Polymer production under supersolution conditions

<u style="single">Inventor</u>: Pat Brant, Gabor Kiss, Chris Friedersdorf, James Lattner, Gary Casty<u style="single">Priority claim</u>This application claims priority under Application No. 60 / 933,007 of June 4, 2007. This application is also a partial continuation application pending simultaneously with US Application No. 10 / 667,585 filed September 22, 2003, which is a US application filed September 20, 2002. Claims priority under US Application Nos. 60 / 412,541 and US Application Nos. 60 / 431,077 filed December 5, 2002. This application is also a partial continuation of US Patent Application No. 11 / 714,546 filed March 6, 2007.<u style="single">Statement of related application</u>

This application is a related application of US Application No. 10 / 667,585 filed on September 22, 2003, which is filed on September 20, 2002, US Application Nos. 60 / 412,541 and 2002. Dec. 5, 2014 Claims priority under US Application No. 60 / 431,077.

This application is also a related application of US Application No. 10 / 667,586 filed September 23, 2003, which is US Application No. 60 / 412,541 filed September 20, 2002. And claims priority under US Application No. 60 / 431,077 of December 5, 2002.

This application is also a related application of US Application No. 11 / 510,871 of August 25, 2006, which is a partial continuation of US Application No. 11 / 177,004 (currently abandoned) filed on July 8, 2005. This US application No. 11 / 177,004 claims the benefit of the priority of US application No. 60 / 586,465 filed on July 8, 2004. U.S. Application No. 11 / 177,004 is a partial continuation of U.S. Application No. 10 / 667,585 on September 22, 2003, and U.S. Application No. 10 / 667,585 is a U.S. Application on September 20, 2002. Claims the benefit of priority under No. 60 / 412,541 and the benefit of priority under US Application No. 60 / 431,077 of December 5, 2002. U.S. Application No. 11 / 177,004 is also a partial continuation of U.S. Application No. 10 / 667,586 filed September 22, 2003, which U.S. Application No. 10 / 667,586 is September 20, 2002. Claims the benefit of priority under US application 60 / 4,12,541 and the benefit of priority under US application 60 / 431,077 of December 5, 2002.

This application is also a related application of US Application No. 60 / 876,193 of December 20, 2006.

<u style="single">Field of invention</u>The present invention relates to a polymerization reaction of propylene under supersolution conditions using a catalyst compound of a central metal and a heteroaryl ligand having a non-metallocene structure.

<u style="single">Background of the invention</u>Polymerization of propylene is commercially useful, and therefore more efficient propylene polymerization methods are required in the art. The state-of-the-art commercial production method is to polymerize propylene by a particle formation production method, which is known in the art of the present application as vapor phase and slurry polymerization. These formulas are very efficient in synthesizing polypropylene, but cannot produce blends of polypropylene with other polymers in-line. That is, the components of each polymer blend cannot produce a blend before they are taken out in their essentially pure state. For this reason, the latest manufacturing methods for producing polyolefin blends, especially blends of polypropylene with other polymers, such as ethylene-propylene or copolymers such as ethylene-hexene-1, have been completely removed. Polypropylene of normal granules is mixed with other completely removed polyolefin blend components of normal granules by melt blending. However, because it is difficult to mix high viscosity molten polymers, molten blends are expensive and not perfectly uniform. Solution polymerization can produce the polypropylene component in a dissolved fluid state, which is also suitable for blending with other polymers produced in a solution state. However, the molecular weight and thermal properties of polypropylene produced by the solution production process are often unsuitable for the production of commercially useful polymer blends. Therefore, an improved solution formula for propylene-containing polymers, especially polypropylene, is needed to allow solution manipulations that allow in-line polymer mixing without unacceptably degrading the performance of the components of the polypropylene blend. The disclosed supersolution production method can overcome these limitations of the current state of the art and produce polypropylene with excellent (low) melt flow rate, high melting point and crystallization temperature. Several manufacturing methods that operate in a uniform state that allow in-line polymer mixing in solution are disclosed. However, these are defective in product quality or too expensive,

US Pat. No. 6,084,041 granted to Andtsjoe et al. Is supercritical under relatively mild conditions (90 ° C to 100 ° C and pressures below 6.89 Mpa) using carrier-supported Ziegler-Natta and metallocene catalysts. The critical propylene polymerization is disclosed.

WO 93/11171 discloses a polyolefin production method comprising continuously supplying an olefin monomer and a metallocene catalyst system to a reactor. The monomer is continuously polymerized to give a mixture of monomer and polymer. The reaction conditions maintain the mixture at a pressure below the cloud point pressure of the system. These conditions create a polymer-rich phase and a monomer-rich phase, maintaining the temperature of the mixture above the melting point of the polymer. The formation of high-viscosity polymer-rich phases often causes problems in the operation of the reactor and subsequent processes due to fouling, unintended bulk phase separation, and reduced heat transfer.

WO 03/040201 discloses the polymerization of propylene with a catalytic compound of a non-metallocene central metal and a heteroaryl ligand under non-supersolution conditions.

Other references related to<u style="single">Olefin Polymerizaition Using Highly Congested ansa-Metallocenes under High Pressure: Formation of Superhigh Molecular Weight Polyplefins, </u>Suzuki, et al., Macromolecules, 2000,33,754-759, EP1123226, WO0012572, WO0037514, EP1195391 and Ethylene Bis (Indenyl) Zirconium ..., Schaverien, CJet al., Organometallics, ACS, Columbus Ohio, vol 20, no. 16, August 2001, pg3436-3452, WO96 / 34023, WO97 / 11098, US Pat. No. 5,084,534, US Pat. No. 2,852,501, WO93 / 05082, European Patent No. 129368B1, WO97 / 45434, Japanese Patent No. 96-208535, US Pat. No. 5,096,867, WO96 / 12744, US Pat. No. 6,225,432, WO02 / 090399, WO02 / 50145, US Pat. No. 2002013440, WO01 / 46273, European Patent No. 1008607, Japanese Patent No. 1998-110003A, US Patent No. 6,562,914, and Japanese Patent No. 1998-341202B2, US Patent No. 5,756,608, US Patent No. 5,969,062, US Patent No. 5,408,017, US Patent No. 6,355,741, WO92 / 14766 , Includes US Pat. Nos. 5,326,835, WO / 2004-02692 and CA 2,118,711 (same as DE4,130,299).

WO02 / 38628 describes catalytic compounds of central metals and heteroaryl ligands with non-metallocene structures and their various uses. WO2006 / 009976 discloses polymerization of various non-metallocene structures in fluorocarbons with catalytic compounds of central metals and heteroaryl ligands. In addition, WO03 / 040095, WO03 / 040202, WO03 / 040233, WO03 / 040442 and US Pat. No. 7,087,690 are catalyst compounds for non-metallocene central metals and heteroaryl ligands, their polymerized products and their various uses. Is stated.

WO94 / 00500, WO2007 / 037944 and Macromol. Chem. Phys. 204 (2003), 1323-1337 disclose various solutions for the synthesis of polypropylene.

The present invention relates to a process for polymerizing an olefin, which comprises contacting propylene with the following at a temperature of 65 ° C to 150 ° C and a pressure between 250 and 5000 psi (1.72 to 34.5 MPa). In other words 1) A catalytic system containing one or more active agents, one or more central metals having a non-metallocene structure, and a catalytic compound of a heteroaryl ligand, and the metal is a group 4, 5, 6 of the periodic table of elements. , Catalytic system selected from lanthanide series or actinide series, 2) 0 to 20% by weight of 1 or more comonomer, selected from the group consisting of ethylene and C4 to C12 olefins (based on the weight of all monomers and comonomer contained in the feedstock). 3) 20-65% by weight diluent or solvent based on the total weight of feedstock sent to the polymerization reactor. 4) A manufacturing method comprising contacting with a scavenger, from 0 to 5% by weight, based on the total weight of the feedstock sent to the polymerization reactor. here, a) The olefin monomer and any comonomer are contained in the polymerization system in an amount of 15% by weight or more. b) The propylene is contained in an amount of 80% by weight or more based on the weight of all monomers and comonomer in the feedstock. c) The polymerization reaction is carried out at a temperature higher than the temperature at which the solid-fluid phase transition of the polymerization system occurs and at a pressure higher than the pressure of 1 MPa lower than the cloud point pressure of the polymerization system. However, it is a condition that the polymerization reaction occurs at (1) a temperature lower than the critical temperature of the polymerization system or (2) a pressure lower than the critical pressure of the polymerization system.

The polymerization system comprises an olefin monomer and any comonomer, any diluent or solvent, any scavenger, and a polymeric product.<u style="single">Definition</u>

For the invention of the present application and claims for it 1. A catalytic system is defined as a combination of one or more catalytic compounds and one or more activators. The term "catalyst compound" is used interchangeably with the terms "catalyst", "catalyst precursor" and "catalyst precursor compound". 2. High density fluid is at least 300kg / m³It is a fluid with a density of. 3. The solid-fluid phase transition temperature is defined as the temperature at which the solid polymer phase separates from the uniform polymer-containing fluid medium at a given pressure below it. The solid-fluid phase transition temperature can be determined by lowering the temperature at a constant pressure from the temperature at which the polymer dissolves well in the fluid medium. The phase transition is observed as when the system becomes cloudy when measured using the methods described below to determine the cloud point. 4. The solid-fluid phase transition pressure is defined as the pressure at which the solid polymer phase separates from the fluid medium containing the polymer at a given temperature when it is below that pressure. The solid-fluid phase transition pressure is determined by reducing the pressure at a constant temperature from the pressure at which the polymer dissolves well in the fluid medium. The phase transition is observed as when the system becomes cloudy when measured using the method described below to determine the cloud point. 5. Fluid-fluid phase transition pressure, below that pressure, is defined as the pressure formed by two fluid phases, a polymer-rich phase and a monomer-rich phase, at a given temperature. The fluid-fluid phase transition pressure can be determined by reducing the pressure from the pressure at which the polymer dissolves well in the fluid medium at a constant temperature. 6. The fluid-fluid phase transition temperature is defined as the temperature at which two phases, a polymer-rich phase and a monomer-rich phase, form at a given pressure below that temperature. The fluid-fluid phase transition pressure can be determined by lowering the temperature from the temperature at which the polymer sufficiently dissolves in the fluid medium at a constant pressure. The phase transition is observed as turbidity in the system when measured using the method described below to determine the cloud point. 7. Cloud point is J.Vladimir Oliveria, C.Dariva and JC Pinto, As described in Ind.Eng, Chem.Res, 29,2000,4627, the pressure at which the polymerization system becomes turbid at a given temperature and below. In the present invention and claims, the cloud point is obtained by irradiating the photovoltaic cell with a helium laser through a selected polymerization system in the cloud point cell and recording the pressure at which a rapid increase in light scattering begins at a given temperature. Be measured. The cloud point temperature is the point at which the polymerization system becomes cloudy at a given pressure. It should be noted that in the field of polymer engineering, "cloud point" usually refers to cloud point pressure, although both cloud point pressure and cloud point temperature are well-defined physical properties. 8. Higher α-olefins are defined as α-olefins with 4 or more carbon atoms. 9. The use of the term "polymerization reaction" includes any polymerization reaction such as homopolymerization reaction and copolymerization reaction. 10. The copolymerization reaction includes any of the polymerization reactions of two or more monomers. 11. The new numbering of the genus of the periodic table is done as published in CHEMICAL AND ENGINEERING NEWS, 63 (5), 27 (1985). 12. When a polymer or oligomer contains an olefin, it means that the olefin contained in the polymer or oligomer is in the form of the olefin polymerized or oligomerized. 13. Oligomers are defined as compositions with 2-120 monomeric units. 14. A polymer is defined as a composition with 121 or more monomer units. 15. A polymerization system is defined as a monomer, a comonomer, a polymer, any inert solvent / diluent, and any scavenger. It should be noted that for convenience and clarity of description, the catalyst system is always discussed separately from the other components in the polymerization reactor in this description. In this respect, the polymerization system is defined narrower than usual here in the field of polymerization reactions in which the present catalyst system is usually considered as a part of the polymerization system. In this definition, the polymerization reactor and the mixture in its fluid consist of a polymerization system and a catalytic system. 16. To be in a supercritical state, the substrate must have a temperature above its critical temperature (Tc) and a pressure above its critical pressure (Pc). If not measured, the critical temperature (Tc) and critical pressure (Pc) are in the Handbook of Chemistry and Physics, Editor-in-Chief of David R. Lide, 82nd Edition 2001-2002, CRC Press, LLC, It is described in New York, 2001. In particular, the Tc and Pc of propylene are 364.9 ° K and 4.6Mpa. If Tc and / or Pc cannot be measured for a given system, then Tc and / or Pc is the mole fraction weighted average of the corresponding Tc'and / or Pc' of the components of the system. It is considered to be. 17. The following abbreviations are used. Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-terriary butyl. , TMS is trimethylsilyl, TIBA is triisobutylaluminum, MAO is methylarmoxane, pMe is para-methyl, flu is fluorenyl, cp is cyclopentadienyl, and Ind is indenyl. 18. The term "continuous" means a system that operates uninterrupted or uninterrupted. For example, a continuous production method for producing a polymer would be one in which the reaction raw materials are continuously introduced into one or more reactors and the polymer product is continuously taken out. 19. Slurry polymerization is a polymerization method in which a solid polymer of particles is formed in a high-density fluid or liquid / vapor polymerization medium. This high density fluid polymerization medium can form a single or two fluid phases. For example, a liquid or supercritical fluid, or a liquid / liquid, or a supercritical fluid / supercritical fluid polymerization medium. In liquid / vapor polymerization media, the polymer is in the liquid (high density fluid) phase. 20. Solution polymerization refers to a polymerization method in which a polymer is dissolved in a liquid polymerization system, such as an inert solvent or monomer or a mixture thereof. Solution polymerization is usually a uniform liquid polymerization system. 21. Supercritical polymerization is a polymerization method in which the polymerization system is in a high-density, critical state. 22. Bulk polymerization refers to a polymerization method in which the high-density fluid polymerization system contains less than 40% by weight of an inert solvent or diluent. The product polymer may be soluble in a high density fluid polymerization system or may form a solid phase. In the terminology used herein, slurry polymerization is one in which solid polymer particles are formed in a high density fluid polymerization system containing less than 40% by weight of an inert solvent or diluent, but bulk slurry polymerization or bulk non-polymerization. It is called a homogeneous polymerization method. A polymerization method in which the polymerized product is dissolved in a high-density fluid polymerization system containing less than 40% of an inert refrigerant or diluent is called a bulk homogeneous polymerization method. A polymerization method in which the polymerized product is dissolved in a fluid polymerization system containing less than 40% by weight of an inert solvent or a diluent is called a bulk solution polymerization method. A polymerization method in which a polymer product is dissolved in a supercritical polymerization system containing less than 40% of an inert solvent or a diluent is called a bulk uniform supercritical polymerization method. 23. A homopolymerization or homopolymerization system is a polymerization system in which a polymerized product is uniformly dissolved in a polymerization medium. Such a system is J. Vladimir Oliveria, There is no turbidity as described in C.Dariva and JCPinto, Ind.Eng, Chem.Res.29,2000,4627. For the purposes of the present invention and its claims, turbidity determines where the selected polymerization system in the cloud point cell is applied to the photovoltaic cell through a helium laser and a rapid increase in light scattering begins for a given polymerization system. Measured by Uniform dissolution in the polymerization medium is shown when there is little or no light scattering (ie, a change of less than 5%). 24. The term "NMCHL catalytic compound" refers to a catalytic compound in which a heteroaryl ligand coordinates a central metal with a non-metallocene structure.

Unless otherwise stated, all molecular weight units (eg Mw, Mn, Mz) are g / mol and all ppm are weight ppm.<u style="single">Detailed description of the invention</u>

The present invention presents propylene at a temperature of 65 ° C to 150 ° C (preferably between 70 ° C and 150 ° C, preferably between 75 ° C and 140 ° C, preferably between 100 ° C and 140 ° C). , 1.72 MPa and 34.5 MPa (preferably between 2 and 30 MPa, preferably between 5 and 25 MPa), relating to a process of polymerizing an olefin, including contacting with: 1) A metal-centered, heteroaryl ligand-coordinated catalytic compound with one or more activators and one or more non-metallocene structures, the metal of which is 4,5, of the Periodic Table of the Elements. A catalytic system comprising a catalyst selected from the Group 6, lanthanide series, or actinide series (preferably Group 4, preferably Hf, Ti or Zr). 2) 0 to 20% by weight (or 0.5 to 15% by weight, or 1 to 10% by weight, or 1 to 5% by weight, based on the weight of the polymerization system selected from the group consisting of ethylene and C4 to C12 olefins. %) 1 or more comonomer (or 0.1 to 20% by weight of comonomer may be included in the feedstock). 3) 20 to 65% by weight (or 25 to 60% by weight, or 30 to 55% by weight) of diluent or solvent (based on the total weight of feedstock added to the polymerization reactor), and 4) 0 to 5% by weight (or 0 to 1% by weight, or 0.001 to 0.01% by weight) scavenger, preferably one or more alkylaluminum compounds (based on the weight of the polymerization system) and / or 0 to 25% by weight (based on the weight of the polymerization system). Or 0 to 5% by weight, or 0 to 1% by weight, or 0.001 to 0.01% by weight) scavenger, preferably one or more alkylaluminum compounds (based on the total weight of feedstock added to the polymerization reactor). here, a) propylene and any comonomer in the polymerization system are 15% by weight or more, preferably 20% by weight or more (preferably 25% by weight or more, preferably 30% by weight or more, preferably 35% by weight or more, preferably 40% by weight or more. % Or more, preferably 45% by weight or more, preferably 50% by weight or more, preferably 55% by weight or more, preferably between 30 and 75% by weight). b) Based on the weight of all monomers and comonomer contained in the feedstock, propylene is (75% by weight or more, preferably 80% by weight or more, preferably 85% by weight or more, preferably 90% by weight or more, preferably 95% by weight). The above) and / or propylene is contained in the polymerization system in an amount of 20% by weight or more, preferably 25% by weight or more, preferably 30% by weight or more, preferably 35% by weight or more, preferably 40% by weight or more. c) The polymerization is carried out at a temperature higher than the solid-fluid phase transition temperature of the polymerization system, a pressure higher than a pressure 1 MPa lower than the cloud point pressure (CPP) of the polymerization system (preferably a pressure higher than 0.5 MPa lower than the CPP, preferably. Occurs at higher pressures than CPP) and d) The polymerization occurs at (1) a temperature lower than the critical temperature of the polymerization system or (2) a pressure lower than the critical pressure of the polymerization system, preferably the polymerization is at a pressure lower than the critical point of the polymerization system. It happens at temperature. Most preferably, the polymerization occurs at (1) a temperature lower than the critical temperature of the polymerization system and (2) a pressure lower than the critical pressure of the polymerization system.

Preferably, the polymerization occurs at a temperature and pressure higher than the solid-fluid phase transition temperature and pressure of the polymerization system. Alternatively, the polymerization occurs at a temperature and pressure lower than the fluid-fluid phase transition temperature and pressure of the polymerization system. The polymerization system is preferably a uniform, single-phase polymerization system, and preferably a uniform high-density fluid polymerization system.

The polymerization is usually carried out under the condition that the product polymer is dissolved in a fluid reaction system containing one or more monomers, a polymerized product and optionally one or more inert solvents and optionally one or more scavengers. Will be done. This fluid reaction medium can form a single fluid phase or two fluid phases. Operation in a single fluid phase is particularly advantageous.

In a useful embodiment, any hydrocarbon, fluorocarbon, or fluorohydrocarbon-inert solvent or mixture thereof is up to 70% by weight of the feedstock added to each polymerization reactor of the production method of the present invention. (Preferably up to 65% by weight, more preferably up to 55% by weight).

In another embodiment, the solvent or diluent is 0 to 80% by weight (or 5 to 70% by weight, or 10 to 70% by weight, or 25 to 70% by weight, or 60 to 65% by weight) of the diluent. And solvent (based on the weight of the polymerization system).

Preferably, the polymerization described herein is a homogeneous polymerization. Solid catalysts can be used if desired, but polymerization with catalysts dissolved in a single liquid phase is usually advantageous, especially in a single fluid phase. The polymerization carried out here is carried out at a pressure and temperature lower than the critical point, preferably the cloud point is lower than the critical point. In systems where the critical point cannot be determined, the critical point must be calculated from the weight average of the individual components.

The reaction temperature is preferably lower than the critical temperature of the polymerization system. Preferably, the temperature is higher than the solid-fluid phase transition temperature of the fluid reaction medium containing the polymer at the pressure of the reactor, or at least 5 ° above the solid-fluid phase transition temperature of the fluid reaction medium containing the polymer at the pressure of the reactor. C Higher temperature, or at least 10 ° C higher than the solid-fluid phase transition point of the fluid reaction medium containing the polymer at reactor pressure. In another embodiment, the temperature is higher than the cloud point of the single-phase fluid reaction medium at the reactor pressure, or more than 2 ° C higher than the cloud point of the fluid reaction medium at the reactor pressure. In yet another embodiment, the temperature is between 60 ° C and 150 ° C, between 60 ° C and 140 ° C, between 70 ° C and 130 ° C, and between 80 ° C. It is between 130 ° C. In some embodiments, the temperature is 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C, 100 ° C, 105 ° C or 110 °. Higher than C. In another embodiment, the temperature is less than 150 ° C, 140 ° C, 130 ° C, or 120 ° C. In another embodiment, the cloud point temperature is below the supercritical temperature of the polymerization system or between 70 ° C and 150 ° C.

The production method of the present invention is carried out in a high-density fluid polymerization medium, preferably in a uniform liquid polymerization medium, under conditions higher than the cloud point of the polymerization reaction medium.

A useful diluent used in the present invention is one or more Cs.₂ -C₂₄Alkanes such as ethane, propane, n-butane, i-butane, n-pentane, i-pentane, n-hexane, mixed hexane, mixed octane, cyclopentane, cyclohexane, etc., monocyclic aromatics such as toluene and xylene. including. The use of hydrocarbon solvents with 4 to 12 carbon atoms is advantageous. The use of alkanes or aromatic hydrocarbon solvents with 4 to 8 carbon atoms is particularly advantageous. In certain embodiments, the diluent comprises one or more ethane, propane, butane, isobutane, isopentane, and / or hexane. In any of the embodiments described herein, the diluent may be recirculatory.

Another useful diluent is also C₄From C₁₅₀Also contains isoparaffin, preferably C₄From C₁₀₀Isoparaffin, preferably C₄From C₂₅Isoparaffin, more preferably C₄From C₁₂Contains isoparaffin. Isoparaffin is a saturated aliphatic hydrocarbon carbon chain at least one C in each saturated aliphatic hydrocarbon carbon chain.₁From C₆It means having a branch of an alkyl chain.

In another embodiment, the diluent comprises fluorinated hydrocarbons. Preferred fluorocarbons used for use in the present invention include perfluoride (PFC or PFC's) and or hydrofluoride (HFC or HFC's), collectively fluoride hydrocarbons. Or "fluorocarbon" ("FC" or "FC's"). Fluorocarbon is defined as a compound consisting mainly of at least one carbon atom and at least one fluorine atom, and optionally a hydrogen atom. Perfluorocarbon is a compound mainly composed of carbon atoms and fluorine atoms, for example, linear branched or cyclic C.₁From C₄₀Contains perfluoroalkanes. Hydrofluorofluoride is essentially a compound consisting of carbon, fluorine and hydrogen. The preferred FC's is Equation C_xH_yF_zRepresented by, x is an integer from 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10, or 1 to 6, or 2 to 20 or 3 to 10, or 3 to 6, most preferably 1. From 3, y is an integer equal to or greater than 0, z is an integer and at least 1, more preferably y and z are integers and at least 1. In the present invention and claims thereof, the terms hydrofluoride and fluorocarbon do not include chlorofluoride.

In one embodiment, a mixture of fluorocarbons is used in the production method of the present invention. A mixture of perfluorohydrocarbon and hydrofluorocarbon is preferably used, and more preferably a mixture of hydrofluorocarbon is used. In yet another embodiment, the hydrofluorocarbons are balanced or unbalanced in the number of fluorine atoms in the HFCs used.

Non-limiting examples of fluorocarbons useful in the present invention include any of the fluorocarbons shown on pages 65, 10-66, and 31 of WO2006 / 009976. In addition to these fluorocarbons described herein, Raymond Will et al.'S CEH Marketing Report, Fluorocarbons, Pages 1-133, published in Chemical Economics Handbook-SRI International, April 2001. Includes fluorocarbons as described in (all incorporated in the book).<u style="single">monomer</u>

The production methods described herein can be used to polymerize any monomer having one or more (non-conjugated) aliphatic double bonds and two or more carbon atoms. Preferred monomers are α-olefins such as ethylene, propylene, butene-1, hexene-1, octene-1, dodecene-1 and decene-1, substituted olefins such as styrene and vinylcyclohexene, and non-conjugated such as vinylcyclohexene. Includes α, ω-diene such as diene, 1,5-hexadiene, 1,7-octadiene, cycloolefin such as cyclopentene and cyclohexene, norbornene and the like.

In a preferred embodiment, the methods described herein may be used to produce homopolymers or copolymers. (For the present invention and claims thereof, the copolymer may contain 2, 3, 4 or more different monomer units.) In one embodiment, the polymer is a homopolymer or copolymer of propylene. Preferably the polymer is a propylene homopolymer. In another embodiment, the polymer is a copolymer comprising propylene and ethylene, preferably the copolymer is less than 50% by weight ethylene, more preferably less than 40% by weight ethylene, preferably less than 30% by weight. It contains ethylene, more preferably less than 20% by weight ethylene. In another preferred embodiment, the copolymer produced here is a copolymer consisting of propylene and up to 10% by weight comonomer based on the weight of the copolymer (preferably up to 8% by weight, preferably up to 6% by weight, Up to 5% by weight, preferably up to 4% by weight, preferably up to 3% by weight, preferably up to 2% by weight). In another embodiment, the copolymer produced here comprises less than 1% by weight ethylene, preferably 0% ethylene. In another preferred embodiment, the copolymer is one or more diolefin comonomer, preferably one or more C.₆From C₄₀Non-conjugated diolefin, more preferably C₆From C₄₀Includes α, ω-diene.

In another preferred embodiment, the copolymer produced here is propylene and up to 10% by weight comonomer (preferably up to 8% by weight, preferably up to 6% by weight, preferably 5% by weight, based on the weight of the copolymer. It is a comonomer consisting of up to%, preferably up to 4% by weight, preferably up to 3% by weight, preferably up to 2% by weight). In another embodiment, the copolymer produced here comprises less than 1% by weight ethylene, preferably 0% ethylene.

In a preferred embodiment, the polymer described above further comprises one or more dienes up to 10% by weight based on the total weight of the composition, preferably 0.00001 to 1.0% by weight, preferably 0.002 to 0.5% by weight, even more preferably. Included in 0.003 to 0.2% by weight. In some embodiments, 500 ppm by weight or less of the diene is added to the polymerization, preferably 400 ppm or less, preferably 300 ppm or less. In other embodiments, at least 50 ppm of diene is added to the polymerization, or 100 ppm or more or 150 ppm or more is added.<u style="single">Introduction of catalyst</u>

The production method described herein is carried out in combination with an activator by a catalytic system containing one or more non-metallocene structures, a central metal and a catalytic compound of a heteroaryl ligand (where the metal is used). , Selected from the 4, 5, 6 groups of the periodic table of elements, the lanthanide series or the actinide series). In the production method of the present invention, one or more catalysts can be used in any reaction apparatus in the polymerization reactor area or in any of the polymerization methods described herein.

In the production method of the present invention, the same or different catalysts or catalyst mixtures can be used in each reactor in the reactor area of the present invention. For practical reasons, the polymerization method of the present invention preferably uses a catalyst of 10 or less, and more preferably a catalyst of 6 or less. In yet another embodiment, a given reactor uses 5 or less catalysts and 3 or less catalysts.

One or more catalysts charged in the production method of the present invention can be uniformly dissolved in a fluid reaction medium or can form a non-uniform solid phase in a reactor. The operation with a uniformly dissolved catalyst is advantageous, especially when the catalyst system not supported on the carrier is uniformly dissolved in the polymerization system. Catalysts that are not supported on a carrier dissolved in the polymerization system are also preferred. When the catalyst is present as a solid phase in the polymerization reactor, the catalyst may or may not be supported. Silica, silica-alumina and other similar carriers are particularly useful as carriers, as further described below. The catalyst can also be supported on structural carriers such as monoliths with straight or curved passages, reactor walls, internal tubes and the like. These structural carriers are well known in the field of heterogeneous catalysts. When the catalyst is supported, operation with dispersed particles is preferred. When the catalyst is supported on dispersed particles, it is preferable to perform an operation in which the catalyst is not recovered. That is, the catalyst is left in the polymerized product of the production method of the present invention.

In the production method of the present invention, both uniform and heterogeneous catalyst combinations can be used simultaneously in one or more reactors in the polymerization reactor area. That is, any of the reactors described in the section on polymerization of the present invention may contain one or more homogeneous catalysts and one or more heterogeneous catalysts at the same time. Similarly, in the production method of the present invention, any combination of the homogeneous catalyst and the heterogeneous catalyst described in the section of the polymerization reaction apparatus of the present invention can be used. These combinations are intended when some or all reactors use a single catalyst, and when some or all reactors use one or more catalysts.

One or more catalysts charged into the production method of the present invention can be supported on the particles, which can be dispersed in a fluid polymerization medium or contained in a fixed catalyst bed. When the supported catalyst particles are dispersed in the fluid reaction medium, they can be left in the polymerized product or before the product is recovered from the fluid reactor effluent in a separation step usually downstream of the polymerization reactor region. Can also be separated from the product. When the catalyst particles are recovered, the catalyst particles can be discarded or reused with or without regeneration treatment.

The catalyst can be introduced into the reactor in a number of ways. For example, the catalyst can be introduced with or separately from the feedstock containing the monomer. The catalyst can also be introduced into the reactor through one or more inlets. If many inlets are used to introduce the catalyst, these inlets can be provided at essentially the same or different locations along the reactor. Further, when a plurality of inlets are used to introduce the catalyst, the composition and supply amount of the catalyst passing through each inlet may be the same or different. Adjustment of catalytic amount and type via different inlets allows adjustment of polymer properties such as molecular weight distribution, composition, composition distribution, crystallinity and the like.

In order to reduce the cost of the catalyst, a compound that decomposes impurities that damage the catalyst and reduce its activity can be optionally supplied to the reactor. These impurity-degradable compounds are called scavengers in the practice of polymerization.

Any type of scanvenger compound capable of decomposing impurities that are harmful to the catalyst and reduce apparent catalyst productivity can be introduced into the reactor.

The scavenger may be the same compound as or different from the compound applicable as a catalytic activator. Useful scavengers include alkyl-aluminum compounds, including alumoxane, preferably this scavenger is of formula AlR.^※₃One or more compounds represented by, where R^※Is C₁From C₂₀Hydrocarbyl group, preferably methyl, ethyl, butyl, hexyl, octyl, nonyl, decyl and dodecyl, preferably the scavenger is one or more trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum and the like. is there. The scavenger may also be the same as the catalytically active agent, for example an almoxane such as almoxane such as methylarmoxane (MAO), more than necessary to fully activate the catalyst. Can be introduced. The scavenger can be introduced with a feedstock containing monomers or with the addition of other feedstocks. The introduction of the scavenger together with the monomer-containing raw material is usually advantageous because the impurities contained in the monomer raw material can react with the scavenger before the monomer raw material comes into contact with the catalyst.

The scavenger can be uniformly dissolved in the polymerization reaction medium or can form a separated solid phase. A scavenger dissolved in a polymerization medium is advantageous.<u style="single">Catalytic system</u>

The production method described herein can be carried out in combination with an activator in a catalytic system containing one or more non-metallocene structures, a central metal and a catalytic compound of a heteroaryl ligand (where the metal is). (Selected from groups 4, 5, 6 of the periodic table of elements, lanthanide series, actinide series). Preferably, the transition metal is a Group 4 metal, in particular Ti or Zr or Hf. More specifically, in certain embodiments of the catalytic compound, the use of hafnium metals is preferred over zirconium metals for heteroaryl ligand catalysts. See WO 2006/38628 for more details on compounds of non-metallocene structures, central metals and heteroaryl ligands.

The catalyst compounds used in the practice of the present invention include catalysts containing an auxiliary ligand-hafnium complex, an auxiliary ligand-zyroxide complex, which can be optionally combined with an activator, in particular olefins, diolefins. Alternatively, it catalyzes the polymerization and copolymerization reaction with a monomer which is another unsaturated compound. Zirconium complexes, hafnium complexes, compositions or compounds using the disclosed ligands are within the scope of catalysts useful in the practice of the present invention. The metal-ligand complex may be neutral or charged. The ligand-to-metal ratio can also vary, and the exact ratio depends on the nature of the ligand and metal-ligand complex. The metal-ligand complexes can take different forms, for example they may be monomers, dimers or higher orders.

For example, a suitable ligand useful for practicing the present invention may be broadly characterized by the following general formula (1).<img file="JP2010520366A_D0001.tif" />Where R¹Is a ring having 4 to 8 atoms generally selected from the group consisting of substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and substituted heteroaryl, such as R.¹Will be characterized by the general formula (2).<img file="JP2010520366A_D0002.tif" />Where Q¹And Q⁵Is the substituent of the ring substituted with an atom other than the atom E, where E is selected from the group consisting of carbon and nitrogen, and Q¹Or Q⁵At least one of them is bulky (defined as having at least two atoms). Q _qRepresents additional substituents that can be substituted on the ring, q is 1,2,3,4 or 5, and Q "is hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl. , Heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl, silyl, boryl, phosphino, amino, thio, sereno, halide, nitro, and combinations thereof. Selected. T is -CR²R³-And-Si R²R³A cross-linking group selected from the group consisting of-, R²And R³Are hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl, silyl, It is independently selected from the group consisting of boron, phosphino, amino, thio, sereno, arylide, nitro and combinations thereof. J'' is generally selected from the group consisting of heteroaryls and substituted heteroaryls, and specific examples for specific reactions are described herein.

Also, for example, in some embodiments, the catalytic ligand used in the practice of the present invention is of the general formula M (L)._nMay be combined with a metal catalytic compound which can be characterized by, M is Hf or Zr, preferably Hf, L are independently arylides (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl, substituted. Cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alcoholix, aryloxy, hydroxy, boryl, silyl, amino, amine, hydride, allyl, diene , Sereno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalic acids, carbonates, nitrates, sulfuric acids and combinations thereof. n is 1,2,3,4,5 or 6.

Preferred ligand-metal complexes useful in the present application are generally characterized by the following equation (3).<img file="JP2010520366A_D0003.tif" />Where M is zirconium or hafnium; R¹And T are as defined above. J'''is a substituted heteroaryl, two atoms bonded to metal M, at least one of these atoms is a heteroatom, and one atom of J''' is donated to M. The other atoms are selected from the group consisting of those bonded by covalent bonds. And, L¹And L²Are independently halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, Hydroxy, Boryl, Cyril, Amino, Amine, Hydride, Allyl, Diene, Sereno, Phosphino, Phosphine, Carboacids, Thio, 1,3-Dionates, Succinic Acids, Carbonates, Nitrate, Sulfates and Groups Selected from a group of combinations.

In the present invention, "non-metallocene" means that the metal of the catalyst is not bound to a substituted or unsubstituted cyclopentadienyl ring. Typical non-metallocene structure catalysts for central metals and heteroaryl ligands are US Provisional Patent Application No. 60 / 246,781 filed on November 7, 2000 and No. 60 / 301,666 filed on June 28, 2001. Described in the issue, these are incorporated herein by reference. In addition, a useful non-metallocene structure, a central metal and a catalyst for heteroaryl ligands (and a useful activator with it) are also described in WO 2003/040201. See especially pages 36, 18-64, 30. Also, catalysts for central metals and heteroaryl ligands of typical non-metallocene structures described in US Patent Application No. 7,087,690, filed November 25, 2003, are incorporated herein by reference.

In the present specification, "catalyst of non-metallocene structure, central metal and heteroaryl ligand" refers to a catalyst generated from the ligand described in the formula (1). As used in this term, "heteroaryl" includes substituted heteroaryl. Terms "hydrocarbyl", "substituted hydrocarbyl", "alkyl", "substituted alkyl", "heteroalkyl", "cycloalkyl", "substituted cycloalkyl", "heterocycloalkyl", "substituted heterocycloalkyl", "aryl" , "Substituted aryl", "heteroaryl", "substituted heteroaryl", "arco-shiki", "silyl", "boryl", "phosphino", "phosphine", "amino", "amine", "thio", "Seleno" and "saturated", "unsaturated" are defined in WO 03/040201, which are incorporated herein by reference.<u style="single">Ligand</u>

Ligands useful in the catalysts used in the practice of the present invention are broadly characterized as monoanionic ligands with amine and heteroaryl or substituted heteroaryl groups. The catalytic ligand used in the practice of the present invention is referred to as a non-metallocene ligand for the present invention and is characterized by the following general formula (1).<img file="JP2010520366A_D0004.tif" />Where R¹Generally consists of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, and combinations thereof. Very widely selected from the herd. In many embodiments, R¹Are substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl and substituted heteroaryl, R¹Is a ring with 4 to 8 atoms in the ring, generally selected from the group consisting of those characterized by the general formula (2). General formula (2)<img file="JP2010520366A_D0005.tif" />Where Q¹And Q⁵Is a substituent at the ortho position of the atom E, E is selected from the group consisting of carbon and nitrogen, and Q¹Or Q⁵At least one of them is bulky (defined as having at least two atoms). Q¹And Q⁵Is independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and silyl, but Q¹And Q⁵Are neither methyl. Q _pIs an additional substituent that can be substituted on the ring, q is 1,2,3,4 or 5, and Q "is hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, Selected from the group consisting of heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alcoholicyl, allyloxyl, silyl, boryl, phosphino, amino, thio, sereno, halide, nitro and combinations thereof. T is -CR²R³-And-SiR²R³A cross-linking group selected from the group consisting of-, R²And R³Hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl, silyl, boryl , Hosphino, Amino, Thio, Sereno, Arylide, Nitro and combinations thereof are independently selected. J'' is generally selected from the group consisting of heteroaryls and substituted heteroaryls, and specific embodiments for a particular reaction are described herein.

In a more specific embodiment, a ligand having a non-metallocene structure suitable for the present invention may be characterized by the following general formula (4).<img file="JP2010520366A_D0006.tif" />Here R¹And T are defined as above, R⁴, R⁵, R⁶And R⁷Each of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl, It is independently selected from the group consisting of silyl, boryl, phosphino, amino, thio, sereno, arylide, nitro and combinations thereof.

In certain more specific embodiments, the ligands of the present invention may be characterized by the following general formula (5).<img file="JP2010520366A_D0007.tif" />Q here¹, Q⁵, R⁴, R⁵, R⁶And R⁷Is as defined above. Q², Q³, Q⁴, R², And R³Are hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl, silyl, It is independently selected from the group consisting of Boryl, Hosphino, Amino, Thio, Sereno, Nitro and combinations thereof.

In another more specific embodiment, the ligand of the present invention suitable for the present application is characterized by the following general formula (6).<img file="JP2010520366A_D0008.tif" />Where R¹, R², R³, R⁴, R⁵And R⁶Is as defined earlier. In this embodiment R⁷Substituents are substituted with aryl or substituted aryl groups and R¹⁰, R¹¹, R¹²And R¹³Is hydrogen, halo, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, silyl. , Boryl, phosphino, amino, thio, sereno, nitro and combinations thereof, independently selected and optionally 2 or more R¹⁰, R¹¹, R¹²And R¹³Groups may be bonded to form a fused ring system with 3 to 50 non-hydrogen atoms. R¹⁴Are hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, silyl, It is selected from the group consisting of boron, phosphino, amino, thio, sereno, arylide, nitro and combinations thereof.

In a more specific embodiment, the ligand of the present invention is characterized by the following general formula (7).<img file="JP2010520366A_D0009.tif" />Here R²--R⁶, R¹⁰--R¹⁴And Q¹--Q⁵Are all as defined above.

In some embodiments, R²Is preferably hydrogen. Also preferably R⁴And R⁵Each of them is hydrogen and R⁶Is hydrogen or R⁷May be combined with to form a fused ring system. Also, R³Is benzyl, phenyl, 2-biphenyl, t-butyl, 2-dimethylaminophenyl (2- (NMe)₂)-C₆H₄-) (Here Me is methyl), 2-methoxyphenyl (2-MeO-C)₆H₄It is preferably selected from the group consisting of-), anthracenyl, mesityl, 2-pyridyl, 3,5-dimethylphenyl, o-tolyl and 9-phenanthrenyl. Also, R¹Is mesityl, 4-isopropylphenyl (4-Pr)ⁱ-C₆H₄-), Naftil, 3,5- (CF₃)₂, -C₆H₃, 2-Me-naphthyl, 2,6- (Prⁱ)₂-C₆H₃-, 2-biphenyl, 2-Me-4-MeO-C₆H₃, 2-Bu^t-C₆H₄-, 2,5- (Bu^t)₂-C₆H₃-, 2-Prⁱ-6-Me-C₆H₃-, 2-Bu^t -6-Me-C₆H₃-, 2,6-Et₂-C₆H₃-, 2-sec-Butyl-6-Et-C₆H₃-Preferably selected from the group consisting of. Also, R⁷Hydrogen, phenyl, naphthyl, methyl, anthranil, 9-phenanthrenyl, mesityl, 3,5- (CF)₃)₂-C₆H₃-, 2-CF₃-C₆H₄-, 4-CF₃-C₆H₄-, 3,5-F₂-C₆H₃-, 4-FC₆H₄-, 2,4-F₂-C₆H₃-, 4- (NMe₂)-C₆H₄-, 3-MeO-C₆H₄-, 4-MeO-C₆H₄-, 3,5-Me₂-C₆H₃-, O-trill, 2,6-F₂-C₆H₃-Or R⁷Is R⁶To form a fused ring system, such as quinoline.

Also optionally, R of 2 or more⁴, R⁵, R⁶Or R⁷The groups may be bonded to form a fused ring system with a pyridine ring and 3-50 non-hydrogen atoms, such as a quinoline group. In these embodiments, R³Are aryl, substituted aryl, heteroaryl, substituted heteroaryl, primary and secondary alkyl groups and PY₂Selected from the group consisting of, Y is selected from the group consisting of aryl, substituted aryl, heteroaryl and substituted heteroaryl.

Arbitrarily, in (6) and (7) of the above equation, R⁶And R¹⁰May combine to form a ring system with 5-50 non-hydrogen atoms. For example, R⁶And R¹⁰When is bonded to methylene, the skeleton of this ring becomes 5 atoms, which may or may not be replaced by other atoms. Also, for example, R⁶And R¹⁰When combined to form ethylene, the skeleton of this ring becomes 6 atoms, which may or may not be replaced by other atoms. Substituents of this ring are halo, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, It can be selected from the group consisting of aryloxy, silyl, boryl, phosphino, amino, thio, sereno, nitro and combinations thereof.

In certain embodiments, the ligand is a novel compound, from which ordinary technicians in the art can identify such compounds. An example of a novel ligand compound comprises a compound generally characterized by equation (5) above, wherein R.²Is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl and substituted aryl. And R³Is the formula-PZ¹Z²Is a phosphine group characterized by Z¹And Z²Is independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl, heterocycloalkyl, heterocycle, aryl, substituted aryl, heteroaryl, silyl, alkoxy, aryloxy, amino and combinations thereof. A particularly preferred embodiment of these compounds is Z¹And Z²Are independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl, aryl and substituted aryl. And more specifically, it is phenyl. Where Q¹, Q³And Q⁵Is selected from the group consisting of alkyl and substituted alkyl, respectively, and each Q²And Q⁴Is hydrogen. And R⁴, R⁵, R⁶And R⁷Are hydrogen respectively. See WO 2006/38628 for more details on useful ligands.

The catalytic ligands of the invention may be synthesized using known procedures. See, for example, Advanced Organic Chemistry, Wiley, New York 1992 (4.sup.th, Ed). In particular, the ligands of the present invention may be synthesized using the two-step procedure disclosed on pages 42-44 of WO 03/040201 and outlined in Scheme 1.<u style="single">Composition</u>

After synthesizing the desired ligand, it can be combined with metal atoms, ions, compounds or other metal catalytic compounds. In some applications, the ligands of the present invention may be combined with metal compounds or catalysts, and the product of such a combination is not determined even if the product is produced. For example, the ligand may be added to the reaction vessel at the same time as the metal and the metal catalyst compound together with the reaction raw material, the activator, the scavenger and the like. In addition, the ligand can be modified before or after the addition of the metal catalyst, for example by a deprotonation reaction or some other modification.

In the above formula, the metal catalytic compound is characterized by the general formula Hf (L) n, where L is independently arylide (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl. , Heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, hydroxy, boryl, silyl, amino, amine, hydride, allyl, diene, sereno , Phosphino, phosphine, carboxylic acids, thio, 1,3-dionates, oxalic acids, carbonates, nitrates, sulfuric acids and combinations thereof. n is 1, 2, 3, 4, 5 or 6. Hafnium catalysts are monomers, dimers or higher-order structures. It is well known that hafnium metals usually contain some zirconium impurities. Therefore, the present invention uses hafnium having a purity suitable for commercial use. Specific examples of suitable hafnium catalysts include, but are not limited to,: HfCl₄, Hf (CH)₂Ph)₄, Hf (CH)₂CMe₃)₄, Hf (CH)₂SiMe₃)₄, Hf (CH)₂Ph)₃Cl, Hf (CH₂CMe₃)₃Cl, Hf (CH₂SiMe₃)₃Cl, Hf (CH₂Ph)₂Cl₂, Hf (CH)₂CMe₃)₂Cl₂, Hf (CH)₂SiMe₃)₂Cl₂, Hf (NMe)₂)₄, Hf (NEt)₂)₄And Hf (N (SiMe)₃)₂)₂Cl₂.. The Lewis base adducts in these examples are also suitable as hafnium catalysts, for example ethers, amines, thioethers, phosphines and the like are suitable as Lewis bases.

For formulas 5 and 6, the metal catalyst compound may be characterized by the general formula M (L) n. Where M is hafnium or zirconium and each L is arylide (F, Cl, Br, I), alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocyclo. Alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, hydroxy, boryl, silyl, amino, amine, hydride, allyl, diene, sereno, phosphino, phosphine, carboxylic acids, thio, 1,3-dionate. Classes, oxalic acids, carbonates, nitrates, sulfates and combinations thereof are independently selected. n is usually 4. It is well known that hafnium metals usually contain some zirconium impurities. Therefore, the present invention uses hafnium or zirconium having a purity suitable for commercial use. Suitable hafnium and zirconium catalysts and specific examples include, but are not limited to: HfCl₄, Hf (CH)₂Ph)₄, Hf (CH)₂CMe₃)₄, Hf (CH)₂SiMe₃)₄, Hf (CH)₂Ph)₃Cl, Hf (CH₂CMe₃)₃Cl, Hf (CH₂SiMe₃)₃Cl, Hf (CH₂Ph)₂Cl₂, Hf (CH)₂CMe₃)₂Cl₂, Hf (CH)₂SiMe₃)₂Cl₂, Hf (NMe)₂)₄, Hf (NEt)₂)₄And Hf (N (SiMe)₃)₂)₂Cl₂, ZrCl₄, Zr (CH)₂Ph)₄, Zr (CH)₂CMe₃)₄, Zr (CH)₂SiMe₃)₄, Zr (CH)₂Ph)₃Cl, Zr (CH₂CMe₃)₃Cl, Zr (CH₂SiMe₃)₃Cl, Zr (CH₂Ph)₂Cl₂, Zr (CH)₂CMe₃)₂Cl₂, Zr (CH)₂SiMe₃)₂Cl₂, Zr (NMe)₄, Zr (NeEt)₂)₄And Zr (N (SiMe)₃)₂)₂Cl₂。

The Lewis base adducts of these examples are also suitable as hafnium catalysts, for example, ethers, amines, thioethers, phosphines and the like are suitable as Lewis bases.

The molar ratio of ligand to metal catalytic compound is typically in the range of about 0.01: 1 to 100: 1, more preferably in the range of about 0.1: 1 to about 10: 1.<u style="single">Metal-ligand complex</u>

The present invention is in part related to the use of metal-ligand complexes with a non-metallocene structure. Generally, the ligand is mixed with a suitable metal catalyst compound, either before or at the same time that the mixture is brought into contact with the reaction material (eg, monomer). When the ligand is mixed with the metal catalytic compound, a metal-ligand complex can be formed, which must be catalyzed or activated to catalyze. The metal-ligand complexes described herein are referred to as 2,1 or 3,2 complexes, the first number representing the number of coordinating atoms and the second number representing the charge of the metal. .. Thus, the 2,1-complex has two coordinating atoms and a single negative charge. In another embodiment of the present invention, it is a complex that generally coordinates 3,2 to the center of the metal, where 3,2 occupies three coordination positions of the metal, two of which are anionic and the rest. Refers to a ligand having a neutral Lewis base type coordination.

First, looking at the metal-ligand complex of 2,1-non-metallocene structure, the metal-ligand complex is characterized by the following general formula (8).<img file="JP2010520366A_D0010.tif" />Where T, J'', R¹, L and n are as defined above. x is 1 or 2. J''heteroaryls may or may not be coordinated, but are represented as bonds. More specifically, the non-metallocene ligand complex may be characterized by equation (9). Equation (9)<img file="JP2010520366A_D0011.tif" />Where R¹, T, R⁴, R⁵, R⁶, R⁷, L and n are defined as above. x is 1 or 2. In one preferred embodiment, x = 1 and x = 3. In addition, the Lewis base adducts of these metal-ligand complexes are within the scope of the present invention, for example, ethers, amines, thioethers, phosphines and the like are suitable as Lewis bases.

More specifically, the metal-ligand complex having a non-metallocene structure of the present invention may be characterized by the general formula (10).<img file="JP2010520366A_D0012.tif" />The parts that can be changed here are generally defined above. So, for example, Q², Q³, Q⁴, R², R³, R⁴, R⁵, R⁶, And R⁷Independently hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl, Independently selected from the group consisting of silyl, boryl, phosphino, amino, thio, sereno, nitro and combinations thereof, optionally 2 or more R⁴, R⁵, R⁶And R⁷May form a fused ring system with a pyridine ring and 3-50 non-hydrogen atoms, for example to form a quinoline group. Also, optionally, R², R³, And R⁴Any combination of the above may be combined to form a ring structure. Q¹And Q⁵Is selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl. However, Q¹And Q⁵Are neither methyl. Each L is halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, hydroxy. , Boryl, Cyril, Amino, Amine, Hydride, Allyl, Diene, Sereno, Phosphino, Phosphine, Carboacids, Thio, 1,3-Dionates, Phosphoric Acids, Carbonates, Nitrate, Sulfates and Combinations thereof Selected independently of the group. n is 1,2,3,4,5 or 6 and x is 1 or 2.

In other embodiments, the 2,1 metal-ligand complex is characterized by the following general formula (11):<img file="JP2010520366A_D0013.tif" />Here, the modifiable site is generally defined above.

In yet another embodiment, the 2,1 metal-ligand complex of the present invention is characterized by the following general formula (12):<img file="JP2010520366A_D0014.tif" />Here, the modifiable site is generally defined above.

In a particularly preferred embodiment, the non-metallocene metal-ligand complex is represented by the formula on pages 50-51 of WO 03/040201.

Turning to the 3,2 metal-ligand non-metallocene complex used in the practice of the present invention, the metal-ligand complex is characterized by the general formula (13).<img file="JP2010520366A_D0015.tif" />Here, M is zirconium or hafnium. R¹And T are defined above. In J''', two atoms are bonded to metal M, at least one of these two atoms is a heteroatom, one atom of J''' is bonded to M by a coordinate bond, and the other atoms are shared. Selected from the group consisting of bound substituted heteroaryls. And L¹And L²Are independently halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, From hydroxy, boryl, silyl, amino, amine, hydride, allyl, diene, sereno, phosphino, phosphine, carboxylic acid, thio, 1,3-dionates, oxalic acids, carbonates, nitrates, sulfates and combinations thereof. It is selected from the group.

More specifically, the 3,2 metal-ligand non-metallocene complex of the present invention is characterized by the following general formula (14).<img file="JP2010520366A_D0016.tif" />Where M is zirconium or hafnium, T, R¹, R⁴, R⁵, R⁶, L¹And L²Is defined above. And E'is carbon or nitrogen and is part of a cyclic aryl, substituted aryl, heteroaryl, or substituted heteroaryl group.

More specifically, the 3,2 metal-ligand non-metallocene complex used in the practice of the present invention may be characterized by the general formula (15). General formula (15)<img file="JP2010520366A_D0017.tif" />Where M is zirconium or hafnium, T, R¹, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, L¹, L²Is defined above.

More specifically, the 3,2 metal-ligand non-metallocene complex of the present invention may be characterized by the following general formula (16).<img file="JP2010520366A_D0018.tif" />Where M is zirconium or hafnium and R², R³, R⁴, R⁵, R⁶, R¹⁰, R¹¹, R¹², R¹³, Q¹, Q², Q³, Q⁴, Q⁵, L¹, And L²Is defined above.

In the above formula, R¹⁰, R¹¹, R¹², And R¹³Is hydrogen, halo, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, allyloxy, silyl. , Boryl, phosphino, amino, thio, sereno, nitro, and combinations thereof are independently selected. Optional R¹⁰, R¹¹, R¹²And R¹³Groups may combine to form a fused ring system with 3-50 non-hydrogen atoms.

In addition, the Lewis base adduct of the metal-ligand complex of the above formula is also suitable. For example, ethers, amines, thioethers, phosphines and the like are suitable as Lewis bases.

The metal-ligand complex can be formed by techniques known to engineers in the art of the present application. In some embodiments, R¹⁴Is hydrogen, and the metal-ligand complex is formed by the metalization reaction (without or otherwise) shown in the reaction scheme on pages 54-55 of WO 03/040201. Specific examples of the 3,2 complex of the present invention include all of those described in WO 03/040201.

The ligand, complex or catalyst may be supported on an organic or inorganic carrier. Suitable carriers include silicas, aluminas, clays, zeolites, magnesium chloride, polyethylene glycols, polystyrenes, polyesters, polyamides, peptides and the like. The polymer carrier may or may not be crosslinked. Similarly, the ligand, complex or catalyst may be supported on a carrier similar to that known to engineers in the art of the present application. In addition, the catalysts of the present invention may be combined with other catalysts in a single reactor and / or used in a series of reactors (parallel or continuous) to form a blend of polymers. You may.

The metal complex used in the present invention is catalytically activated in combination with an activation co-catalyst or using activation techniques. Suitable activation co-catalysts used herein are neutral Lewis acids such as alumoxane (modified or unmodified), Group 13 element compounds substituted with hydrocarbyl groups of C1-C30, especially tri (hydrocarbyl) aluminum-. Or tri (hydrocarbyl) boron compounds and their halogenated (including perhalogenated) derivatives, each hydrocarbyl group or halogenated hydrocarbyl group having 1 to 10 carbons. More specifically, it is a perfluorolated tri (aryl) boron compound, and most specifically, tris (pentafluorophenyl) boron. Also, non-coordinating, compatible, non-coordinating ion-forming compounds (including the use of such compounds under oxidizing conditions), especially compatible non-coordinating anions ammonium, phosphonium, The use of salts of oxonium, carbonium, sililium or sulfonium, or compatible non-coordinating anion and ferrocene ion salts are used. In addition, a combination of a three-dimensional bulky electrolyte (described in more detail later), the above-mentioned activation co-catalyst and the technique used thereof is used. The above activation co-catalysts and activation techniques have already been described for different metal complexes in the following references. US Pat. No. 5,153,157 and US Pat. No. 5,064,802, EP-A-277,003, EP-A-468,651 (same as US Pat. No. 07 / 547,718), US Pat. No. 5,721,185 and US Pat. No. 5,350,723. ..

The almoxane used as an activation auxiliary catalyst in the present invention is of the formula (R).⁴_X(CH₃) yAlO_nAnd R⁴Is a linear, branched or cyclic C1 to C6 hydrocarbyl group, x contains integers from 0 to about 1, y from about 1 to 0, and n from about 3 to about 25. Preferred alumoxane compounds, called modified methylarmoxane, are R.⁴Is a linear, branched or cyclic C3 to C9 hydrocarbyl group, x is from about 0.15 to about 0.50, y is from about 0.85 to about 0.5, and n contains an integer between 4 and 20. More preferably, R⁴Is isobutyl, tertiary butyl, or n-octyl, x is from about 0.2 to about 0.4, y is from about 0.8 to about 0.6, and n contains integers from 4 to 15. The above mixture of alumoxane may also be used in the practice of the present invention.

Most preferably, alumoxane is (R)⁴_X(CH₃) yAlO)_n And R⁴Is isobutyl or tertiary butyl, x is about 0.25, y is about 0.75, and n is about 6 to about 8.

A particularly useful armoxane is the so-called modified armoxane, preferably modified methylarmoxane (MMAO), which is completely soluble in alkane solvents, such as heptane, with very small amounts of trialkylaluminum, if any. Techniques for synthesizing such modified alumoxane are disclosed in US Pat. No. 5,041,584 (incorporated by citation). Almoxane useful as an activation co-catalyst in the present invention may also be made as disclosed in US Pat. Nos. 4,542,199, 4,544,762, 4,960,878, 5,015,749, 5,041,583, 5,041,585. good. Various alumoxans are available from distributors, such as the Akzo-Nobel company, and include MMAO-3A, MMAO-12 and PMAO-IP.

A combination of neutral Lewis acids, in particular trialkylaluminum compounds with 1 to 4 carbons in each alkyl group and halogenated tri (hydrocarbyl) boron with 1 to 10 carbons in each hydrocarbyl group. Combinations with compounds, especially tris (pentafluorophenyl) borane, and non-polymerizable, non-coordinating ion-forming compounds with neutral Lewis acids, especially tris (pentafluorophenyl) borane, are also useful. It is an activation auxiliary catalyst.

A suitable ion-forming compound useful as an auxiliary catalyst in one embodiment of the present invention is a non-coordinating anion, A, which is compatible with a cation, which is a Bronstead acid capable of giving a proton.^-including. As used herein, the term "non-coordinating" does not coordinate to catalytic complexes containing Group 4 metals or catalytic derivatives resulting from them, or only weakly coordinates to such complexes. , Still means an anion or substance that remains active enough to be sufficiently easily replaced by a neutral Lewis base. Non-coordinating anions move anionic substituents or parts thereof to said cations, especially when functioning as charge-neutralizing anions in cationic metal complexes, thereby forming neutral complexes. Anion that never happens. "Compatible anions" do not decompose and become neutral when the initially formed complex decomposes, and interferes with the subsequent polymerization of interest and other uses of the complex. Not an anion.

Preferred anions include a charged metal or a single coordination complex containing a metallic center, the anion capable of neutralizing the charge of an active catalytic species (metal cation) and having this activity. The catalyst species may be formed when these two components are combined. Also, the anion should be sufficiently active to be replaced by an olefinic, diolefinic and acetylene unsaturated compound or another neutral Lewis base such as ether or nitrile. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus and silicon. Compounds containing anions containing coordination complexes containing single metal or metalloid atoms are, of course, well known, and many such compounds containing one boron atom, especially in the anion portion, are commercially available. Has been done.

In one embodiment of the present invention, the activation co-catalyst may be represented by the following general formula. : [L^*-H]⁺_d[A^d-] Where L^*Is a neutral Lewis base, [L^*-H]⁺Is Bronstead Acid, A^d-Is d^-A non-coordinating, compatible anion with a charge of, and d is an integer from 1 to 3. More preferably, A^d-Is the formula [M'^{k +}Q_n^’]^d-Where k is an integer from 1 to 3, n'is an integer from 2 to 6, n'-k = d, and M'is an element selected from Group 13 of the periodic table of elements. , Each Q is hydride, dialkylamino, halide, hydrocarbyl, hydrocarbyloxy, halogen-substituted hydrocarbyl, halogen-substituted hydrocarbyloxy and halogen-substituted silylhydrocarbyl groups (perhalogenated hydrocarbyl-, perhalogenated hydrocarbi). Selected independently of (including loxi-, and silylhydrocarbyl peroxide groups), this Q has up to 20 carbons. However, the number of halogenated Q (Q halide) is 1 or less. An example of a suitable hydrocarbyl oxide Q group is disclosed in US Pat. No. 5,296,433.

In a more preferred embodiment, d is 1, that is, the counterion has a single negative charge, A.^-Is. The boron-containing activation co-catalyst, which is particularly useful in the preparation of the catalyst of the present invention, may be represented by the following general formula. [L^*-H]⁺[BQ₄]^-Here [L^*-H]⁺Is as already defined. B is boron in oxidation state 3 and Q is a hydrocarbyl-, hydrocarbyloxy-, hydrocarbyl fluoride-, hydrocarbyloxy fluoride-, or silylhydrocarbylfluoride group with up to 20 non-hydrogen atoms. However, when Q is hydrocarbyl, it is at most one case. Most preferably, Q is an arylfluoride group, in particular a pentafluorophenyl group, in each case.

Preferred [L^*-H]⁺The cations include N, N-dimethylanilinium and tributylammonium. Another suitable ion-forming, activating co-catalyst comprises a cationic oxidant represented by the following formula and a salt of a non-coordinating, compatible anion. (Ox.^{e +})_d(A^d-)_e Here Ox.^{e +}Is a cationic oxidant with an e + charge, where e is an integer from 1 to 3. And A^d-And d are as defined above.

Examples of cationic oxidants are ferrosenium, hydrocarbyl-substituted ferrosenium, Ag.⁺, Or Pb⁺²including. Preferred A^d-A preferred embodiment of the above is an anion, in particular a tetrakis (pentafluorophenyl) boric acid ester, defined above for a Bronstead acid containing an activation co-catalyst.

Another suitable ion-forming, activating co-catalyst is of the formula [C].⁺A^-It contains a compound which is a salt of a non-coordinating and compatible anion with a carbenium ion represented by. Here [C]⁺Is a C1-C20 carbenium ion, A^-Is as defined earlier. The preferred carbenium ion is a trityl cation, i.e., triphenylmethylium.

For more stable ion-forming and activation co-catalyst, formula R₃Si (X')_q⁺A^-It contains a compound which is a salt of a non-coordinating and compatible anion with a silylium ion represented by. Where R is C1-C10 hydrocarbyl, and X', q and A^-Is as defined above.

Preferred silylium salt activation co-catalysts are trimethylsilylium tetrakis (pentafluorophenyl) borate ester, triethylsilylium (tetrakispentafluoro) phenylborate ester and their ether-substituted adducts. The silylium salt activation co-catalyst is trimethylsilylium tetrakis (pentafluorophenyl) borate ester, triethylsilylium (tetrakis pentafluoro) phenylborate ester and their ether-substituted adducts. The silylium salt has already been disclosed to the public in J. Chem.Soc. Chem.Comm., 1993,383-384, along with Organometallics, 1994,13,2430-2443 by Lambert, JB et al.

Certain complexes of alcohols, mercaptans, silanols and oximes and tris (pentafluorophenyl) borate esters are also effective catalytic activators and may be used according to the present invention. Such co-catalysts are disclosed in US Pat. No. 5,296,433.

The molar ratio of catalyst / co-catalyst used is preferably 1: 10,000 to 100: 1, more preferably 1: 5,000 to 10: 1, and most preferably 1: 100 to 1: 1. In one embodiment of the present invention, the co-catalyst can be used in combination with a tri (hydrocarbyl) aluminum compound having 1 to 10 carbons in each hydrocarbyl group. A mixture of activation co-catalysts may also be used. The advantageous performance of removing impurities such as oxygen, water and aldehydes from the polymerization mixture makes it possible to use these aluminum compounds. Preferred aluminum compounds are trialkylaluminum compounds having 1 to 6 carbons in each alkyl group, particularly those in which the alkyl group is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl. .. The molar ratio of the metal complex to the aluminum compound is preferably 1: 10,000 to 100: 1, more preferably 1: 1000 to 10: 1, preferably 1: 500 to 1: 1 or 200: 1 to 1: 1 or From 50: 1 to 1: 1. The most preferred borane activation cocatalyst contains a strong Lewis acid, especially tris (pentafluorophenyl) borane.

In certain embodiments disclosed herein, two or more different catalysts can be used, including the use of mixed catalysts. When using multiple catalysts in addition to the catalyst of the non-metallocene central metal and the heteroaryl ligand, how one or more olefin monomers can be copolymerized to form an interpolymer or homopolymer. Can also be used in the embodiments of the present invention in combination with a catalyst of a non-metallocene central metal and a heteroaryl ligand. For certain embodiments, it is preferred that additional selection criteria such as molecular weight achievement and / or comonomer incorporation performance are met. A catalyst consisting of a heteroaryl ligand having a substituent different from the central metal of two or more non-metallocene structures can be used in the practice of certain embodiments disclosed in the present application. Suitable catalysts that can be used in combination with the non-metallocene central metal and heteroaryl ligand catalysts disclosed in the present application are metallocene catalysts and distorted catalysts, multi-site catalysts (Ziegler-Natta catalysts) and theirs. Includes, but is not limited to, variants of.

Certain suitable classification catalysts are disclosed in US Pat. No. 5,064,802, US Pat. No. 5,132,380, US Pat. No. 5,703,187, US Pat. No. 6,034,021, EP 0468651, EP 0514828, WO 93/19104 and WO 95/00526. It is a catalyst that has been used. Other suitable classification catalysts are the metallocene catalysts disclosed in US Pat. No. 5,044,438, US Pat. No. 5,057,475, US Pat. No. 5,096,867 and US Pat. No. 5,324,800. It should be noted that these catalysts may be considered as metallocene catalysts and both are sometimes referred to as single-site catalysts in the art.

Another suitable classification of catalyst is a metal complex containing a substituted indenyl group as disclosed in US Pat. No. 5,965,756 and US Pat. No. 6,015,868. Other catalysts are disclosed in simultaneous continuation applications. That is, US Application 09 / 230,185 and US Application 09 / 715,380, and US Provisional Applications 60 / 215,456, 60 / 170,175 and 60 / 393,862. All disclosures of these earlier patent applications are incorporated herein by reference in their entirety. These catalysts tend to have the ability to achieve relatively high molecular weight.

Other catalysts, co-catalysts, catalyst systems and activation techniques that may be used in the practice of the inventions disclosed herein are WO 96/23010, published August 1, 1996, March 25, 1999. WO 99/14250 published in, WO 98/41529 published on September 24, 1998, WO 97/42241 published on November 13, 1997, Scollard et al.<u style="single">J.Am.Chem.Soc</u> 1996,118,10008-10009, European Patent No. 0468537 published November 13, 1996 B1, WO97 / 22635 published on June 26, 1997, EP0949278A2 published on October 13, 1999, EP0949279A2 published on October 13, 1999, EP1063244A2 published on December 27, 2000, US patent No. 5,408,017, US Patent No. 5,767,208, US Patent No. 5,907,021, WO88 / 05793 published on August 11, 1988, WO88 / 05793 published on August 11, 1988, WO93 / published on December 23, 1993. 25590, U.S. Patent No. 5,599,761, U.S. Patent No. 5,218,071, WO 90/07526 published on July 12, 1990, U.S. Patent No. 5,972,822, U.S. Patent No. 6,074,977, U.S. Patent No. 6,013,819, U.S. Patent No. 5,296,433, US patent 4,874,880, US patent 5,198,401, US patent 5,621,127, US patent 5,703,257, US patent 5,728,855, US patent 5,731,253, US patent 5,710,224, US patent 5,883,204, US patent No. 5,504,049, U.S. Patent No. 5,962,714, U.S. Patent No. 5,965,677, U.S. Patent No. 5,427,991, WO93 / 21238 published on October 28, 1993, WO94 / 03506 published on February 17, 1994, October 1993. WO93 / 21242 released on 28th, WO94 / 00500 released on January 6, 1994, WO96 / 00244 released on January 4, 1996, WO98 / 50392 released on November 12, 1998, May 16, 2002 Published WO 02/38628, Wang et al.<u style="single">Organometallics</u> 1998,17,3149-3151, Younkin et al.,<u style="single">Science</u> 2000,287,460-462, by Chen and Marks<u style="single">Chem.Rev.</u>Disclosure in 2000,100,1391-1434, by Ittel et al.<u style="single">ChemRev</u>. 2000, 100, 1391-1434, Alt and Koppl, Chem. Rev. 2000, 100, 1205-1221, Resconi et al., Chem. Rev 2000, 100, 1253-1345. , Disclosure by Ittel et al., Chem Rev. 2000,100, 1169-1203, by Coates.<u style="single">ChemRev</u>. 2000, 100, 1223-1251, Brady, III, et al., U.S. Pat. No. 5,093,415, Murray et al., U.S. Pat. No. 6,303,719, Saito et al., U.S. Pat. No. 6,303,719. Includes those disclosed in No. 5,874,505 and WO 96/13530 published May 9, 1996. Catalysts and co-catalysts disclosed in U.S. Application 09 / 230,185 dated January 15, 1999, U.S. Patent No. 5,965,756, U.S. Patent No. 6,150,297, and U.S. Application No. 09/715,380 filed November 17, 2000. , Catalytic systems are also useful. All disclosures of these previously mentioned patents and / or patent applications are incorporated herein by reference in their entirety to the extent that they are not inconsistent with the present specification.

In a preferred embodiment, the polymerization system contains less than 5% by weight, preferably less than 4% by weight, more preferably less than 3% by weight, more preferably less than 2% by weight, more preferably less than 1% by weight, more preferably of the polar species. Contains 1000 wt ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm and more preferably less than 10 ppm. Polar species include oxygen-containing compounds (excluding alumoxane) such as alcohols, oxygen, ketones, aldehydes, acids, esters and ethers.

In another embodiment, the polymerization system contains trimethylaluminum and / or triethylaluminum in 5% by weight, 4% by weight, more preferably 3% by weight, more preferably 2% by weight, more preferably 1% by weight, more preferably. It contains less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, more preferably less than 10 ppm.

In another preferred embodiment, the polymerization system is methylaluminum and less than 5% by weight trimethylaluminum or triethylaluminum, preferably less than 4% by weight, more preferably less than 3% by weight, more preferably less than 2% by weight, more. This preferably less than 1% by weight, more preferably less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, More preferably, it contains less than 10 ppm.<u style="single">Polymerization process</u>

The present invention relates to a method for polymerizing an olefin, which comprises contacting one or more olefins having at least three carbons with a catalyst compound and an activator in a catalytic system containing one or two fluid phases in a reactor. In a preferred embodiment, the fluid reaction medium is in a liquid state, forming a single liquid phase. One or more continuous or parallel reactors may be used in the present invention. The catalyst compound and activator are sent as a solution or slurry, or separately to the reactor, activated in the line just before reaching the reactor, or pre-activated and activated in one. It is pumped to the reactor as a solution or slurry. The preferred operation is that the two solutions are activated in the line. The polymerization is carried out in a single reactor operation and the monomer, comonomer, catalyst / activator, scavenger and any modifier are continuously linked in a single reactor or in two or more reactors in series or in parallel. Is added to. When the reactors are linked in a continuous cascade, the catalytic compound can be added to the first of the continuous reactors. The catalytic compound may also be added to more than one reactor in a reactor cascade (eg, a continuous reactor cascade), with one component added to the first reaction and the other component added to the other downstream reactor. Alternatively, an additional catalyst (same or dissimilar) is added to the downstream reactor.

The continuous reactor cascade has two or more reactors that are continuously connected, and the effluent of the upstream reactor is fed to the next reactor downstream of the reactor cascade. In addition to the effluent of the upstream reactor, the feedstock of any reactor can be increased by any combination of additional monomers, catalysts, scavengers, or new or recycled solvents. In a parallel reactor array, the reactors or continuous cascade reactors that form a branch of the parallel reactor array are called a reactor train.

The polymerization method described in the present application proceeds well in a tubular reactor and an autoclave (also referred to as a stirring tank reactor). The autoclave reactor can be operated in batch or continuous mode. Continuous operation is preferred in commercial production in order to obtain better productivity and thereby reduce manufacturing costs. The tubular reactor group is preferred for continuous operation. Autoclave reactors typically have a device length to diameter ratio of 1: 1 to 20: 1 (preferably 4: 1 to 20: 1) and are typically equipped with a high speed (up to 2000 RPM) multi-blade stirrer. When the autoclave has a low reactor length-to-diameter ratio (eg, less than 4), the feed stream is typically charged at only one point of the reactor side length. Larger diameter reactors may have multiple inlets at approximately identical positions on the side length of the reactor, but these are radially dispersed for faster mixing of the components and feed components within the reactor. Has been done. In the case of a stirring tank reactor, it is possible and often preferable to charge the catalyst separately from another charging port. Such input prevents the possibility of forming high heat points in the non-stirring supply zone between the mixing point and the stirring zone of the reactor. It is also possible and sometimes preferable to charge at two or more points of the reactor side length. For example, the lateral length to diameter ratio is about 4: 1 to 20: For a reactor of 1, the reactor may contain up to 6 different inlets. In addition, in relatively large autoclaves, one or more side clamps support the high speed stirrer. These fixtures can also divide the autoclave into two or more zones. The mixing blades of the stirrer are different for each zone, and different degrees of plug flow and back mixing are performed in the separated zones almost independently. Two or more autoclaves with one or more zones can be linked in a continuous cascade to increase residence time or adjust polymer structure. As mentioned above, a series of reactor cascades typically consists of two or more reactors connected in succession, with at least one upstream reactor effluent fed to the next reactor downstream of this cascade. In addition to the effluent of the upstream reactor, the feedstock for any reactor in a continuous cascade can be increased by a combination of additional monomers, catalysts or new solvents or reusable feed streams. Two or more monomer reactors can also be arranged in parallel. Such average Each sequence of the column sequence is called a reactor row. These reactor trains then include themselves one reactor or reactor continuous cascade to form a combination of continuous and parallel reactors.

The tubular reactor may be used in the manufacturing method disclosed in the present application. The tubular reactor is equipped with external cooling and one or more inlets along the (tubular) reaction zone. As in an autoclave, these inlets act as inlets for monomers (eg, propylene), one or more comonomer, catalysts, or mixtures thereof. In tubular reactors, external cooling often increases monomer conversion compared to autoclaves. In autoclaves, low surface-to-volume ratios prevent large amounts of heat from being removed. The tubular reactor has a special outlet valve that can transmit a shock wave of pressure backwards along the tube. The shock wave facilitates the removal of polymer residues formed on the reaction wall during operation. Alternatively, the tubular reactor may be formed with a smooth, unpolished internal surface to accommodate wall adhesion. The tubular reactor may generally operate at pressures up to 360 Mpa, may have a length of 100-2000 m or 100-4000 m, and may have an inner diameter of 12.5 cm (or less than 10 cm). Generally, tubular reactors have a reactor length-to-diameter ratio of 10: 1 to 50,000: 1 and may include up to 10 different inlets along the lateral length (preferably 1 to 10 different injections). Positions, or different injection positions from 1 to 6).

A sequence of reactors combining a tubular reactor and an autoclave can also be used in the manufacturing process of the invention. In such an example, the autoclave usually precedes a tubular reactor, or the two reactors belong to another sequence of reactors in a parallel reactor arrangement. In such a system, the catalyst and / or raw material components may be added at several points in the autoclave, especially along the tube length.

In both autoclaves and tubular reactors, the feedstock is cooled to near room temperature or below room temperature for maximum cooling during loading, thereby producing maximum polymer within maximum operating temperature limits. Is preferable. In the operation of the autoclave, it operates at the start of operation. However, if the first mixing zone is demixed, the pretreatment heater does not necessarily have to operate after the reaction reaches steady state. In a tubular reactor, the first part of the double tube is uncooled and heated, and then continuously operated. A useful tubular reactor is plug Characterized by flow). The plug flow is a flow pattern in which the difference in flow velocity in the radial direction is the smallest. In both multi-zone autoclaves and tubular reactors, the catalyst can be charged at one or more points along the reactor, rather than at the inlet alone. The catalyst raw materials charged at the inlet and other inlets may be the same or different in content, density, concentration, etc. Designed polymers can be made by choosing to feed different catalyst raw materials. At the outlet valve of the reactor, the pressure drops below the pressure at which critical phase separation occurs. Therefore, the downstream separator may include a high polymer layer and a low polymer layer. Normally, the conditions in this separator remain supercritical and the temperature remains higher than the crystal temperature of the polymer product. The autoclave or tubular reactor effluent is depressurized as it enters the high pressure separator (HPS).

In any of the plurality of reactor systems described only in the present application, only one reactor needs to contain a catalytic compound of a non-metallocene-structured central metal and a heteroaryl ligand described in the present application. Any of the other reactors may contain any other polymerization catalyst such as Ziegler-Natta polymerization catalyst, metallocene catalyst, Philippe type catalyst and the like. Other useful catalysts are described in WO 2004/026921, pages 21, paragraphs [0081] to 72, paragraph [00118]. A preferred catalyst for use in any of the reactors is a chiral metallocene catalytic compound used in combination with an activator. In a preferred embodiment, both a non-metallocene central metal and a catalyst compound of a heteroaryl ligand and a chiral metallocene compound are used. In another embodiment, a catalyst compound of a non-metallocene structure central metal and a heteroaryl ligand and a chiral metallocene compound are used in a continuous reaction apparatus or a parallel apparatus. A particularly useful metallocene compound is Me₂Si-Bis (2-R, 4-Phl-Indenyl) MX₂Where R is an alkyl group (eg, methyl group), Phl is phenyl or substituted phenyl, M is Hf, Zr, or Ti, and X is a halogen or alkyl group (eg Cl or methyl). Particularly useful metallocene compounds include 2-dimethylsilyl-bis (2-methyl, 4-phenyl-indenyl) zirconium dimethyl and 2-dimethylsilyl-bis (2-methyl, 4-phenyl-indenyl) zirconium dichloride.

At the outlet valve of the reactor, the pressure drops and the polymer begins to separate inactive substances such as unreacted monomers, comonomer, ethane, propane and solvents such as hexane and toluene. The temperature in this device is maintained above the crystallization point of the polymer product, but the pressure may be below the critical point. The pressure should be high enough to condense the monomer, eg propylene, with standard cooling water. The liquid recirculation flow can then be recirculated to the reactor by a liquid pump system rather than the supercompressor required for the polyethylene device. The relatively low pressure in this separator lowers the monomer concentration in the liquid polymer phase and greatly reduces the polymerization rate. In some embodiments, this polymerization rate may be low enough to allow the system to operate without the addition of catalytic toxins or "killers". If a catalytic killer is required (eg to prevent reactions during high pressure recirculation), measures must be taken to remove any potential catalytic toxins from the recycled high concentration propylene monomer containing stream. For example, the use of fixed floor adsorbents or removal with alkylaluminum.

Alternatively, HPS can be operated above the critical pressure of the monomer or monomer mixture, but may be performed within the monomer / polymer two-phase region. This is an economically preferred method when the polymer is produced by a modified high pressure polyethylene plant (HPPE). The reused HPS component at the top undergoes cooling and dewaxing before returning to the second compressor.

The polymer from this intermediate or high pressure device is then fed to the low pressure separator through other decompression steps. The temperature of this device is maintained above the melting point of the polymer and the polymer from this device can be fed directly to the extruder or static mixer as a liquid. The pressure in this device is kept low and is sent to the above capacitor and pump system to recover unreacted monomers and the like using a compressor.

In addition to the autoclave reactor and the tubular reactor, or a combination of these reactors, a loop reactor can be used in the manufacturing process disclosed herein. In this type of reactor, the polymer is removed by continuously entering the monomer at different points along the loop while the in-line pump continuously circulates the contents (reaction solution). Raw material / product retrieval rate controls total average residence time. The cooling jacket removes heat of reaction from the loop. Generally, the inlet temperature of the raw material is close to or lower than the ambient temperature to cool the exothermic reaction in the reactor operating at a temperature higher than the polymer crystallization temperature. This loop reactor has a diameter of 41 to 61 cm, a length of 100 to 200 meters, and can operate at a pressure of 25 to 30 Mpa. In addition, the in-line pump continuously circulates the polymerization system within the loop reactor. Alternatively, the loop reactor operates at a pressure of 1.5 to 30 Mpa.

U.S. Pat. No. 6,355,741 discusses a reactor with at least two loops that is useful in practicing the present invention when one or two loops operate under supercritical conditions. U.S. Pat. No. 5,326,835 describes the process for producing bimodal polymers. The first reactor of this process is a loop-type reactor that occurs on low-boiling hydrocarbons with inert polymerization. After the loop reactor, the reaction medium moves to the gas phase reactor where the gas phase polymerization occurs. Polymers exhibit a bimodal molecular weight distribution because two very different environments make up the polymer. The two-step method can be improved for use by the procedure of the present invention. For example, the loop-type reactor in the first step can use propylene as a monomer and a propylene-based reaction medium instead of the inert low-boiling hydrocarbon.

PCT public WO19 / 14766 is a step (a) a step of continuously supplying an olefin monomer and a catalyst system to the reaction device together with a metallocene component and an auxiliary catalyst component, and (b) this in the polymerization zone reaction device under the condition of increasing the pressure. A step of continuously polymerizing the monomers, (c) a step of continuously removing the polymer / monomer mixture from the reactor, (d) a step of continuously separating the monomers from the molten polymer, (e) a phase with a large amount of monomers under reduced pressure. It describes a production method consisting of a step of forming a phase containing a large amount of polymer and (f) a step of separating a monomer from a reactor. The polymerization zoning technique described in the above production method can be carried out using the production conditions of the present invention.

The polymerization method disclosed in the present application may have a short reaction device residence time of 0.5 seconds, a long residence time of many hours, or a residence time of 1 second to 120 minutes, or 1 minute to 60 minutes, or 5 minutes to 30 minutes. In another embodiment, when operated with one or more reactors, the residence time of either reactor (or all reactors combined) is also less than 30 minutes, preferably less than 20 minutes, preferably less than 10 minutes, preferably less than 10 minutes. Is less than 5 minutes.

The conversion rate is obtained by dividing the total amount of polymer collected during the reaction time by the amount of monomer added to the reactor. The conversion rate from monomer to polymer in the above-mentioned production method can be as high as 90%. For practical reasons, for example, a low conversion may be preferable in order to reduce the viscosity. Also, for practical reasons, for example, the maximum conversion rate may be preferred in order to reduce the cost of monomer reuse. Therefore, the manufacturing method of the invention is 80% or less, or 60% or less, between 3-80%, or between 5-80%, or between 10-80%, or between 15-80%, or 20. Between -80%, or between 25-60%, or between 3-60%, or between 5-60%, or between 10-60%, or between 15-60%, or 20-60 Between%, or between 10-50%, or between 5-40%, or between 10-40%, or between 20-50%, or between 15-40%, or between 20-40% During, or between 30-40% conversion rates, the implementation conversion rate may be preferably higher than 5%, or higher than the 10% conversion rate, and preferably higher than the 20% conversion rate.<u style="single">Comonomer, dual catalysts and polymer structure</u>

Polymers may be designed for reactors with multiple inlets for catalysts and raw materials. The use of two or more catalysts with different molecular weights and structural performance allows for a wide range of product compositions (eg, linear polymers mixed with bimodal, branched long chain polymers).

When a large number of reactors are used, polymer blends can be produced. In some embodiments, a blend of homopolymer and copolymer is made by using at least two juxtaposed or contiguous reactors. Homopolymers can be polypropylene, polybutene, polyhexene, polyoctene and the like. In a preferred embodiment, the homopolymer is polypropylene. Copolymers are made from any combination of two or three components of ethylene, propylene, butene-1, hexene-1, octene-1, styrene, norbornene, 1,5-hexadiene, and 1,7-octadien. In a more preferred embodiment, the copolymer is made from a two-component combination of ethylene, propylene, butene-1, hexene-1, styrene, norbornene, 1,5-hexadiene and 1,7-octadien. In another preferred embodiment, the copolymer is an ethylene-propylene, propylene-butene-1, propylene-hexene-1, propylene-butene-1, ethylene-butene-1, ethylene-hexene-1, ethylene-octene-1 copolymer. Is. When the polymer blend is made in a continuous reactor, a single monomer-containing feedstock is fed to one or more upstream reactors and a comonomer feedstock is added to one or more downstream reactors. Parallel reactor arrangements are advantageous in the production of polymer blends, as adjusting the ratio of homopolymers to copolymers is difficult with continuous reactors.<u style="single">Catalyst deactivation</u>

When the polymerization is complete, the reactor effluent is reduced in pressure to an intermediate pressure well below the cloud point pressure. This separates the polymer-rich phase and the propylene-rich phase to be further purified. Propylene is compressed as it is returned to the reactor. Sometimes it is necessary to heat the reactor effluent before reducing the pressure to avoid separation of the solid polymer phase that causes fouling.

This separation is usually done in a device known as a high pressure separator (HPS). The vessel also has a considerable residence time, so the catalytic activity is inactivated by the addition of water, alcohol, or polar species such as sodium / calcium stearate. The choice and amount of deactivator will vary depending on the nature of the product as well as the need to remove propylene and comonomer for reuse, given the low volatility of the deactivator.

Alternatively, intermediate separation can be performed at a pressure well below the critical point, resulting in a lower monomer concentration in the high pressure separator, which can result in relatively low reactivity. A relatively small amount of continuous polymerization in this device may not be a problem, so if an undesired reaction does not occur in a high or intermediate pressure recycling system, a catalytically deactivated compound as is done in the PE process. Addition could be omitted. If the deactivating compound is not added, the removal of the deactivating agent can be omitted.<u style="single">Selection of purity of propylene raw material</u>

Propylene is generally available in two levels of purity. 99.5% polymer quality and about 93-95% chemical quality. The choice of raw material determines the level of propane required from recycling to avoid excessive dilution of the raw material by the inert propane. The presence of propane in the reactor and HPS increases the pressure of the cloud point curve for a given temperature, but reduces the efficiency of polymerization by reducing the concentration of propylene (and other olefins) in the reactor. The increase in cloud point pressure due to propane widens the operating conditions of HPS. Copolymerization of propylene with a limited amount of ethylene has a similar effect of increasing cloud point pressure due to the low levels of ethylene in the HPS.<u style="single">Low pressure separation operation</u>

The low pressure separator (LPS) can be used in the manner described herein. The LPS, which operates at a pressure slightly higher than the atmospheric pressure described above, has light components, reaction raw materials, and the like so that it becomes a polymer melt having a low content of volatile components when it enters the final extruder or static mixer. It's just a simple quasi-critical flash of oligomers.<u style="single">Polymer products</u>

The polymer produced by the production method of the present invention may have any structure such as a block, a linear type, a star type, a branched type, and a combination thereof. Some embodiments of the invention produce polypropylene and polypropylene copolymers with a unique microstructure. The production method of the present invention can be carried out so that a novel isotactic and syndiotactic composition can be produced. In another embodiment, the method of the present invention makes a crystalline polymer.

The polymers produced in the present application usually have a melting point of up to 170 ° C, preferably 70 ° C to 165 ° C (also called the melting temperature). The polymers produced in the present application are 2,000 to 1,000,000 g / mol, or 10,000 to 1,000,000 g / mol, 15,000 to 600,000 g / mol, or 25,000 to 500,000 g / mol, or 35,000 to 350,000 g / mol. It usually has a weight average molecular weight. Alternatively, the polymer produced in the present application may have a Mw of 30,000 or more, preferably 50,000 g / mol or more, preferably 100,000 g / mol or more. In a preferred embodiment, the polymer produced in the present application may have a melting point of 80 ° C. or higher, preferably 100 ° C. or higher, preferably 125 ° C. or higher.

The manufacturing method of the invention is heat of fusion ΔH of 1-60 J / g, 2-50 J / g or 3-40 J / g._fTo produce a polymer with. In another embodiment, the method of manufacture of the present invention comprises a heat of fusion of up to 110 J / g, preferably 60 to 100 J / g, more preferably 75 to 90 J / g, ΔH._fTo produce a polymer with.

The production method described in the present application can produce a polymer containing little or no ash derived from a catalyst or carrier. In a preferred embodiment, the polymer produced in the present application comprises less than 1 wt% silica, preferably less than 0.1 wt% silica, preferably less than 100 wtppm silica, preferably less than 10 wtppm silica. In a preferred embodiment, the polymer produced in the present application comprises less than 1% metal, preferably less than 0.1 wt% metal.

The invention of the present application also It relates to a method of polymerizing an olefin, which comprises contacting propylene with the following at a temperature of 1.65 ° C to 150 ° C, a pressure between 1.72Mpa and 43.5Mpa. 1) A catalytic system containing one or more active agents, one or more central metals having a non-metallocene structure, and a catalytic compound of a heteroaryl ligand. A system selected from the system or the actinide system. 2) Optionally, one or more comonomer components selected from the group consisting of ethylene and C4 to C12 olefins (preferably 0 to 20 wt% based on the weight of all monomers and comonomer contained in the raw material). 3) 20-65 wt% diluent or solvent based on the total weight of raw materials supplied to the polymerization reactor. 4) Optionally, a scavenger (preferably 0-5 wt% scavenger) based on the total weight of the raw material fed to the polymerization reactor. here, a) 15 wt% or more of olefin monomer and one of the comonomer (preferably 30 wt% or more) Included in the polymerization system b) Contains 80 wt% or more of propylene based on the weight of all monomers and comonomer contained in the raw material, and c) The polymerization occurs at a temperature higher than the solid-liquid phase transition temperature of the polymerization system and at a pressure higher than the cloud point pressure of this polymerization system of 1 Mpa or less. d) The polymerization reaction occurs at: (1) a temperature below the critical temperature of the polymerization system, or (preferably) (2) a pressure below the critical pressure of this polymerization system. 2. The method of paragraph 1 in which the solvent contains C4 to C7 hydrocarbons. 3. The method of paragraph 1 or 2, further comprising obtaining a polymer having a Mw of 30,000 or more, preferably 50,000 or more, preferably 100,000 or more. 4. The method of paragraphs 1, 2 or 3, further comprising obtaining a polymer having a melting point of 80 ° C. or higher, preferably 100 ° C. or higher, preferably 125 ° C. or higher. 5. The method described in any of paragraphs 1 to 4, wherein propylene is contained in the polymerization system in an amount of 20 wt% or more, preferably 25 wt% or more, preferably 30 wt% or more. 6. The method described in any of paragraphs 1-5, where the temperature is between 70 ° C and 140 ° C, preferably between 80 ° C and 130 ° C. 7. The method described in any of paragraphs 1-6, wherein the pressure is between 2 and 30 Mpa, preferably between 2.5 and 25 Mpa. 8. The method described in any of paragraphs 1-7, wherein the solvent and diluent are hexane. 9. The method described in any of paragraphs 1 to 8 in which propylene is contained in the raw material in an amount of 75 wt% or more, preferably 80 wt% or more. Ten. method described in any of paragraphs 1-9, wherein the solvent comprises C4 to C7 hydrocarbons, which are saturated aliphatic hydrocarbons. 11. The method described in any of paragraphs 1-10, where the temperature is higher than the cloud point temperature of the polymerization system and the pressure is less than 30Mpa. 12. The method described in any of paragraphs 1-11, wherein the metal is a metal selected from Hf, Ti and Zr. 13. The method described in any of paragraphs 1-12, wherein the solvent and / or diluent is contained in an amount of 50 to 65 wt% based on the weight of the raw material. 14. The method described in any of paragraphs 1-13, wherein the comonomer is contained in the raw material in an amount of 0.1 to 20 wt%. 15. The method described in any of paragraphs 1-14, wherein the raw material consisting of monomer, comonomer, solvent and diluent is 55-100 wt% propylene monomer and 0-45 wt% ethylene, butene, Hexene, 4-methylpentene, dicyclopentadiene, norbornene, C₄-C₂₀₀₀Α-olefin, C₄-C₂₀₀₀Α, internal-diolefin and C₄-C₂₀₀₀Contains one or more comonomer selected from the group consisting of α, ω-diolefins. 16. The method described in any of paragraphs 1-15, wherein the comonomer comprises one or more ethylene, butene, hexene-1, octene-1, dodecene-1 or decene-1. 17. The method described in any of paragraphs 1 to 16 in which a catalytic compound of a central metal and a heteroaryl ligand having a non-metallocene structure contains a ligand represented by the formula (1). How to be a metallocene.<img file="JP2010520366A_D0019.tif" />Here R¹Is expressed by equation (2).<img file="JP2010520366A_D0020.tif" />Where Q¹And Q⁵Is a substituent that binds to the ring other than the atom E, Q¹Or Q⁵At least one of them has at least two atoms. E is selected from the group containing carbon and nitrogen. q is 1,2,3,4 or 5. Q^’’Hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl, silyl, boryl It is selected from the group consisting of (boryl), phosphino, amino, thio, sereno, arylide, nitro, and combinations thereof. T is -CR²R³-And-SiR²R³A cross-linking group selected from the group consisting of-. R²And R³Are independently hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, respectively. , Aryloxyl, Cyril, Boryl, Phosphino, Amino, Thio, Sereno, Halide, Nitro and combinations thereof. J'' is selected from the group consisting of heteroaryls and substituted heteroaryls. 18. A catalytic compound of a central metal and a heteroaryl ligand having a non-metallocene structure according to the method described in any of paragraphs 1 to 17 is represented by the formula 3.<img file="JP2010520366A_D0021.tif" />Where M is zirconium or hafnium, R¹, T, R²And R³Is as defined in paragraph 3. J'''' is selected from the group consisting of substituted heteroaryls with two atoms bonded to metal M, at least one of these atoms is a heteroatom and one atom of J'''' is a donating bond. Is bound to M, and the others are bound by covalent bonds. L¹And L²Independently, halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, hetecycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, Aryloxy, hydroxy, Boryl, Cyril, Amino, Amine, Hydride, Allyl, Diene, Sereno, Phosphino, Hosphin, Carboacids, Thio, 1,3-Dionates, Phosphoric Acids, Carbonates, Nitrate, Sulfates and Theirs Selected from the group consisting of combinations of groups. 19. The catalyst of the non-metallocene central metal and the heteroaryl ligand is represented by equation (4) in the method described in any of paragraphs 1-18.<img file="JP2010520366A_D0022.tif" />Here, M, L¹And L²Is as defined in paragraph 4. R⁴, R⁵, R⁶Independently, hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, allyloxyl. , Cyril, Boryl, Hosphino, Amino, Thio, Sereno, Nitro and combinations thereof, optionally 2 or more R⁴, R⁵And R⁶The groups may combine to form a fused ring with 3-50 non-hydrogen atoms fused to a pyridine ring, or optionally R.², R³And R⁴Any combination of groups may be combined to form a ring structure. R¹, T, R²And R³Is as defined in paragraph 3, and E "is carbon or nitrogen and is part of a cyclic aryl, substituted aryl, heteroaryl or substituted heteroaryl group. 20. In the method of any of paragraphs 1-19, the catalytic compound is represented by one or both of the following formulas.<img file="JP2010520366A_D0023.tif" />21. The method described in any of paragraphs 1-20, wherein the activator comprises almoxane, preferably methylalmoxane. twenty two. The method described in any of paragraphs 1 to 21, wherein the activators are triethylammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, tripropylammonium tetrakis (pentafluorophenyl) borate, N, N-Dimethylanilinium n-butyltris (pentafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4, 6-Tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, di- (i-propyl) ammonium tetrakis (penta) Fluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium Tetrax (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, diphenyloxonium tetrakis (pentafluorophenyl) Borate, di (o-trill) oxonium tetrakis (pentafluorophenyl) borate, di (2,6-dimethylphenyl) oxonium tetrakis (pentafluorophenyl) borate, diphenylsulfonium tetrakis (pentafluorophenyl) borate, di (o-trill) ) Sulfonium tetrakis (pentafluorophenyl) borate, di (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, trimethylsilylium tetrakis (pentafluorophenyl) borate, and triethylsilirium (tetrakis pentafluoro) phenyl borate A method that includes one or more of them. 23. The method described in any of paragraphs 1-22, wherein the activator is trimethylammonium. Tetraphenylborate, Triethylammonium tetraphenylborate, Tripropylammonium tetraphenylborate, Tri (n-butyl) ammonium tetraphenylborate, Tri (tert-butyl) ammonium tetraphenylborate, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) Borate, Tripropylammonium Tetrakiss (Pentafluorophenyl) Borate, Tripropylammonium Tetrax- (2,3,4,6-Tetrafluorophenyl) Borate, Tri (n-Butyl) Ammonium Tetrakiss (Pentafluorophenyl) Borate, Tri ( sec-butyl) Ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium Tetraquis (pentafluorophenyl) borate, N, N-diethylanilinium Tetrakis (pentafluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) Tetrakis (pentafluorophenyl) borate, N, N-dimethyl-(2,4,6-trimethylanilinium) Tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis -(2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, dimethyl (tert-butyl) ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, dimethyl (tert-butyl) ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis- 2,3,4,6-tetrakisfluorophenyl) borate, N, N-dimethylanilinium Tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium Tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate , Trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate, tri (tert-butyl) ammonium Tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium Tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanili) Nium) Tetrakis (perfluoronaphthyl) borate, trimethylammonium Tetrakis (perfluorobiphenyl) borate, triethylammonium Tetrax (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorophenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl Anilinium tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorophenyl) borate, trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tripropylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) Borate, tri (n-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tri (tert-butyl) ammonium Tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-dimethylanilinium Tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, di- (iso- Propropyl) ammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluoro) Phenyl) borate, tropyrium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate, benzene (diazonium) tetraphenylborate, tropylium Tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, triethylsilium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluoro) Phenyl) borate, tropyrium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triphenylcarbenium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triphenylphosphonium tetrakis- (2) , 3,4,6-Tetrafluorophenyl) Borate, Triethylsilylium Tetrakis- (2,3,4,6-Tetrafluorophenyl) Borate, benzene (Diazonium) Tetrakis- (2,3,4,6-Tetrafluoro) Phenyl) borate, tropyrium tetrakis (perfluoronaphthyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilylium Tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, tropyrium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethyl Syrilium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, tropirium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (3,5-bis (trifluoro)) Methyl) phenyl) borate, triphenylphosphonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triethylsilylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate or benzene (diazonium) tetrakis ( A method comprising one or more of 3,5-bis (trifluoromethyl) phenyl) borates. 24. The method described in any of paragraphs 1-20, wherein the activator comprises N, N-dimethylanilinium tetra (perfluorophenyl) borate and / or triphenylcarbenium tetra (perfluorophenyl) borate. How to be a waste. 25. The method described in any of paragraphs 1-24, wherein a diluent or solvent is present and the diluent or solvent comprises a fluorinated hydrocarbon. 26. The method described in any of paragraphs 1-25, wherein the polymerization occurs in a tubular reactor. 27. The method of paragraph 26, in which the tubular reactor has a length-to-inner diameter ratio of 10: 1 to 50,000: 1. 28. The method of paragraph 26 or 27, wherein the reactor has 1 to 10 different loading positions or 1 to 6 different loading positions. 29. The method of paragraphs 26, 27 or 28, wherein the tubular reactor has an inner diameter of 100-4000 meters, preferably 100-2000 meters, and / or less than 12.5 cm, preferably less than 10 cm. How to be. 30. The method of paragraph 26, 27, 28 or 29, wherein the tubular reactor operates in multiple zones. 31. The method described in any of paragraphs 1-25, wherein the polymerization reaction occurs in an autoclave reactor. 32. The method of paragraph 31, wherein the autoclave reactor has a length-to-inner diameter ratio of 1: 1 to 20: 1, preferably 4: 1 to 20: 1. 33. In the method of paragraph 31, the autoclave reactor has a length to inner diameter ratio of 4: 1 to 20: 1, and the reactor has up to 6 different loading positions. 34. The method of paragraph 31, 32 or 33, wherein the autoclave reactor is operated in multiple zones. 35. The method of paragraphs 31, 32, 33 or 34, wherein the method (a) continuously supplies the olefin monomer, the catalytic compound, and the activator to the autoclave reactor and (b) 1.5 Mpa or more. The monomer is continuously polymerized under pressure, (c) the polymer / monomer mixture is continuously removed from the reactor, (d) the pressure is reduced to form a monomer-rich phase and a polymer-rich phase, and (e) continuously. It involves separating the monomer from the polymer and (f) circulating the optionally separated monomer into the polymerization step. 36. The method of any of paragraphs 1 to 25, wherein the polymerization is carried out in a loop reactor. 37. The method of paragraph 36, wherein the loop reactor has a diameter of 41 to 61 cm and a length of 100 to 200 meters. 38. The method of paragraph 36 or 37, wherein the loop reactor is operated at a pressure of 1.5 to 30 Mpa. 39. The method of paragraphs 36, 37 or 38, wherein the in-line pump continuously circulates the polymerization system through the loop reactor. 40. The method of paragraphs 36, 37, 38 or 39, wherein the method (a) continuously supplies the olefin monomer, the catalytic compound, and the activator to the loop-type reactor, and (b) 1.5 Mpa or more. The monomer is continuously polymerized under pressure, (c) the polymer / monomer mixture is continuously removed from the reactor, (d) the pressure is reduced to form a monomer-rich phase and a polymer-rich phase, and (e) the monomer is formed. A method that involves continuous separation from the polymer and (f) recirculation of the optionally separated monomers into the polymerization step. 41. The method described in any of paragraphs 1-39, wherein the polymerization occurs in multiple reactors. 42. The method described in any of paragraphs 1 to 41, wherein the polymerization method comprises two or more parallel reactors. 43. The method of paragraph 42, wherein one or more reactors arranged in parallel are agitated autoclave reaction measures. 44, paragraph 42 or 43, wherein one or more parallel reactors include a loop reactor. 45. The method of paragraph 42, 43 or 44, wherein one or more reactors arranged in parallel are tubular reactors. 46. The method of any of paragraphs 1-45, wherein the polymerization method uses two or more continuously arranged reactors. 47. The method of paragraph 41, 42 or 46, wherein the polymerization reaction is carried out in a tubular reactor and then in one or more autoclave reactors. 48. The method of paragraph 41, 42 or 46, wherein the polymerization reaction is carried out in a tubular reactor followed by one or more loop reactors. 49. The method of any of paragraphs 1-48, where the residence time in any one reactor (or the sum of all reactors) is less than 30 minutes, preferably less than 20 minutes, preferably less than 20 minutes. A method that is less than 10 minutes, preferably less than 5 minutes. 50. The method of any of paragraphs 1-49, wherein propylene is contained in the polymerization system at 30-40 wt%. 51. The method of any of paragraphs 1 to 50, wherein the solvent and diluent are contained in the polymerization system at 60 to 70 wt%. 52. A method according to any one of paragraphs 1 to 51, wherein the catalyst system is dissolved in the polymerization reaction system. 53. The method of any of paragraphs 1-52, wherein the catalytic system further comprises one or more metallocene catalytic compounds. 54. The method of any of paragraphs 1-53, wherein the product of the polymerization reaction method has a weight average molecular weight (Mw) of up to 2,000,000 g / mol as measured by gel permeation chromatography. How to be. 55. The method of any of paragraphs 1-54, wherein the product of the polymerization method has a melting point peak temperature of up to 170 ° C as measured by a differential scanning calorimeter. 56. The method of any of paragraphs 1-55, wherein the metal is selected from Group 5 of the Periodic Table of the Elements. 57. The method of any of paragraphs 1-55, wherein the metal is selected from Group 6 of the Periodic Table of the Elements. 58. The method of any of paragraphs 1-55, wherein the catalytic compound of the central metal and the heteroaryl ligand of the non-metallocene structure is a metal of either the actinide or lanthanide series of the periodic table of elements. A method that includes. 59. In the method of any of paragraphs 1-58, the propylene is applied to the reactor effluent from 2.5 to 10 M (molar), or 3 to 10 M, or 3.5 to 8 M, or 3.5 to 6 M, or The method that is included in 4-5M. 60. The method of any of paragraphs 1-59, wherein the raw material composition is about 35 wt% propylene, about 65 wt% isohexane, and optionally the reaction temperature is about 101 ° C.

<u style="single">Example</u>All operations were performed in a dry box with less than 10 ppm oxygen and water. All solvents were degassed with nitrogen and dried on a Na / K alloy before use. Catalytic compound A (shown below) was prepared according to the procedure generally described in WO 03/040201 A1, pages 90, lines 21-93, line 9.<u style="single">Catalyst precursor compound A</u><img file="JP2010520366A_D0024.tif" /><u style="single">Example 1-3</u>

In order to dry the reactor, a 37 cc autoclave reactor containing a magnetic rotor was heated under a dry nitrogen stream for about 1 hour to 120 ° C. The reactor was cooled and subsequently hexane (15.8 mL, 11.49 g, 133.3 mmol) and tri-n-octyl aluminum (0.080 mmol; added to a 4.2 mL solution of hexane) were added as scavengers. As a result, the total amount of hexane in the reactor is 20 mL. The total amount of tri-n-octylaluminum used is the target Al: M (where M = Zr or Hf) molar ratio of 300: 1 or less (ideally targeting ~ 200: 1). Each was adjusted as follows. The reactor is propylene gas (purity&gt; 99%, Airgas It was replaced with Corporation) and sealed to maintain the atmosphere of propylene. The reactor is then heated to 105 ° C, at which point additional liquid propylene (16.0 mL; 8.176 g) is added with a syringe pump to raise the pressure to ~ 600 psi (4.1 Mpa) and the contents are agitated. Was done. Toluene stock solution (0.001 g / ml) of catalyst precursor compound A and toluene stock solution (0.001 g / ml) of [N, N-dimethylanilinium] [Tetrakis (heptafluoronaphthyl) borate] in a nitrogen-substituted dry box. ) Was prepared separately. Using these stock solutions, i.e., catalyst precursor compound A (2.713 mL, 2.713 mg, 0.004 mmol) and [N, N-dimethylanilinium] [tetrakis (heptafluoronaphthyl) borate] (5.496 mL, 5.496 mg). , 0.0048 mmol) was dried and immediately added to a flask containing toluene (1.791 mL) to prepare an active catalyst solution. The mixture was stirred at room temperature for about 15 minutes. Next, in a dry box, 5.5 mL of this solution was filled into a pre-dried syringe pump, sealed and mounted on this 37 cc reactor. This activated catalytic toluene solution (~ 1 mL; 0.0004 mmol) was introduced via a syringe pump via a supply line (~ 1000 psi; 6.9 MPa) with a pressure higher than the reactor pressure (~ 600 psi; 4.1 MPa). After the addition of the catalyst, propylene was added to maintain a minimum pressure of 1000 psi (6.9 MPa). The temperature and pressure of the reactor were maintained for 30 minutes. Reactor pressure 1000 psi (6. Propylene was added to maintain 9 MPa). The reaction was terminated by discharging the contents into an outlet collection vessel attached to the reactor outlet line. After cooling, the product was recovered from the outlet collection vessel and reactor. The product was dried in a vacuum oven for 12 hours and the product was characterized by gel permeation chromatography (GPC) and differential scanning calorimetry (DSC).<img file="JP2010520366A_D0025.tif" />Activator B = [N, N-dimethylanilinium] [Tetrakis (Heptafluoronaphthyl) borate] TNOAl = tri-n-octylaluminum, Cat.A = catalyst precursor compound A<u style="single">Analytical method</u><u style="single">Differential scanning calorimetry (DSC)</u>

The phase transition is measured using a differential scanning calorimetry (DSC) when heated and cooled from the solid state and the molten state respectively. Crystallization temperature (Tc) and melting point (T)_m), The measurements were made using TA Instrument MDSC 2920 or Q1000 Tzero-DSC, and the data were analyzed using standard analytical software provided by the vendor. 3 to 10 mg of polymer was encapsulated in a flat aluminum dish and placed in the instrument at room temperature. The sample is cooled to -70 ° C and then 10 ° C / It was heated to 210 ° C at a heating rate of minutes. Each sample was maintained at a temperature of 210 ° C for 5 minutes and had a common thermal history. The crystallization behavior was evaluated by cooling the sample from the molten state to a temperature lower than the ambient temperature at a cooling rate of 10 ° C / min. The sample was kept cold for 10 minutes and well equilibrated in the solid state to a steady state. The second heating data was measured by heating this melt-crystallized sample in-situ at 10 ° C / min. The second heating data gives the phase behavior of the sample crystallized under the heat history conditions thus controlled. The melting points listed in Table 1 are the peak melting point temperatures of the second melt, unless otherwise stated. For polymers showing multiple peaks, the higher melt peak temperature is listed.

The area under the curve is the heat of fusion (H) that can be used to calculate the degree of crystallinity (also known as percent crystallinity)._f) Is used to determine. To determine the crystallinity of polypropylene, 8.7 kJ / mol as the equilibrium heat of fusion of 100% crystalline polypropylene (single crystal measurement) reported in B. Wunderlich, Thermal Analysis , Academic Press, Page 418, 1990. The value of is used. The percent crystallinity of polypropylene polymer is calculated using the formula [Area under curve (J / g) x42 g / mol / 8700 (J / mol)] x100%. Other polymers For, the percent crystallinity is calculated using the formula [area under curve (joules / gram) / B (joules / gram)] x100, where B is the heat of fusion of the homopolymer of the major monomer component. These values for .B may be obtained from John Wiley and Sons, New York, 1999, Polymer Handbook, 4th Edition.<u style="single">Gel Permeation Chromatography (GPC-DRI)</u>

This analysis was performed using a Waters GPCV 2000 (gel permeation chromatograph) with triple detection. These three detections are continuous, first with the Wyatt DAWN EOS MALLS 18 Angle Laser Light Scattering Detector, followed by the DRI (Differential Refractometer) detector, followed by the Differential Viscosity Detector. The output signal of the detector is collected by Wyatt's ASTRA software and analyzed using a GPC analyzer. Detailed GPC conditions are listed in Table 2.

Standards and samples were prepared in an inhibited TCB (1,2,4-trichlorobenzene). Four NBS polyethylene preparations were used to calibrate the GPC. The standard is specified in Table 2. These samples were accurately weighed, diluted to a concentration of ~ 1.5 mg / mL and recorded. The specimens and samples were placed in PL Labs 260 Heater / Shaker at 160 ° C for 2 hours. These were filtered and analyzed through a 0.45 micron steel filter cup.<img file="JP2010520366A_D0026.tif" />

All documents described in this application, including the application documents and / or test procedures on which priority is based, are incorporated herein by reference, except for any inconsistencies with this specification. Although some embodiments of the invention have been described and described, as evidenced by the general description and specific embodiments described above, various modifications are possible without departing from the essence and scope of the invention. .. Therefore, it is not intended to limit the invention by these descriptions. Also, in Australian law, the term "comprising" is synonymous with the term "including".