be bonded to the metal atom M, such as at least one leaving group Q. In view of the objectives of the present description and the appended claims, the term “leaving group” refers to any ligand that can be cleaved from a bulky metallocene type compound ligand, resulting in the formation of a metallocene-type catalytic cation with a bulky ligand capable of polymerizing one or more olefins. In one embodiment, Q may denote a monoanionic mobile ligand forming a sigma bond with M.

Non-limiting examples of Q ligands include residues of weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals, each of which contains from 1 to 20 carbon atoms, hydrides, halogen atoms, and the like. and their combinations. In another embodiment, two or more Q ligands form part of a fused ring or ring system. Other examples of Q ligands include those substituents on R as defined above, including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methoxy, ethoxy, propoxy, phenoxy, bis (N-methylanilide), dimethylamide, dimethylphosphide radicals etc. Depending on the oxidation state of the metal atom, the value of n is 0, 1 or 2, as a result of which the above formula (I) corresponds to a neutral catalytic compound of the metallocene type with a bulky ligand.

In one embodiment, the catalytic compounds of the metallocene type with a bulky ligand according to the invention include those compounds of formula (I) in which L ^A and L ^B are linked together by a bridging group A, as a result of which this formula takes the following form:

These bridged compounds of formula (II) are known as bridged metallocene-type catalytic compounds with a bulky ligand. L ^A , L ^B , M, Q and n are as defined above. Non-limiting examples of bridging group A include bridging groups containing at least one atom of groups 13 to 16, often called a divalent residue, in particular, although their list is not limited to at least one of the carbon, oxygen, nitrogen atoms, silicon, boron, germanium and tin, and their combination. A preferred bridging group A comprises a carbon, silicon or germanium atom, a most preferred group A comprises at least one silicon atom or at least one carbon atom. Bridge group A may also contain substituent groups R, the meanings of which are indicated above, including halogen atoms. Non-limiting examples of bridge group A can be represented using the formulas R ′ ₂ C, R ′ ₂ Si, R ′ ₂ SiR ′ ₂ Si, R ′ ₂ Ge, R′P, where R ′ independently represents a radical that is a hydride residue , hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl substituted organometallic residue, halocarbyl substituted organometallic residue, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen atom, or two R 'groups may be connected to the ring system or

In one embodiment, the bulky ligand metallocene type catalyst compounds are those compounds in which the R substituents of the bulky ligands L ^A and L ^B in formulas (I) and (II) are substituted with the same or different number of substituents in each of the bulky ligands. In another embodiment, the bulky ligands L ^A and L ^B in formulas (I) and (II) are different.

Other catalytic compounds and catalytic systems of the metallocene type with a bulky ligand that can be used according to the invention include those that are presented in US patent No. 5064802, 5145819, 5149819, 5243001, 5239022, 5276208, 5296434, 5321106, 5329031, 546. 5677401, 5723398, 5753578, 5854363 and 5856547, 5858903, 5859158 and 5929266, in PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 and in European publications EP A-0578838, EP A-0638595, EP B-0513380, EP A1-0816372, EP A2-0839834, EP B1-0632819, EP B1- 0748821 and EP B1-0757996, which are all fully included in the present described as references.

In one embodiment, bulky ligand metallocene-type catalytic compounds that can be used according to the invention include metallocene-type compounds containing one bulky ligand with a bridged heteroatom. Catalysts and catalyst systems of these types are presented, for example, in PCT publications WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506, WO 96/00244 and WO 97/15602, in US patent No. 5057475, 5096867 , 5055438, 5198401, 5227440 and 5264405 and in the European publication EP A-0420436, which are all fully incorporated into this description by reference.

In this embodiment, the catalytic compounds of the metallocene type with a bulky ligand correspond to the formula

where M denotes a metal atom of groups 3 to 16 or a metal atom from a series of actinides or lanthanides of the Periodic table of elements, the preferred value of M is the transition metal atom of groups 4 to 12, the more preferred value of M is the transition metal atom of groups 4, 5 or 6 and the most preferred value of M is a group 4 transition metal atom in any oxidation state, in particular a titanium atom; L ^C is a substituted or unsubstituted bulky ligand bound to M; J is linked to M; A is associated with L ^C and J; J is a heteroatomic auxiliary ligand; A represents a bridging group; Q is a monovalent anionic ligand; and n denotes an integer of 0, 1 or 2. In the above formula (III), L ^C , A and J form a fused ring system. In one embodiment, in formula (III), L ^C has the same meanings as above for L ^A , A, M, and Q in formula (III) have the meanings indicated above for formula (I). In formula (III), J is a heteroatom-containing ligand in which J is an element of group 15 with a coordination number of three or an element of group 16 of the Periodic table of elements with a coordination number of two. In a preferred embodiment, J contains a nitrogen, phosphorus, oxygen or sulfur atom, with a nitrogen atom being most preferred.

In yet another embodiment, the bulky ligand metallocene type catalyst compound is a complex of a metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-linked ligand, and one or more heteroallyl residues, such as those described in US Pat. Nos. 5,527,752 and 5747406 and in EP B1-0735057, all of which are fully incorporated herein by reference.

In one embodiment, the catalytic compound of the metallocene type with a bulky ligand corresponds to the formula

where M denotes a metal atom of groups 3 to 16, preferably a transition metal atom of groups 4 to 12, and most preferably a transition metal atom of groups 4, 5 or 6; L ^D is a bulky ligand that is bound to M; each Q is independently linked to M, and Q ₂ (YZ) forms a singly charged polydentate ligand; A or Q is a monovalent anionic ligand also linked to M; X is a monovalent anionic group when n is 2, or X is a divalent anionic group when n is 1; n is 1 or 2.

In the formula (IV), L and M have the meanings indicated above for the formula (I). Q has the meanings given above for formula (I), preferred values of Q are selected from the series consisting of —O—, —NR—, —CR ₂ - and —S—; Y is either C or S; Z values are selected from the series including —OR, —NR ₂ , —CR ₃ , —SR, —SiR ₃ , —PR ₂ , —H, substituted and unsubstituted aryl groups, with the proviso that when Q is —NR—, Z is selected from the group consisting of —OR, —NR ₂ , —SR, —SiR ₃ , —PR _2, and —H; R values are selected from the groups consisting of carbon, silicon, nitrogen, oxygen and / or phosphorus, with a preferred R value being a hydrocarbon group containing 1-20 carbon atoms, most preferably an alkyl, cycloalkyl or aryl group; n is an integer of 1-4, preferably 1 or 2; X is a monovalent anionic group when n is 2, or X is a divalent anionic group when n is 1; the preferred value of X is carbamate, carboxylate or other heteroallyl residue displayed by the combination of Q, Y or Z.

In another embodiment, bulky ligand metallocene type catalyst compounds are heterocyclic ligand complexes whose bulky ligands, rings or ring systems, include one or more heteroatoms or a combination thereof. Non-limiting examples of heteroatoms include elements of groups 13 to 16, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorus and tin atoms. Examples of such voluminous ligand metallocene type catalyst compounds are presented in WO 96/33202, WO 96/34021, WO 97/17379, WO 98/22486 and EP A1-0874005 and US Pat. Nos. 5637660, 5539124, 5554775, 5756611, 5233049, 5744417 and 5856258, all of which are incorporated herein by reference.

In another embodiment, the bulky ligand metallocene type catalyst compounds are those complexes that are known as bidentate ligand transition metal catalysts containing pyridine or quinoline residues, such as those presented in US Application Serial No. 09/103620, filed 23 June 1998, which is incorporated herein by reference. In yet another embodiment, bulky ligand metallocene-type catalytic compounds are those disclosed in PCT Publications WO 99/01481 and WO 98/42664, which are incorporated herein by reference in their entirety.

In one embodiment, the catalytic compound of the metallocene type with a bulky ligand corresponds to the formula

where M denotes a metal atom selected from groups 3 to 13 or from a series of lanthanides or actinides of the Periodic table of elements; Q is associated with M and each Q is a monovalent, divalent or trivalent anion; X and Y are associated with M; one or more X and Y are heteroatoms, preferably both X and Y are heteroatoms; Y is contained in the heterocyclic ring J, where J includes from 2 to 50 non-hydrogen atoms, preferably from 2 to 30 carbon atoms; Z is bonded to X, where Z contains from 1 to 50 non-hydrogen atoms, preferably from 1 to 50 carbon atoms, and in a preferred embodiment, Z represents a cyclic group containing from 3 to 50 atoms, preferably from 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a bridging group associated with at least one of X, Y and J, preferably X and J; q is 1 or 2; n is an integer from 1 to 4 depending on the oxidation state of M. In one embodiment, in which X is an oxygen or sulfur atom, a Z moiety is optional. In another embodiment, in which X represents a nitrogen or phosphorus atom, a Z moiety is contained. In one embodiment, the preferred value of Z is an aryl group, more preferably a substituted aryl group.

Other bulky ligand metallocene type catalyst compounds

In one embodiment encompassed by the scope of the present invention, bulky ligand metallocene type catalyst compounds include Ni ²⁺ and Pd ²⁺ complexes presented in Johnson et al., "New Pd (II) - and Ni (II) Based Catalysts for Polymerization of Ethylene and α-Olifins, "J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson et al., "Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium (II) Catalysts", J. Am. Chem.Soc. 1996, 118, 267-268, and in applications WO 96/23010, published August 1, 1996, and WO 99/02472 and in US patent No. 5852145, 5866663 and 5880241, which are all fully incorporated into this description as links. These complexes can be either dialkyl ether addition products or alkylated reaction products of the described dihalide complexes, which can be activated to a cationic state by the activators of the present invention described below.

Bulk ligand metallocene type catalysts also include those compounds of metals of groups 8 to 10 with diimine-based ligands that are presented in PCT publications WO 96/23010 and WO 97/48735 and in Gibson et al., Chem. Comm., C. 849-850 (1998), all of which are incorporated herein by reference.

Other bulky ligand metallocene type catalysts are imidocomplexes with metals of groups 5 and 6, presented in EP A2-0816384 and in US patent No. 5851945, which are incorporated herein by reference. In addition, bulky ligand metallocene type catalysts include bridged bisarylamide compounds of Group 4 elements as presented by D.H. McConville et al. In Organometallics 1195, 14, 5478-5480, which is incorporated herein by reference. Other bulky ligand metallocene type catalysts are disclosed as bis (hydroxyaromatic nitrogen ligands) in US Pat. No. 5,852,146, which is incorporated herein by reference. Still other metallocene-type catalysts containing one or more atoms of group 15 elements include those presented in WO 98/46651, which is incorporated herein by reference.

In one embodiment of the invention, it is also possible to include, among the above-described catalysts, a metallocene type with a bulky ligand of their structural or optical or enantiomeric isomers (meso- and racemic isomers are presented, for example, in US Pat. No. 5,852,143, incorporated herein by reference) and mixtures thereof.

Activator and activation methods for catalytic compounds of the metallocene type with a bulky ligand

The above-described bulky ligand metallocene-type catalyst compounds are typically activated in various ways in order to obtain catalyst compounds having a free coordination site that provides coordination, incorporation and polymerization of olefin (olefins), activated polymerization catalysts.

Taking into account the objectives of the description of this application and the attached claims, the term "activator" is defined as referring to any compound, component or method, the use of which makes it possible to activate any of the above metallocene-type catalytic compounds with a bulky ligand according to the invention. Non-limiting examples of activators include Bronsted acids, non-coordination ionogenic activators, ionizing activators, and any other compounds, including Bronsted bases, aluminum alkyls, conventional type cocatalysts and combinations thereof, which are capable of converting a neutral catalytic metallocene type compound with a bulky ligand into a catalytically active metallocene compound cation with a bulky ligand. The scope of the present invention encompasses the use of aluminoxane or a modified aluminoxane as an activator and / or the use of ionizing activators, neutral or ionic, such as tris (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, trisperfluorophenylboron metal-containing precursor and trisperfluorinated-nano-octo-adeno-fluoro-nano-octylated compounds, trisperfluorinated-nano-naphthyl-octanoyl compounds anions (see WO 98/43983) and their combinations, which necessarily ionize a neutral catalytic compound metallocene type with a bulky ligand.

One of the options also provides an activation method using ionizing ionic compounds that do not contain an active proton, but are capable of forming both a metallocene-type catalytic cation with a bulky ligand and a non-coordination anion, as described in EP A-0426637 and EP A- 0573403 and in US patent No. 5387568, all of which are incorporated herein by reference.

There are many methods for producing alumoxane and modified alumoxanes, non-limiting examples of which are presented in US Pat. , 5693838, 5731253, 5731451, 5744656, 5847177, 5854166 and 5856256, in European publications EP A-0561476, EP B1-0279586, EP A-0594218 and EP B1-0586665 and in PCT publication WO 94/10180, which are all in full are included in the present description by reference.

Organoaluminum compounds that can be used as activators include triethylaluminum, triisobutylaluminum, trimethylaluminum, tri-n-hexylaluminum and the like.

Ionizing compounds may include an active proton or some other cation associated, but not coordinated, or only weakly coordinated with the remaining ion of the ionizing compound. Such compounds and the like. are presented in European publications EP A-0570982, EP A-0520732, EP A-0495375, EP B1-0500944, EP A-0277003 and EP A-0277004, in US patents No. 5153157, 5198401, 5066741, 5206197, 5241025, 5384299 and 5502124 and in patent application US serial number 08/285380, filed August 3, 1994, which are all fully incorporated into this description by reference.

Other activators include those compounds that are presented in PCT publication WO 98/07515, such as tris (2,2 ’, 2’ ’— nonafluorodiphenyl) fluoroaluminate, this publication being incorporated herein by reference in their entirety. The invention also provides for the use of combinations of activators, for example, combinations of aluminoxanes with ionizing activators (see, in particular, EP B1-0573120, PCT WO 94/07928 and WO 95/14044 and patents US 5153157 and 5453410, which are all fully included in the present description by reference). Other activators include aluminum / boron complexes presented in application EP B1-608830, which is incorporated herein by reference. WO 98/09996, incorporated herein by reference, provides activation of metallocene-type catalytic compounds with a bulky ligand perchlorates, periods and iodates, including their hydrates. WO 98/30602 and WO 98/30603, which are incorporated herein by reference, disclose the use of lithium (2,2′-bisphenyldithrimethylsilicate) 74THF as an activator for a bulky ligand metallocene type catalyst compound. EP B1-0781299 proposes the use of a silylium salt in combination with a non-coordination compatible anion. To convert a neutral catalytic compound of a metallocene type with a bulky ligand or a precursor to a compound with a metallocene type cation with a bulky ligand capable of polymerizing olefins, activation methods such as using radiation are also contemplated (see application EP B1-0615981 included in the present description by reference), electrochemical oxidation, and the like. Other activators and methods for activating a bulky ligand metallocene type catalyst compound are presented, for example, in US Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and PCT Publication WO 98/32775, which are incorporated herein by reference.

The scope of the present invention also covers the possibility of combining the above-described metallocene-type catalytic compounds with a bulky ligand with one or more catalytic compounds corresponding to formulas (I) to (V), with one or more activators or combinations with the above activation methods.

The invention further provides the possibility of combining other catalysts with catalytic compounds of the metallocene type with a bulky ligand according to the invention (see, for example, US patent No. 4937299, 4935474, 5281679, 5359015, 5470811 and 5719241, which are all fully included in the present description as links). Any of the metallocene-type catalytic compounds with a bulky ligand according to the invention also provides for the possibility of the presence of at least one fluoride or fluorine-containing leaving group, as described in application US serial number 09/191916, filed November 13, 1998

In another embodiment of the invention, one or more bulky ligand metallocene type catalyst systems or catalyst systems can be used in combination with one or more conventional type catalyst compounds or catalyst systems. Non-limiting examples of mixed catalysts and catalyst systems are presented in US Pat. fully incorporated into the present description by reference.

Substrates, carriers and general carrier technology

The above-described catalytic compounds and conventional transition metal catalyst systems and catalytic systems and catalytic metallocene-type catalyst systems with a bulky ligand can be combined with one or more support materials or carriers using one of the application methods well known in the art, or as described below. Thus, for example, in the most preferred embodiment, the bulky ligand metallocene type catalyst system or catalyst system is in a supported form, for example, supported on, supported on, supported on, supported by, embedded in, adsorbed to, on it or absorbed in it.

The terms “substrate” and “carrier” are used interchangeably and apply to any substrate material, preferably to a porous substrate material, more preferably to an inorganic substrate or organic substrate. Inorganic substrates are preferred, for example, inorganic oxides and inorganic chlorides. Other supports include resinous support materials, such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinylbenzene, polyolefin and other polymeric compounds, zeolites, clays, talc and any other organic or inorganic support material, etc., as well as their mixtures. The most preferred supports are inorganic oxides, which include oxides of metals of groups 2, 3, 4, 5, 13 and 14. Preferred supports include silica, alumina, silica / alumina, magnesium chloride, and mixtures thereof.

Other effective carriers include magnesium oxide, titanium dioxide, zirconia, montmorillonite (see EP B1-0511665) and the like. Combinations of these support materials can also be used, for example, silicon dioxide / chromium, silicon dioxide / aluminum oxide, silicon dioxide / titanium dioxide, and the like.

, предпочтительно от примерно 50 до примерно 500

, а наиболее предпочтительно от примерно 75 до примерно 350

.A preferred carrier, most preferably an inorganic oxide, has a specific surface area in the range of from about 10 to about 700 m ² / g and a pore volume in the range of from about 0.1 to about 4.0 cc / g and an average particle size in the range from about 5 to about 500 microns. In a more preferred embodiment, the specific surface area of the carrier is in the range from about 50 to about 500 m ² / g and the volume is from about 0.5 to about 3.5 cc / g and the average particle size is from about 10 to about 200 microns. In a most preferred embodiment, the specific surface area of the carrier is in the range from about 100 to about 400 m ² / g and the pore volume is from about 0.8 to about 3.0 cc / g, and the average particle size is from about 5 to approximately 100 microns. The average pore size of the carrier according to the invention, as a rule, is in the range from about 10 to about 1000

preferably from about 50 to about 500

and most preferably from about 75 to about 350

.

Examples of applying a bulky ligand metallocene type catalyst systems of the invention to a carrier are presented in US Pat. 5629253, 5639835, 5625015, 5643847, 5665665, 5698487, 5714424, 5723400, 5723402, 5731261, 5759940, 5767032, 5770664 and 5846895, in US patent applications serial numbers 271598, filed July 7, 1994, and 788736, 1997, and PCT publications WO 95/32995, WO 95/14044, WO 96/06187, WO 97/02297 and EP B1-0685494, all of which are incorporated herein by reference in their entirety. Examples of applying conventional transition metal catalyst compounds to a carrier are also well known in the art.

There are various other methods in the art for applying a polymerization catalyst compound or catalyst system of the invention to carriers. For example, a catalytic metallocene-type compound with a bulky ligand according to the invention may include a polymer-bound ligand, as set forth in US Pat. Nos. 5,473,202 and 5,770,755, which are incorporated herein by reference in their entirety; the bulky ligand metal-foam type catalyst system of the invention can be spray dried as set forth in US Pat. No. 5,648,310, which is incorporated herein by reference in its entirety; the carrier used together with the bulky ligand metallocene type catalyst system of the invention is functionalized as set forth in European publication EP A-0802203, which is incorporated herein by reference in its entirety; or at least one substituent or leaving group is selected as set forth in US Pat. No. 5,688,880, which is incorporated herein by reference in its entirety.

In a preferred embodiment of the invention, there is provided a supported bulky metallocene type catalyst system with a bulky ligand comprising an antistatic agent or surface modifier that is used to prepare a supported catalyst system as described in PCT Publication WO 96/11960, which is incorporated herein by reference in its entirety. description by reference. The catalyst systems of the invention can be prepared in the presence of an olefin, for example hexene-1.

In another embodiment, a bulky ligand metallocene type catalyst system can be combined with a carboxylate metal salt, for example, aluminum carboxylates such as aluminum mono, di and tristearates, aluminum octo octates, oleates and cyclohexyl butyrates, as described in US Serial No. 09 / 113216, filed July 10, 1998

A preferred method for preparing a bulky ligand supported metallocene type catalyst system of the invention is described below, which can be found in US patent applications Serial Nos. 265533, filed June 24, 1994, and 265532, filed June 24, 1994, as well as in applications PCT WO 96/00245 and WO 96/00243, which were published on January 4, 1996, which are all fully incorporated herein by reference. In this preferred method, the catalytic compound of the metallocene type with a bulky ligand is suspended in a liquid to obtain a metallocene solution, and a solution comprising an activator and a liquid is separately prepared. As the liquid, any compatible solvent or other liquid can be used which is capable of forming a solution or the like with the metallocene type catalyst compounds with a bulky ligand and / or activator according to the invention. In a most preferred embodiment, a cycloaliphatic or aromatic hydrocarbon is used as the liquid, most preferably toluene. Solutions of a metallocene type catalytic compound with a bulky ligand and an activator are mixed and added to a porous carrier or a porous carrier is added to these solutions so that the total volume of a metallocene type catalytic compound solution with a bulky ligand and a solution of an activator or solution of a metallocene type catalytic compound with a bulky ligand and activator was less than four times the pore volume of the porous carrier, more preferably less than three times the volume, even more respectfully less than two times, and the preferred ranges are from 1.1 to 3.5 times range and most preferably from 1.2 to 3 times range.

Methods for determining the total pore volume of a porous support are well known in the art. The details of one of these methods are discussed in Volume 1 of Experimental Methods in Catalytic Research (Academic Press, 1968) (see specifically, pp. 67-96). This preferred method involves the use of the classic BET instrument for determining nitrogen absorption. Another method well known in the art is described in Innes, Total Porosity and Particle Density of Fluid Catalysts by Liquid Titration, Volume 28, No. 3, Analytical Chemistry 332-334 (March 1956).

The molar ratio between the metal of the activator component and the metal of the metallocene-type catalytic compounds with a bulky ligand is in the range from 0.3: 1 to 1000: 1, preferably from 20: 1 to 800: 1, and most preferably from 50: 1 to 500: 1 . When the activator is an ionizing activator, such as activators based on anionic tetrakis (pentafluorophenyl) boron, the preferred molar ratio between the metal of the activator component and the metal component of the metallocene type catalyst with a bulky ligand is in the range from 0.3: 1 to 3: 1.

In one embodiment, before carrying out the main polymerization process in the presence of a conventional transition metal catalyst system and / or a bulky ligand metallocene type catalyst system of the invention, olefin (s) are preferably prepolymerized, preferably C ₂ -C ₃₀ olefin (s) or alpha α-olefin (s-olefins), preferably ethylene or propylene, or combinations thereof. The prepolymerization can be carried out periodically or continuously in the gas, solution or suspension phase, including the creation of high pressure. The prepolymerization can be carried out using any olefin monomer or combination of monomers and / or in the presence of any molecular weight controlling agent, such as hydrogen. Examples of prepolymerization methods can be found in US patents No. 4748221, 4789359, 4923833, 4921825, 5283278 and 5705578, in European publication EP B-0279863 and PCT publication WO 97/44371, which are all fully incorporated into this description by reference. In this embodiment, either prepolymerization is carried out in the presence of a solid compound, preferably a solid acid compound, or this solid compound, preferably a solid acid compound, is added after prepolymerization, but before the main polymerization process, or is simply added to the reactor together with an already prepared, prepolymerized catalyst, or in the form of their combination. Considering only the objectives of the present description and the appended claims, prepolymerization is considered as a method of immobilizing a catalyst system and, therefore, is considered as preparing a supported catalyst system. In a most preferred embodiment, a solid compound, preferably a solid acid compound, is contacted with a pre-prepared polymerization catalyst supported on a carrier.

Connections

There are many compounds that can be used to control the kinetics of catalysis in the polymerization of olefins. In a preferred embodiment, an object of the invention is the use of a substantially solid compound, preferably a solid compound, which, in the presence of a polymerization catalyst, undergoes a phase transformation during the polymerization process at a predetermined temperature to form a substantially liquid compound, preferably a liquid compound. In one embodiment, at 80 ° C. for 20 minutes, the mass loss of the solid compound does not exceed, as determined by standard thermogravimetric analysis (TGA), 20 wt.%, Preferably less than 10 wt.%, More preferably less than 5 wt.%, even more preferably less than 2 wt.%, and most preferably less than 1 wt.%. According to another embodiment of the invention, this solid compound has a dielectric constant that exceeds 2, preferably exceeds 5, more preferably exceeds 10, and / or a melting point in the range from 0 to 200 ° C, preferably from 10 to 180 ° C, more preferably from 40 to 150 ° C., and most preferably from 80 to 130 ° C. The most preferred compound is an acid, and in particular a Bronsted solid acid.

Acid compounds

In a preferred embodiment, the solid compound is an acidic compound, preferably Bronsted acid, and when combined or contacted with the polymerization catalyst before it is introduced into the polymerization process, is substantially or completely unable to interact with the polymerization catalyst. However, when the polymerization catalyst and the solid compound enter the polymerization medium at a temperature exceeding the polymerization temperature, this solid compound becomes a liquid that deactivates the polymerization catalyst. Considering the objectives of the present description and the appended claims, the concepts of "polymerization temperature" and "reactor temperature" are used interchangeably. The solid / liquid phase transition conditions depend, for example, on the particular polymerization process and / or on the feed mechanism for introducing them into the polymerization reactor.

Acidic compounds can be represented by the following general formula:

where XH is an acid, preferably Bronsted acid (Bronsted, JN Rec. Trav. Chim. 1923, 42, 718), with a pKa of less than 20, preferably less than 15, more preferably less than 10, and most preferably less than 5. Some Bronsted acids classes include ketones, alcohols, ammonium salts, nitriles, nitro compounds, acetylenes, phonols, carboxylic acids and mineral acids. Examples of compounds of these classes include acetophenone, adamantanol, anilinium chloride, diphenylacetonitrile, picrolonic acid, phenylacetylene, phenol, benzoic acid and tungsten acid. Carboxylic acids are most preferred, including o-toluic acid, tropic acid, 4-octyloxybenzoic acid, 4-bromophenylacetic acid, 2-phenoxybenzoic acid, 3,4,5-triethoxybenzoic acid and 2,4-dimethoxybenzoic acid.

Acids with a high density of functional groups, such as malic acid and glutaric acid, are particularly preferred.

Non-limiting examples of acidic compounds include 3-methyladipic acid, DL-malic acid, tropic acid, glutaric acid, ketoglutaric acid, pimelic acid, mandelic acid, 3-tert-butyl adipic acid and L-malic acid. The most preferred acids of the invention are in solid form in which their vapor pressure is low or absent.

The conditions under which a liquid acidic compound is formed from a solid acidic compound can be controlled, for example, by selecting the acidic compound to be used. This can be achieved by selecting the acid compound according to the melting point. In one embodiment, the melting point of the acidic compound is in the range of 50 to about 130 ° C, preferably in the range of 60 to about 120 ° C, more preferably in the range of 70 to about 110 ° C, and most preferably in the range of 80 to about 105 ° C.

In another embodiment, the melting point of the acidic compound exceeds 60 ° C, preferably exceeds 70 ° C, more preferably exceeds 75 ° C, and most preferably exceeds 80 ° C.

In one embodiment, the acid compound melts at a temperature that is more than 5 ° C higher than the polymerization temperature.

In one preferred embodiment, the acid is selected from one or more compounds of the series comprising tropic acid, glutaric acid, methyladipic acid, L-malic acid, 4-octyloxybenzoic acid, 3-tert-butyladipic acid, ketoglutaric acid and DL-malic acid.

In one embodiment, more than one solid compound is used, preferably more than one acidic compound. Such a path makes it possible, for example, to control the kinetics of catalysis during polymerization under two different temperature conditions.

Insolubility in hydrocarbons during reactions in suspension and solution phases is mandatory. If necessary, you can add a second component (auxiliary agent), which contributes to the phase transformation of a solid acid into its liquid or practically liquid form.

In one embodiment, the acid has a melting point such that the acid remains solid in the temperature range from 25 ° C to the temperature normal in the reaction conditions in the reactor during polymerization. Normal polymerization temperature varies depending on the particular method used and / or the resulting polymer. The polymerization temperature in the gas phase process is typically in the range from 50 to about 120 ° C., more preferably from about 60 to about 110 ° C., most preferably from about 65 to about 100 ° C. Other values of the polymerization temperature are discussed in the present description. below.

The most preferred acidic compounds are polar acidic compounds, which typically include dibasic and tribasic acids, which are characterized by very low vapor pressure, low solubility in hydrocarbons, preferably no vapor pressure. Acidic compounds that exhibit low toxicity are also preferred.

Other preferred properties of acidic compounds meet the following requirements: 1) the possibility of regulation, due to which the set phase transformation temperature can be adapted to this process; 2) low toxicity; 3) non-volatility in the solid state; 4) the speed of the reaction in a narrow temperature range; 5) the speed of the phase transition from solid to liquid; 6) the lack of influence of the type of catalyst; 7) performance under various conditions in the reactor; 8) uniform distribution throughout the reactor and (preferably) elimination of ingress into the recirculation line; 9) the absence of a noticeable effect on the granulation process; 10) the absence of an undesirable effect on the properties of the polymer at subsequent technological stages; and 11) the ease of handling.

In a preferred embodiment, the acidic compound is a polar compound, wherein the acidic compound has at least one —OH functional group. The most preferred of these polar compounds are insoluble in aliphatic hydrocarbons. The most preferred acid is L-malic acid.

Methods of using a combination of compounds

The use according to the invention of a solid compound, preferably a solid acid compound, can be varied. Thus, for example, an acidic compound can be added or introduced, with or without a polymerization catalyst, directly into the polymerization process. The acidic compound can be added to the reactor separately and / or simultaneously with the polymerization catalyst, preferably with a supported polymerization catalyst. In one embodiment, the acidic compound is contacted with the catalyst compound before being introduced into the reactor. Other options may include applying an acidic compound to the support material, followed by introducing the support material into the polymerization reactor.

In one embodiment, the solid acidic compound may be introduced into the recycle stream of the gas phase polymerization process either below the distribution plate or into a zone within the reactor in which there is a high tendency to form deposits. In the present description, details of the gas phase polymerization process are discussed below.

However, in yet another embodiment, a solid compound, preferably a solid acid compound, is used in combination with a non-supported catalyst system, or even a supported catalyst system form.

In a most preferred embodiment, the acidic compound is used with a supported catalyst system. The most preferred method for preparing a supported catalyst system of the invention typically involves combining, contacting, combining, binding and / or mixing any of the above catalyst compounds, preferably a metallocene type catalyst compound with a bulky ligand, using any of the previously described techniques.

In one embodiment of the process of the invention, the catalytic compound is combined, contacted, coupled, combined and / or mixed with an acidic compound. In a most preferred embodiment, a conventional transition metal type catalyst or a bulky ligand metallocene type supported catalyst supported on a support is used as the catalytic compound. In one embodiment, the acidic compound is in suspension in the mineral oil with or without a catalyst system, preferably with a supported catalyst system that is introduced into the polymerization process.

In another embodiment, the steps of the method of the invention comprise preparing a polymerization catalyst, preferably preparing a supported polymerization catalyst, and introducing the polymerization catalyst, preferably the supported polymerization catalyst, into contact with a polar solid acidic compound, preferably an acid. In a preferred embodiment, the polymerization catalyst comprises a catalytic compound, an activator and a carrier, and the preferred polymerization catalyst is a metallocene type catalyst with a bulky ligand on a support.

In one embodiment of the process of the invention, the acidic compound is contacted with a catalyst system, preferably a supported catalyst system, most preferably a metallocene type catalyst system with a bulky ligand supported, at normal temperature and pressure. The preferred contact temperature for combining the polymerization catalyst and the acid compound is in the range from 0 to about 100 ° C, more preferably from 15 to about 75 ° C, most preferably at about normal temperature and pressure.

In a preferred embodiment, the contacting of the polymerization catalyst and a solid polar compound, preferably an acidic compound, is carried out in an atmosphere of an inert gas such as nitrogen. However, it is possible to combine the polymerization catalyst and the acid compound in the presence of olefin (s), solvents, hydrogen, and the like.

In one embodiment, during the preparation of the catalyst composition, the acid can be added at any stage, as long as this solid acid does not interact with the composition during preparation.

In one embodiment of the process of the invention, the polymerization catalyst and the acid compound are combined in a liquid medium, for example, mineral oil, toluene, hexane, isobutane or a mixture thereof can be used as the liquid. In a more preferred embodiment of the process, the acid compound is combined with a polymerization catalyst that is prepared in a liquid, preferably in suspension, or combined with a substantially dry or dried polymerization catalyst that is placed in a liquid and resuspended.

Preferably, the polymerization catalyst is contacted with the acidic compound for a period of time greater than a second, preferably from about 1 minute to about 48 hours, more preferably from about 10 minutes to about 10 hours, and most preferably from about 30 minutes to about 6 hours. By the contacting period is meant only the mixing time.

In one embodiment, the molar ratio between the solid polar compound, preferably the solid acid compound, and the metal of the polymerization catalyst is in the range from 5000 to about 0.2, preferably from about 1000 to about 0.5, more preferably from about 500 to about 1, and most preferably from about 250 to about 10.

In another embodiment, the ratio between the mass of the solid polar compound, preferably the solid acid compound, and the mass of the polymerization catalyst (including the support in the case of a supported polymerization catalyst) is in the range from 100 to 0.001, preferably from about 10 to about 0.01, more preferably from 5 to 0.1, and most preferably from 2 to about 0.2.

The mixing technology and equipment proposed for use in the method according to the invention are well known. The mixing technology may include any means of mechanical mixing, for example, shaking, stirring with a stirrer, tumbling and rolling. Another contemplated technology involves the use of fluidization, for example in a fluidized bed reactor in which circulating gases provide mixing. Non-limiting examples of mixing equipment for combining a solid polymerization catalyst and acidic compounds include a stirrer with a tape screw blade, a static mixer, a two-cone mixer, a tumbling drum, a drum roll mill, an emulsion breaking apparatus, a fluidized bed mixer, a spiral mixer and a conical mixer a screw.

In a preferred embodiment of the invention, the catalyst system of the invention is supported on a carrier, and the supported catalyst system is preferably a substantially dried preformed, substantially dry and / or free-flowing product. In a particularly preferred embodiment of the process of the invention, a preformed supported catalyst system is contacted with a solid polar compound, preferably a solid acid compound. This acidic compound may be in solution, suspension or in a dry state, and in a preferred embodiment, the acidic compound is in a substantially dry or dried state. If the acid is in solution, this acid remains almost solid.

In one embodiment, the invention provides a method for co-injection of a non-supported polymerization catalyst and a solid polar compound, preferably a solid acid compound, into a reactor. In one embodiment, the polymerization catalyst is used in a non-supported form, preferably in the form of a liquid, such as that presented in US Pat. Nos. 5,331,036 and 5,693,727 and in European Publication EP A-0593083, all of which are incorporated herein by reference. The liquid polymerisation catalyst can be introduced into a solid polar compound reactor, preferably a solid acid compound, together or separately using the injection methods presented in PCT publication WO 97/46599, which is incorporated herein by reference in its entirety. When a non-supported metallocene type catalyst system with a bulky ligand is used, the molar ratio between the metal of the activator component and the metal of the metallocene type catalyst compound with a bulky ligand is in the range from 0.3: 1 to 10000: 1, preferably from 100: 1 to 5000 : 1, and most preferably from 500: 1 to 2000: 1.

In one embodiment, the productivity of the polymerization catalyst exceeds 1500 g of polymer per gram of catalyst, preferably exceeds 2000 g of polymer per gram of catalyst, more preferably exceeds 2500 g of polymer per gram of catalyst, and most preferably exceeds 3000 g of polymer per gram of catalyst. In one embodiment, when the solid polar compound, preferably the solid acid compound of the invention, undergoes a phase transformation, the productivity of the polymerization catalyst is reduced to a level of less than 1500 g of polymer per gram of catalyst, preferably less than 1000 g of polymer per gram of catalyst, more preferably less than 500 g of polymer per gram of catalyst, even more preferably less than 100 g of polymer per gram of catalyst, even more preferably less than 25 g of polymer per gram of catalyst, and most preferably to a level that is lower than the determined or equal to 0 g of polymer per gram of catalyst.

In one embodiment, a binder is used to hold the solid polar compound, preferably the solid acid compound, together with a catalyst or simply to facilitate the phase conversion of the solid into a liquid or gas, preferably into a liquid. The binder can be added to the catalyst in any of a number of ways. So, for example, a binder can be added immediately after preparation of the catalyst, when it is still in a suspended state, or before evaporation of any liquid in which the catalyst was prepared. When a binder is used, it is preferably added to the dried pre-prepared, supported polymerization catalyst. Non-limiting examples of binders include polyethylene oxide, polyethylene / propylene oxide, mineral oil, silica, alumina, silicone oil, various waxes such as carnauba wax, surfactants such as sodium dodecylbenzenesulfonate, and chelating agents such as EDTA.

A solid polar compound, preferably a solid acid compound, in combination with a polymerization catalyst supported on a carrier can be combined with agents that inevitably contribute to the dissipation of the accumulated static charge and / or modify the rheological properties of the material and / or increase the flowability of the powders, reducing the degree of compaction of the powder layer by weakening adhesion between particles and reducing friction between particles. Non-limiting examples of such agents include silica, such as Cabosil, clays, surfactants, such as fatty acid esters, metal salts of fatty acids, silica, metal halides, solvated metal halides, amines, polyoxyethylene and polyoxypropylene, their derivatives and sulfonates .

Polymerization process

The catalyst composition comprising a solid compound, preferably the solid acid compound of the invention described above, is suitable for use in any prepolymerization and / or polymerization process over a wide range of temperatures and pressures. The temperature may be in the range from -60 to about 280 ° C, preferably from 50 to about 200 ° C, and the generated pressures can be in the range from 1 to about 500 atm or higher.

Polymerization processes include processes in solution, gas phase, suspension phase, under high pressure or a combination thereof. Particularly preferred is the polymerization in the gas phase or suspension phase of one or more olefins, at least one of which is ethylene or propylene.

In one embodiment, the method of the present invention is intended to carry out the polymerization process in solution, under high pressure, in suspension or in the gas phase of one or more olefin monomers containing from 2 to 30 carbon atoms each, preferably from 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention is particularly suitable for the polymerization of two or more olefin monomers such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and decene-1.

Other monomers that can be used in the method of the invention include ethylenically unsaturated monomers, diolefins containing 4 to 18 carbon atoms each, conjugated and non-conjugated dienes, polyenes, vinyl monomers and cyclic olefins. Non-limiting examples of monomers that are suitable for use in the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.

In a most preferred embodiment of the method according to the invention, an ethylene copolymer is obtained, in which case ethylene and a comonomer comprising at least one alpha olefin containing from 4 to 15 carbon atoms, preferably from 4 to 12 carbon, are polymerized during the gas phase process atoms, and most preferably from 4 to 8 carbon atoms.

In another embodiment of the process of the invention, ethylene or propylene is polymerized with at least two other comonomers, one of which may (but not necessarily) be a diene, to produce a ternary copolymer.

In one embodiment, the invention is applicable, in particular, to a process such as a gas phase or slurry propylene polymerization process individually or together with one or more other monomers, including ethylene and / or other olefins containing from 4 to 12 carbon atoms each. Polypropylene polymers can be prepared using, in particular, bridged metallocene type catalysts with a bulky ligand, as described in US Pat. Nos. 5296434 and 5278264, both of which are incorporated herein by reference.

In the gas phase polymerization process, as a rule, a continuous cycle is used, in one part of the reactor system of which a circulating gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor due to the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle through a cooling system outside the reactor. Typically, in a gas-phase process for producing polymers with a fluidized bed, a gaseous stream comprising one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reaction conditions. This gaseous stream from the fluidized bed is diverted and returned to the reactor. At the same time, a polymer product is withdrawn from the reactor, and fresh monomer is added instead of the polymerized monomer (see, for example, US Pat. are included in the present description by reference).

The overpressure in the reactor during the gas phase process can vary from about 100 psi (690 kPa) to about 500 psi (3448 kPa), preferably in the range of about 200 psi (1379 kPa) ) to about 400 psi (2759 kPa), more preferably in the range of about 250 psi (1724 kPa) to about 350 psi (2414 kPa).

During the gas phase process, the temperature in the reactor can vary from about 30 to about 120 ° C, preferably from about 60 to about 115 ° C, more preferably in the range from about 70 to about 110 ° C, and most preferably in the range from about 70 to about 95 ° C.

Other gas-phase processes for which the method of the present invention is intended include polymerization processes with sequential steps or multi-stage processes. Methods of gas-phase processes for which the present invention is intended to be carried out include those described in US Pat. all fully incorporated herein by reference.

In a preferred embodiment, the reactor used in carrying out the present invention, and the method according to the invention provide the possibility of obtaining from more than 500 pounds of polymer per hour (227 kg / h) to about 200,000 pounds / h (90900 kg / h) or more polymer, preferably more than 1000 lbs / h (455 kg / h), more preferably more than 10,000 pounds / h (4,540 kg / h), even more preferably more than 25,000 pounds / h (11,300 kg / h), more preferably more than 35,000 pounds / h (15,900 kg / h h), however, even more preferably more than 50,000 pounds / h (22,700 kg / h), and most preferably from more than h 65,000 lbs / h (29,000 kg / h) up to more than 100,000 lbs / h (45,500 kg / h).

During the course of the suspension polymerization process, a pressure in the range of from about 1 to about 50 atmospheres and even higher and a temperature in the range of from 0 to about 120 ° C. are usually created. In the course of the suspension polymerization, a suspension of the solid powder polymer is prepared in a liquid polymerization diluent, in which ethylene and comonomers are introduced, and often hydrogen is added along with the catalyst. The suspension, including the diluent, is periodically or continuously removed from the reactor, the volatile components are separated from the polymer and optionally, after distillation, returned to the reactor. As a liquid diluent in the polymerization medium, as a rule, an alkane containing from 3 to 7 carbon atoms, preferably a branched alkane, is used. The medium used in the polymerization should be liquid and relatively inert. When a propane medium is used, the process should be carried out at a temperature and under pressure that exceed the critical parameters of the reaction diluent. The preferred medium used is hexane or isobutane.

The preferred polymerization method used in carrying out the invention is called powder polymerization or a suspension method in which a lower temperature is maintained than that at which the polymer passes into solution. Such a method in the art is well known and described, for example, in US patent No. 3248179, which is fully incorporated into this description by reference. Other suspension polymerization methods include those using a loop reactor and methods using a plurality of mixing reactors arranged in series, in parallel, or with a combination of these arrangements. Non-limiting examples of slurry processes include processes with continuous reactors with circulation or mixing. Other examples of suspension methods are presented in US patent No. 4613484, which is fully incorporated into this description by reference.

In one embodiment, the reactor used in the suspension method of the invention and the method of the invention provide more than 2,000 pounds of polymer per hour (907 kg / h), more preferably more than 5,000 pounds / hour (2268 kg / h), and most preferably more than 10,000 lbs / h (4,540 kg / h). In another embodiment, the slurry reactor used in the method of the invention produces more than 15,000 pounds of polymer per hour (6804 kg / h), preferably from more than 25,000 pounds / h (11,340 kg / h) to about 100,000 pounds / h (45,500 kg / h).

Examples of methods carried out in solution are presented in US patent No. 4271060, 5001205, 5236998 and 5589555, which are fully incorporated into this description by reference.

In a preferred embodiment of the method according to the invention, the process, preferably the suspension or gas phase process, is carried out in the presence of a bulky ligand metallocene type catalyst system and in the absence or practically no cleaning additives, such as triethyl aluminum, trimethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum diethylaluminium chloride, dibutylzinc and the like. This preferred method is presented in PCT Publication WO 96/08520 and US Pat. Nos. 5,712,352 and 5,763,543, which are incorporated herein by reference in their entirety.

The polymer product according to the invention

The polymers obtained according to the method according to the invention can be used for a wide variety of products and end uses. The polymers obtained according to the method according to the invention include linear low density polyethylene, elastomers, plastomers, high density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers.

Polymers, typically ethylene-based polymers, have a density in the range of 0.86 to 0.97 g / cc, preferably in the range of 0.88 to 0.965 g / cc, more preferably in the range of 0.900 to 0 96 g / cc, even more preferably in the range of 0.905 to 0.95 g / cc, even more preferably in the range of 0.910 to 0.940 g / cc, most preferably greater than 0.915 g / cc, more preferably more than 0.920 g / cc, and most preferably more than 0.925 g / cc. Density is determined in accordance with ASTM D-1238.

The polymers obtained according to the method according to the invention, as a rule, have a molecular weight distribution, the ratio between the weight average molecular weight and number average molecular weight (Mw / Mn) from more than 1.5 to about 30, preferably from more than 2 to about 10, more preferably from greater than about 2.2 to less than about 8, and most preferably from 2.5 to 8.

In addition, the polymers according to the invention, as a rule, are characterized by a narrow compositional distribution, as determined by the index of the compositional distribution width (PSKR). Other details of the determination of the PCR of the copolymer are known to those skilled in the art (see, for example, PCT application WO 93/03093, published February 18, 1993, which is incorporated herein by reference in its entirety).

In one embodiment, the polymers of the invention obtained using a bulky ligand metallocene type catalyst have PSCR values typically in the range of greater than 50 to 100%, preferably up to 99%, more preferably in the range of 55 to 85%, more preferably from 60 to 80%, even more preferably more than 60%, and even more preferably more than 65%.

In another embodiment, polymers prepared using a bulky ligand metallocene type catalyst system have a PCR of less than 50%, preferably less than 40%, and most preferably less than 30%.

In one embodiment, the polymers of the present invention have a melt index (IR) or (I ₂ ), which is determined according to ASTM D-1238-E, in the range from 0.01 to 1000 dg / min, preferably from about 0.01 to about 100 dg / min, more preferably from about 0.1 to about 50 dg / min, and most preferably from about 0.1 to about 10 dg / min.

In one embodiment, the polymers of the invention are characterized by a melt index ratio (I ₂₁ / I ₂ ) (I ₂₁ determined according to ASTM D-1238-F) from 10 to less than 25, preferably from about 15 to less than 25.

In a preferred embodiment, the polymers of the invention are characterized by preferred melt ratio ratios (I ₂₁ / I ₂ ) (I ₂₁ determined according to ASTM D-1238-F) greater than 25, more preferably greater than 30, even more preferably greater than 40, nevertheless still more preferably greater than 50, and most preferably greater than 65. In one embodiment, the polymer of the invention may have a narrow molecular weight distribution and a wide composition distribution, or vice versa. Such polymers can be those that are presented in US patent No. 5798427, which is incorporated into this description by reference.

In yet another embodiment, propylene-based polymers are prepared according to the method of the invention. These polymers include atactic polypropylene, isotactic polypropylene, semi-isotactic and syndiotactic polypropylene. Other propylene polymers include propylene block and high impact copolymers. Propylene polymers of these types are well known in the art (see, for example, US Pat. Nos. 4,794,096, 3,248,455, 4,367,851, 5,036,034 and 5,459,117, all of which are incorporated herein by reference).

The polymers of the invention can be combined and / or extruded together with any other polymer. Non-limiting examples of other polymers include linear low density polyethylenes obtained by catalysis using conventional Ziegler-Natta and / or bulky ligand metallocene type catalysts, elastomers, plastomers, low density high pressure polyethylene, high density polyethylene, polypropylene and the like.

The polymers obtained according to the method according to the invention, and mixtures thereof can be used in molding processes such as extrusion and co-extrusion of film and sheets and fiber spinning, as well as blow molding, injection molding and rotor molding. Film materials include films made by blow molding and casting, films made by co-extrusion and layering, which can be used as shrink films, sticky films, stretch films, cushion films for welding, oriented films, packaging for snacks, bags for harsh conditions operation, bags for groceries, packaging for baked and frozen food products, packaging for medical purposes, industrial sealing materials, meme wounds, etc., used in the contact and non-food contact. The manufacture of fibers includes melt spinning, melt spinning and hollow fiber melt spinning processes for use in woven and non-woven forms in the manufacture of filters, towel fabrics, clothing for medical professionals, geotextiles, etc. Extruded products include tubes for medical purposes, wire and cable coatings, geomembranes and pool lining materials. Molded products include single and multi-layer bottle-shaped products, large containers, large hollow products, rigid food containers, toys, etc.

Examples

For a better understanding of the essence of the present invention, including its characterizing advantages, the following examples are offered.

Catalyst

The polymerization catalyst used in the examples below was prepared analogously to the following preparation method. The bridged metallocene-type catalytic compound with a bulky ligand is dimethylsilylbis (tetrahydroindenyl) zirconium dichloride [Me ₂ Si (H ₄ -ind) ₂ ZrCl ₂ ], available from Albemarle Corporation, Baton Rouge, pc. Louisiana. This catalytic compound [Me ₂ Si (H ₄ -ind) ₂ ZrCl ₂ ] is applied to Crosfield ES-70 grade silica, dehydrated at 600 ° C., whose moisture loss upon calcination (PVP) is approximately 1.0% by weight. PVP is determined by measuring the weight loss of the carrier material, which is heated and held at a temperature of about 1000 ° C for about 22 hours. The average particle size of Crosfield ES-70 silica is 40 μm and is available from Crosfield Limited, Warrington, England.

The first step in the process of preparing said metallocene type catalyst with a bulky ligand on a support comprises preparing a precursor solution. 460 pounds (209 kg) of the sparged and dried toluene are introduced into the reactor with the stirrer turned on, after which 1060 pounds (482 kg) of methylaluminoxane (MAO) in toluene are added in a concentration of 30 wt.% (Available from Albemarle, Baton Rouge, pc. Louisiana). As a catalytic compound, 947 pounds (430 kg) of a toluene dimethylsilylbis (tetrahydroindenyl) zirconium dichloride concentration of 2 wt.% And an additional 600 pounds (272 kg) of toluene are charged to the reactor. Next, the precursor solution is stirred at 80-100 ° F (26.7-37.8 ° C) for one hour.

While stirring said precursor solution, 850 pounds (386 kg) of Crosfield silicon dioxide dehydrated at 600 ° C. is slowly added to this precursor solution and the mixture is stirred for 30 minutes at 80-100 ° F (26.7-37.8 ° C). After 30 minutes of stirring, 240 pounds (109 kg) of toluene solution of AS-990 [N, N-bis (2-hydroxyethyl) octadecylamine, C ₁₈ H ₃₇ N (CH ₂ CH ₂ OH) ₂ ], available in product form Kemamine AS-990 from Witco Corporation, Memphis, PCs. Tennessee concentration of 10 wt.% Together with an additional 110 pounds (50 kg) of toluene wash liquid and then the contents of the reactor are stirred for 30 minutes while heating to 175 ° F (79 ° C). After 30 minutes, a vacuum is applied and the polymerization catalyst mixture is dried at 175 ° F. (79 ° C.) for about 15 hours to give a free-flowing powder. The final weight of the polymerization catalyst is 1,200 pounds (544 kg), the Zr content in it is 0.35 wt.%, And Al is 12.0 wt.%.

Process

A one-liter reactor made of 316 stainless steel with a spiral stirrer with a pneumatic drive, an external casing for heating with water vapor, and an internal casing for acetone coolant was dried by exposure at 115 ° C and simultaneous purging with nitrogen at a flow rate of 500 cc / s for 30 min. After cooling to 90 ° C under inert conditions, 100 g of polyethylene was loaded into it [granular product of Union Carbide DSX4810 grade (available from Union Carbide Corporation, Denbury, Connecticut) on a Cr basis with a density of 0.948, I ₁₀ = 10, unstabilized] and four times with nitrogen, a pressure of 100 psi (690 kPa) was applied and discarded. Then, a solution of 100 μmol of triisobutylaluminum (TIBA) was added, the reactor was tightly closed and three times ethylene was pressurized at 100 psi (690 kPa) and discharged, after which working conditions were created in the reactor: a temperature of 80 ° C and a pressure of 107 psi. inch (738 kPa).

In a nitrogen-filled glove box, a 1/4 inch (2 cm) stainless steel tube insulated between two valves and connected to a nitrogen tank was charged into a catalyst loading vessel containing 60.7 mg of a polymerization catalyst on a carrier, which described above, and connected to a reactor opposite the nitrogen purge tube. Then, three times in the reactor, ethylene was created and depressurized. Then, operating conditions were created in the reactor, a temperature of 80 ° C. and a pressure of 107 psi (738 kPa), and a catalyst was injected into it. After 38 minutes, the temperature was raised to 100 ° C. over 5 minutes and maintained for 40 minutes. Given the objectives of the experiments presented below, the ideal acid compound on the catalytic activity at 80 ° C probably has no effect, but significantly reduces the catalytic activity at 100 ° C.

Table 1 presents the data from control experiments in which no acid compound was used together with the polymerization catalyst. The results of control experiments show that in the range of elevated temperatures, in these examples, 100 ° C, without acid, the catalytic activity was significant.

Examples 8, 9 and 10

45 mg of L-malic acid was charged into a catalyst loading vessel and, in this experiment, was injected under nitrogen pressure for a 20-minute exposure period at 80 ° C.

The data in table 2 illustrate the effect of acid at elevated temperatures. The "rubble" indicator was also reduced, which indicated improved continuity.

In the following tables, the “rubble” characterizes unwanted polymer particles with a size greater than 10 mesh (about 2 mm).

The data of the following experiments from 11 to 20 are also shown in table 3.

Examples 11 and 12

The experiment was carried out analogously to example 8, except that L-malic acid was mixed with the polymerization catalyst. This shows that another acid addition option is also effective.

Examples 13 to 15

The experiment was carried out analogously to example 8, except that instead of L-malic acid, glutaric acid was used. This demonstrates the effectiveness of another acid in reducing the polymerization rate at 100 ° C.

Example 16

The experiment was carried out analogously to example 13, except that only 23 mg of acid was used. This illustrates the possibility of controlling the degree of deactivation by the amount of acid used.

Example 17

The experiment was carried out analogously to example 13, except that glutaric acid was mixed with a polymerization catalyst. This illustrates another way of adding acid.

Example 18

The experiment was carried out analogously to example 16, except that glutaric acid was mixed with the polymerization catalyst. This again illustrates another way of adding acid.

Example 19

The experiment was carried out analogously to example 8, except that 3-methyladipic acid was used instead of L-malic acid. This example demonstrates the use of another acid that effectively reduces the polymerization rate at 100 ° C.

Example 20

The experiment was carried out analogously to example 8, except that instead of L-malic acid, 4-octyloxybenzoic acid was used, which demonstrates the use of another acid to effectively reduce the polymerization rate at 100 ° C.

Example 21

The experiment was carried out analogously to example 8, except that instead of L-malic acid, the product Irganox 565 (Ciba Specialty Chemicals, Territown, NY) was used. This shows that to reduce the polymerization rate at 100 ° C, another chemical agent may be effective.

Example 22

The experiment was carried out analogously to example 8, except that instead of L-malic acid, xylitol was used. This shows that to reduce the polymerization rate at 100 ° C, another chemical agent may be effective.

Example 23

The experiment was carried out analogously to example 8, except that pentaerythritol tetrabenzoate was used instead of L-malic acid. This shows that to reduce the polymerization rate at 100 ° C, another chemical agent may be effective.

Example 24

The experiment was carried out analogously to example 8, except that instead of L-malic acid, hydroquinonbis (2-hydroxyethyl) ether was used. This shows that to reduce the polymerization rate at 100 ° C, another chemical agent may be effective.

Although the present invention has been presented and illustrated with reference to specific embodiments, it will be apparent to those skilled in the art that the very essence of the invention leads to variations that are not necessary to illustrate in the present description. So, for example, depending on the product obtained during the polymerization process, it is possible to use another combination of acids. In addition, it is possible to use two or more polymerization reactors arranged in series or in parallel, a suspension and / or gas phase can be used where other combinations of acidic compounds can be used. Moreover, to deactivate the polymer discharged from the polymerization reactor, solid acid can be used after the reactor. Together with the acidic compound of the invention, two or more polymerization catalysts can also be used. For this reason, in order to determine the actual scope of the present invention, reference should only be made to the attached claims.

Claims (33)

1. A catalytic composition comprising a polymerization catalyst and a solid compound in which the solid compound at a temperature higher than the polymerization temperature undergoes a phase transition that deactivates the polymerization catalyst. 2. The catalytic composition according to claim 1, in which the phase transition consists in converting a solid into a liquid. 3. The catalyst composition according to claim 1, in which the polymerization catalyst is applied to a substrate. 4. The catalytic composition according to claim 1, in which the mass loss of the solid compound, as determined by thermogravimetric analysis at 80 ° C for 20 minutes, is less than 20 wt.%. 5. The catalytic composition according to claim 1, in which the dielectric constant of the solid compound exceeds 2. 6. The catalyst composition according to claim 1, in which the solid compound is an acid compound. 7. The catalytic composition according to claim 6, in which the acidic compound contains at least one functional group —OH. 8. The catalytic composition according to claim 6, in which the acidic compound is L-malic acid. 9. The catalytic composition according to claim 6, in which the acidic compound is a Bronsted acid. 10. A method for polymerizing olefin (s) in a reactor at a polymerization temperature in the presence of a polymerization catalyst and a solid compound, where this solid compound at a temperature higher than the polymerization temperature undergoes a phase transition that deactivates the polymerization catalyst with respect to the polymerization of olefin (olefins). 11. The method of claim 10, wherein the solid compound is an acid compound containing at least one functional group —OH. 12. The method according to claim 11, wherein the acidic compound is L-malic acid. 13. The method of claim 10, wherein the polymerization catalyst is applied to the substrate. 14. The method of claim 10, wherein the polymerization catalyst comprises a metallocene-type catalyst compound with a bulky ligand. 15. A method for continuously polymerizing one or more olefins in a reactor at a polymerization temperature in the presence of a polymerization catalyst, comprising the steps of: (a) introducing a polymerization catalyst into the reactor and (b) introducing a solid compound, wherein the solid compound is subjected to a temperature higher than the polymerization temperature phase transition before turning it into a liquid compound. 16. The method according to clause 15, in which stage (a) and stage (b) are carried out simultaneously. 17. The method according to clause 16, in which before introducing into the reactor a solid compound and a polymerization catalyst are combined. 18. The method according to 17, in which the solid compound is an acidic compound. 19. The method according to p, in which the acidic compound contains at least one functional group-OH. 20. The method according to clause 15, in which the polymerization catalyst comprises a catalytic compound of the metallocene type with a bulky ligand and an activator. 21. A catalytic composition for the polymerization of olefins, comprising a metallocene-type catalytic compound with a bulky ligand, an activator, a support and a solid acid compound which, at a temperature higher than the polymerization temperature, undergoes a phase transition that deactivates the polymerization catalyst. 22. The catalytic composition according to item 21, in which the acidic compound is a Bronsted acid. 23. The catalytic composition according to item 21, in which, when it is heated to a temperature exceeding 65 ° C, the solid acid compound forms a liquid. 24. The catalytic composition according to item 21, where this catalytic composition is heated by the heat of the polymerization process to a temperature exceeding the polymerization temperature of the process. 25. A method of preparing a catalyst composition comprising the following steps: (a) mixing a polymerization catalyst with an activator; (b) the addition of a solid polar compound, which, at a temperature higher than the polymerization temperature, undergoes a phase transition in which the solid polar compound is not reactive during preparation. 26. The method according A.25, in which the solid polar compound is an acidic compound. 27. The method according A.25, which includes an additional step of adding a substrate. 28. The method according A.25, in which after stage (a) the mixture is combined with the substrate. 29. The method according A.25, in which at a temperature exceeding the polymerization temperature, the solid polar compound is non-reactive. 30. The method according A.25, in which the polymerization catalyst is a catalytic compound of the metallocene type with a bulky ligand. 31. The method of polymerization of one or more olefins in the presence of a catalytic composition comprising a polymerization catalyst and a solid polar compound in a reactor operating at a polymerization temperature and under polymerization pressure, to obtain a polymer product comprising at least one phase transition of a solid polar compound at a temperature exceeding the polymerization temperature, in a practically liquid state. 32. The method according to p, in which the solid polar compound is an acidic compound containing at least one functional group-HE. 33. The method according to p, in which the polymerization temperature is in the range from 65 to 120 ° C.