aluminoxane-based catalyst activators containing carbocationic agents and their use in polyolefin ca

专利摘要:
catalyst activators based on aluminoxane containing carbocationic agents and use thereof in polyolefin catalysts the present invention relates to an activator composition comprising (i) an organoaluminium compound; (ii) a carbocationic compound of formula r1 (x) n; wherein r1 is a hydrocarbyl; n varies from 1 to the number of possible substitutions of the hydrocarbyl group and each x is a labile leaving group; and (iii) an aluminoxane. the activator composition may also contain a vehicle support. this invention also provides a catalyst composition that comprises the activator composition described above and a transition metal component. this invention also provides methods of polymerizing a monomer which comprises carrying out such polymerization in the presence of one or more catalytic compositions according to the present invention.
公开号:BR112013022702A2
申请号:R112013022702
申请日:2012-03-08
公开日:2020-05-19
发明作者:Luo Lubin；P Diefenbach Steven；Wu Xiao
申请人:Albemarle Corp；
IPC主号:

专利说明:

“ALUMINOXAN-BASED CATALYST ACTIVATORS CONTAINING CARBOCATIONIC AGENTS AND USE OF THEM IN POLYOLEFINE CATALYSTS”
Background of the invention
Partially hydrolyzed alkyl aluminum compounds known as aluminoxanes (AO) are used to activate transition metals for olefin polymerization activity. One of these compounds, methyl aluminoxane (MAO), is an aluminum cocatalyst / activator often chosen in the industry. Considerable effort has been expended to improve the effectiveness of catalyst systems based on the use of aluminoxanes or modified aluminoxanes for olefin polymerization. Representative patents and publications in the field of use of aluminoxane include the following: US patent 5,324,800 to Welborn and others; US patent 4,752,597 to Turner; US Patents 4,960,878 and US 5,041,584 to Crapo et al.: WO 96102580 to Dall'occo et al; EP 0 277 003 and EP 0 277 004 by Turner; Hlatky, Truner and Eckman, J. Am. Chem. Soo., 1989, 111, 2728-2729; Hlatky and Upton, Macromolecules, 1996, 29, 8019-8020, US patent 5,153,157 to Hlatky and Truner; US patent 5,198,401 to Turner, Hlatky and Eckman; Brintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, 34, 1143-1170; and the like. Despite technological advances, many aluminoxane-based polymerization catalyst activators do not yet have the activation efficiencies required for commercial application, and require an unacceptably high aluminum load on an industrial scale, are expensive (especially MAO), and have other impediments for commercial implementation.
Lewis-based stabilized dialkyl aluminum cations derived from non-aluminoxane systems and their activation characteristics are described by Klosin and others in WO 2000/011006 and in Organometallics, 19 (2000), 4684-4686. The ionic MAO compound was isolated from regular nonionic MAO by treatment with a bidentate (or chelating) agent, for example, octamethyltrisiloxane by Sangokoya and others
2/44 (WO 2003/082879 and WO 2007/005400). Subsequently, by fixing the THE complex and dimethyl aluminum cation formed through the reaction of trityl-tetrakis (pentafluorophenyl) borate with trimethyl aluminum (TMA) in tetrahydrofuran (THF) in regular MAO treated with THF, Luo and others identified the THF complex and dimethyl aluminum cation formed in the THF treated MAO (WO 2009/029857 and US 2009/0062492). In addition, Luo and others also demonstrated that, through the treatment of a dimethyl aluminum cation precursor agent, so called, the number of dimethyl aluminum cations in MAO could be significantly increased and, consequently, the activation efficiency of the MAO would be greatly improved (Luo et al. In WO 2009/029857 and US 2009/0062492). More recently, through the design of a metallocene with starting groups detectable by NMR, the dimethyl aluminum cation precursor in MAO has been identified as the main active species to activate a metallocene by extracting the dimethyl aluminum cation precursor from of MAO to form a cationic bimetallic complex of metallocene leaving group bond, shown as A in reaction 1, as an example, which is further converted into a stable, fully alkylated, chelated cationic bimetallic complex, like B in reaction 1 ( Luo, et al., Advances in Polyolefins 2009, Meeting Abstract, Santa Rosa, California, 2009). Such fully alkylated stable cationic bimetallic complexes have since been recognized as the main metallocene-derived species formed when a metallocene is activated with MAO, for example, cationic bimetallic zirconocene species (Babushkin & Brinztinger, J. Am, Chem, Soc. , 2002, 124, 12869) and the cationic bimetallic titanocene species (Bryliakov, Talsi, and Bochmann, Organometallics, 2004,23,149).
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Precursor of dimethyl aluminum cation
Me*
Metallocene MAO (M = Ti, Zr, or Hi)
Dimethyl aluminum cation complex (1) ©
Cp ^ ³ z ^CH 3] XX (®)
Cp CHj CH ₃ J „MAO
Thus, there is a need to obtain AO-type compositions that have higher efficiencies to activate transition metals for polymerization of olefins compared to conventional, in particular, compositions with more active species, comprising the dialkyl aluminum cation or its precursor in aluminoxane activators, through more economically perfect methods to significantly reduce the aluminoxane ratio in a practical catalytic system to reduce the production cost of metallocene / single site catalysts.
Summary of the invention
The present invention relates to an activator composition comprising: (i) at least one supported aluminoxane intermediate (Component I), (ii) a compound having the formula R ¹ (X) n (Component II); wherein R ¹ is a hydrocarbyl group having from about 1 to about 20 carbon atoms; n is 1 to the number of possible substitutions of the hydrocarbyl group and each X can be anywhere in R ¹ and is independently halogen, -OSi (R ² ) 3, -N (Si (R ² ) 3) 2, -N (R ² ) 2; -SR ² ; -P (R ² ) 2; -CN or -OR ³ ; wherein each R ² is independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms; each R ³ is independently a hydrocarbyl having 1 to 20 carbon atoms, where when at least one R ² is a hydrocarbyl group; R ¹ and R ² or R ¹ and R ³ can be linked together to form a cyclic group; with the proviso that at least one X is not directly linked to an aryl group, and with the proviso that when X is not halogen, X is linked to a secondary or tertiary carbon, or a -CH2-aryl group; and (iii) a trihydrocarbyl aluminum compound having the formula AIR ₃ (Component III), where each R is
4/44 independently a C1-C20 hydrocarbyl group ·
The present invention also provides an unsupported activator composition, as well as a catalyst composition comprising the activator compositions and a transition metal component. The present invention also provides methods for polymerizing monomers comprising carrying out such polymerization in the presence of one or more catalyst compositions according to the present invention.
Detailed description of the invention
The present invention relates to an activator composition comprising: (i) at least one supported aluminoxane intermediate (Component I), (ii) a compound having the formula R ¹ (X) n (Component II); wherein R ¹ is a hydrocarbyl group having from about 1 to about 20 carbon atoms; n is 1 to the number of possible substitutions of the hydrocarbyl group and each X can be anywhere in R ¹ and is independently halogen, -OSi (R ² ) 3, -N (Si (R ² ) 3) 2, -N (R ² ) 2; -SR ² ; -P (R ² ) 2; -CN or -OR ³ ; wherein each R ² is independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms; each R ³ is independently a hydrocarbyl having from 1 to 20 carbon atoms, where when at least one R ² is a hydrocarbyl group; R ¹ and R ² or R ¹ and R ³ can be linked together to form a cyclic group; with the proviso that at least one X is not directly linked to an aryl group, and with the proviso that when X is not halogen, X is linked to a secondary or tertiary carbon, or a -CH2-aryl group; and (iii) a trihydrocarbyl aluminum compound having the formula AIR ₃ (Component III), wherein each R is independently a C 1 -C ₂₀ hydrocarbyl group.
The present invention also relates to a composition comprising: (i) a trihydrocarbyl aluminum compound having the formula AIR ₃ , wherein each R is independently a C ₁ -C ₂₀ alkyl; (ii) a compound having the formula R ¹ (X) _n ; wherein R ¹ is a hydrocarbyl group having about 3 to about 20 carbon atoms; n is 1 to the number of possible substitutions for the hydrocarbyl group and each X can be substituted anywhere in R ¹ and is
5/44 independently -OSi (R ² ) ₃ , -N (Si (R ² ) 3) 2, -N (R ² ) 2; -SR ² ; -P (R ² ) ₂ ; -CN or -OR ³ ; wherein each R ² is independently hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms; each R ³ is independently a hydrocarbyl having from 1 to 20 carbon atoms, where when at least one R ² is a hydrocarbyl group; R ¹ and R ² or R ¹ and R ³ can be linked together to form a cyclic group; with the proviso that at least one X is not directly linked to an aryl group, and with the proviso that at least one X is linked to a secondary or tertiary carbon, or a -CH ₂ -aryl group; and (iii) an aluminoxane.
The term "hydrocarbyl" as used here includes a hydrocarbon radical, which can be optionally substituted with a heteroatom (for example, oxygen, nitrogen, sulfur, phosphorus), or silicon in the chain. Examples of hydrocarbyl include, but are not limited to, alkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkyl, cycloalkenyl and combinations thereof.
The term "alkyl", as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tbutyl, pentyl and hexyl.
The term "aryl", as used herein, unless otherwise indicated, includes an organic radical derived from an aromatic hydrocarbon by removing a hydrogen, such as phenyl, naphthyl, indenyl and fluorenyl. "Arila" encompasses groups of fused rings in which at least one ring is aromatic.
The term "aralkyl" as used here indicates an "arylalkyl" group. Non-limiting example of an aralkyl group is benzyl (C ₆ H ₅ CH ₂ -) and methylbenzyl (CH ₃ C ₆ H4CH ₂ -).
The term "alkaryl" as used here indicates an "alkyl-aryl" group. Non-limiting examples of alkaryl are methyl-phenyl, dimethyl-phenyl, ethyl-phenyl, propyl-phenyl, isopropyl-phenyl, butyl-phenyl, isobutyl-phenyl and t-butyl-phenyl.
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The term "alkenyl", as used herein, unless otherwise indicated, includes portions of alkyl having at least one carbon-carbon double bond, where alkyl is as defined above. Examples of alkenyl include, but are not limited to, ethylene and propenyl.
The term "cycloalkyl", as used herein, unless otherwise indicated, includes portions of non-aromatic saturated cyclic alkyl, where alkyl is as defined above. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
The term "cycloalkenyl" as used herein, unless otherwise stated, includes portions of non-aromatic cyclic alkenyl, where alkenyl is as defined above. Examples of cycloalkyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl.
Unless otherwise indicated, all of the above hydrocarbon-derived groups may have from about 1 to about 20 carbon atoms (e.g., C 1 -C ₂₀ alkyl, C ₆ -C ₂ o aryl, C ₇ - alkaryl C _20, C ₇ C ₂₀ aralkyl) or 1 to about 12 carbon atoms (e.g., C _r C ₂ alkyl, C ₆ -C ₂ aryl, C ₇ -C ₂ alkaryl, aralkyl C ₇ -C | ₂ ), or from 1 to about 8 carbon atoms, or from 1 to about 6 carbon atoms, or from 1 to about 4 carbon atoms.
Supported aluminoxane intermediates (Compound I)
One of the components in the activator composition is a supported aluminoxane intermediate, which is derived from three components: 1) at least one support (or vehicle), 2) at least one organoaluminium compound, and 3) at least one oxygen source . The three components can be brought into contact in any order.
Preferably, the organoaluminium compound can be contacted with the oxygen source to form a soluble aluminoxane before contacting a support. The aluminoxane formed can contain at least a portion of hydrocarbyl having from one to about twenty carbon atoms. Such
7/44 aluminoxanes include, but are not limited to, alkyl aluminoxanes, cycloalkylaluminoxanes, arylaluminoxanes, aralkylaluminoxanes, or any combination thereof. Hydrocarbil-aluminoxanes can exist in the form of linear or cyclic polymers. In one aspect of the invention, aluminoxanes can be oligomeric materials, sometimes referred to as polyalkylaluminoxanes, containing the repeating unit (C),
and the chain end unit (D),
which can also have an AIR3 coordinated to meet the four coordinates of the aluminum center (D ’),
where R is a C1-C20 hydrocarbyl group and n is an integer from about 4 to about 20. The exact structure of aluminoxanes has not been defined and they can contain linear, cyclic, cross-linked species, or any combination thereof. Non-limiting examples of hydrocarbilaluminoxanes for use in the invention include methyl aluminoxanes (MAO), modified MAOs, ethylaluminoxanes (EAO), isobutylaluminoxanes (IBAO), n-propylaluminoxanes, noctilaluminoxanes, phenylaluminoxanes, or any combination thereof. Hydrocarbylalumininoxes can also contain up to about 20 mol percent (based on aluminum atoms) of portions derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, aryldisiloxanes, alkyl- disyloxanes, and the like to further improve activity, solubility
8/44 and / or stability.
Aluminoxanes can be prepared as is known in the art by the partial hydrolysis of hydrocarbyl aluminum compounds. Hydrocarbyl aluminum compounds or mixtures of compounds capable of reacting with water to form an aluminoxane can be employed in the present invention. This includes, for example, trialkyl aluminum, triaryl aluminum, mixed alkyl aryl aluminum, or any combination thereof. Hydrocarbyl aluminum compounds can be hydrolyzed by adding solids containing water or free water, which can be hydrates or porous materials that have absorbed water. Since it is difficult to control the reaction by adding water, even with vigorous stirring of the mixture, free water can be added in the form of a solution or dispersion in an organic solvent. Suitable hydrates include salt hydrates, such as, but not limited to, CuSO ₄ .5H ₂ O, Al2 (SO ₄ ) ₃ .18H2O, FeSO ₄ .7H ₂ O, AICI ₃ .6H ₂ O, AI (NO ₃ ) ₃ .9H ₂ O, MgSO ₄ .7H ₂ O, MgCl ₂ «6H ₂ O, ZnSO ₄ .7H ₂ O, Na ₂ SO ₄ .10H ₂ O, Na ₃ RO ₄ « 12H ₂ O, LiBr.2H ₂ O , LiCI.H ₂ O, Lil.2H ₂ O, Lil »3H ₂ O, KF.2H2O, NaBr.2H ₂ O, or any combination thereof. Alkali metal or alkaline earth metal hydroxide hydrates can also be employed with the present invention. Such alkali metal or alkaline earth metal hydroxide hydrates include, but are not limited to, NaOH.H ₂ O, NaOH.2H ₂ O, Ba (OH) ₂ .8H ₂ O, KOH.2H ₂ O, CsOH.H ₂ O, LiOH.H ₂ O, or any combination thereof. Mixtures of salt hydrates and alkali metal or alkaline earth metal hydroxide hydrates can also be used. The molar ratios of free water or water in hydrate or in porous materials, which include inorganic oxides, such as alumina or silica, to total alkyl aluminum compounds in the mixture can vary widely. In one aspect of the present invention, such molar ratios are in the range of about 2: 1 to about 1: 4. In another aspect of the present invention, such molar ratios are in the range of about 4: 3 to about 2: 7.
In one aspect of the present invention, aluminoxanes have saturated hydrocarbyl groups (i.e., alkyl or cycloalkyl groups) having from one to
9/44 about twenty carbon atoms. In another aspect of the present invention, the saturated hydrocarbyl groups of the aluminoxanes have from one to about eight carbon atoms.
The aluminoxanes that can be employed in the present invention include, but are not limited to, methyl aluminoxane, ethyl aluminoxane, npropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, decyl -aluminoxane, dodecylaluminoxane, tetradecylaluminoxane, hexadecylaluminoxane, octadecylaluminoxane, phenylaluminoxane, tolylaluminoxane or any combination thereof.
Aluminoxane can contain up to about 15 mol percent (based on aluminum) of portions formed from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, alkyldisiloxanes, and the like to improve its activity, solubility and / or stability. In another aspect of the present invention, the portion is a bulky phenol. Suitable bulky phenols include, but are not limited to, 2,6-dimethyl-4- (1,1-dimethyl-propyl) phenol, 2,6-diisobutyl-
4-methyl-phenol, 2,6-diisopropyl-phenol, 2,4,6-triisopropyl-phenol, 2,6-diisobutyl-phenol, 2,4,6-triisobutyl-phenol, 2,6, -di-tert-butyl-phenol, 2,4,6-tri-tert-butyl-phenol or any combination thereof.
More preferably, the supported aluminoxane intermediate can be prepared by bringing the oxygen source and the support into contact before contacting the hydrocarbil-aluminum. This includes the use of a support containing an oxygen source, for example, non-calcined silica that contains physically absorbed water. The amount of oxygen source on a support can be controlled, either by adding a controlled amount of oxygen source to the oxygen source on a support, for example, by adding water to the non-calcined silica, or by adding a controlled amount of oxygen source to a support free of oxygen source, for example, adding water to a calcined silica free of physically absorbed water.
The least preferable method is to contact the support with the organoaluminium compound before contacting the oxygen source.
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a) Support (Component 1-a)
Supports or vehicles useful in compositions according to the present invention comprise inorganic vehicles or organic vehicles. Such vehicles can be calcined (temperature above 200 ° C) in such a way that they do not contain water; or they can be non-calcined or calcined at low temperature in such a way that they contain water and particularly are those in which the absorbed water has not been perfectly eliminated. In addition, vehicles containing water can be used in such a way that a predetermined amount of water has been added after the absorbed water is completely or not completely eliminated from them. The present invention provides that such water-containing vehicles can contain up to a percentage of water in such a way that the free water is not leaching out of the vehicle. As discussed, such vehicles containing water can be non-calcined or calcined at low temperature. As used here, a non-calcined vehicle is a vehicle that was not intentionally subjected to the calcination treatment, and a "low temperature calcined" vehicle is a vehicle that has been calcined at a temperature of less than 200 ° C, or up to about 100 ° C, or about 50 C. The calcination time can be up to about 24 hours. In addition, calcination can be carried out in any atmosphere, for example, in an atmosphere of air or an inert gas, or under vacuum.
Water-containing supports that are useful in activator compositions according to the present invention comprise inorganic vehicles or organic vehicles. A plurality of vehicles can be used as a mixture, and the vehicles of the present invention can comprise water as absorbed water or in hydrate form. A vehicle of the present invention can be porous and have a total pore volume of not less than 0.1 ml / g of silica, or not less than 0.3 ml / g. A vehicle of the present invention can have a total pore volume of about 1.6 ml / g of silica. The average particle diameter of the vehicle can be from about 5 micrometers to about 1000 micrometers, or from about 10 micrometers to about 500 micrometers.
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A silica useful in the present invention is porous and has a surface area in the range of about 10 m ² / g of silica to about 1000 n / g including the range of about 10 m ² / g of silica to about 700 m / g slc m total pore volume in the range of about 0.1 cm = / g silica to about 0 _c m ³ / g silica, and an average particle diameter in the range of about 10 micrometers at about 500 micrometers. A silica useful in the present invention can have a surface area in the range of about 50 m ² / g to about 500 / g, a pore volume in the range of about 0.5 cm ³ / g to about 3.5 cm Ig .and an average particle diameter in the range of about 15 micrometers to about 150 micrometers. Suitable silica can have a surface area in the lump of about 200 m ² / g to about 350 m ² / g, a pore volume in the range of about 1. cm '/ g to about 2.0 cm ³ / g , and an average particle diameter in the range of about 10 micrometers to about 110 micrometers.
An average pore diameter of a typical porous silicon dioxide vehicle useful in the present invention is in the range of about 10 Angstroms to about 1000 Angstroms, or about 50 Angstroms to about Angstroms, or about 175 Angstroms to about 350 Angstroms. A _typical content of hydroxyl groups is about 2 mmol OH / g silica to about 10 mmol OH / g silica, with or without the presence of water bound by hydrogen as determined by the following Grignard reaction. Most of these active OH groups readily react with Gngnard benzyl-magnesium chloride to produce toluene, and this reaction can be used to quantify the concentration of active OH groups in a specific silica. Alternatively, methyl-alumm.o can be used for the titration instead of a Grignard reagent. A typical content of hydroxyl groups is about 2 mmol OH / g silica to about 10 mmol OH / g silica, or about 3 mmol OH / g silica to about 8 mmol OH / g silica, or from about 3.3 mmol OH / g silica to about 7.2 mmol OH / g silica.
Examples of inorganic vehicles, which may be useful in the present invention, include inorganic oxides, magnesium compounds, clay minerals and the like. Inorganic oxides can comprise silica, alumina, silica-, magnesia, titania. zirconia and a ^. Inorganic examples useful in the present invention include, without limitation, S1O2, 3. ZrO TiO2 B2O3, CaO, ZnO, BaO, ThO ₂ and double oxides thereof, for example, S ^, SiO ₂ -MgO, SiO2 -102, S ^ IO ^ «. of ₅ magnesium compounds useful in this invention include MgCk, MgCl (O Zares. Examples of clays minerals useful in this invention - bentonite, kibbite clay, geyloam clay, allophane. brs.ngent, micas, montmorillonites, vermicu.lta, chlorites paligorsklta, caul.nita, nacnta, d.ckita, examples of organic vehicles that can be useful in the present invention include acrylic poilomer, styrene polymer, etHen polymer, propylene polymer and the like. Examples of acrylic polymers that can be useful in the present invention include monomers of polymers such as acnlrco - metíía acrylate, methyl methacrylate, met- and the like, and copolymers of monomers and crosslinking polrmenzave.s compounds having at least two unsaturated Hgaçôes polrmeros Examples which may styrene. Useful in the present invention include styrene polymer monomers, such as styrene, vinyl-toluene, ethyl-vinyl-benzene and the like, and monomer numbers and polymeric crosslinking compounds at least two unsaturated bonds. Examples of a crosslinkable polymerizable compound having at least two unsaturated bonds include divinyl-benzene, trivinyl-benzene, divinyl-toluene, divinyl-ketone, dialyl maleate phthalate, Ν, Ν'-methylene-bis-acrylamide , eblene glycol dimethacrylate, polyethylene glycol dimethacrylate and the like.
The organic vehicle useful in the present invention has at least one polar functional group. Examples of suitable polar functional groups include primary amino group, secondary amino group, imino group, amide group, imide group, hydrazide group, amidino group, hydroxyl group, hydroperoxy group, carboxyl group, form.la group, methyloxycarbonyl group, carbamoyl group, sulfo group, sulfine group, sulfene group,
13/44 - ' ^9wo : “: zZ of imidazolyl, group of pipendila, group of round 9 When the organic vehicle has onginally peo - ° - - ^{0 PO S} CI: Z— —.if the group of funconars J _treatment imioo appropriate, organic vehicle as u _ introducing the chemical treatment may be any method capable of treating a r acrylic polymer (e.g., poiiacr, ion tnia) in _{umeste you} dodepas, emumas ₌ -a - 100 ° C or more, for example, from 120 C to 15U polar υ per unit gram in the organic vehicle having a group un of 0.01 to 50 mmol / g, or 0.1 to 20 mmol / g.
_b Oxygen source (Component lb)
The oxygen source can be supplied by water in the vehicle. Case »* - ---“ * as is already known to experts in this area and based on the teachings of this specification. Providing a few and — the limiting factors are: the oxygen source can be in the form of free water, either in the gaseous phase, or in the condensed phase (liquid or solid), the oxygen source can be in the form of coordinated water, such as such as hydro metal salts, for example, LiOH (H ₂ O) „), water absorbed in compounds containing groups h, drox _in molecular sieves, and the like, and can be compounds containing carbon, or hydroxy, in which the atom of oxygen only binds directly to both a tertiary carbon and a hydrogen, for example, 'BuOH, Ph ₃ COH, es, miares, or to a tertiary carbon and an Al, after reacting with a trialqu.l-alum.nro , for example, PhC (O) Me, PhCOOH, and the like. Depending on the
14/44 ™ »..—; ·“ XTÁ.: -,., ... ««. » «” «<·“ ““ „., A
....— »·’ · “..
^Raza _d ° ° and approximately 1: 1.2 or PCDE be a reason that the mode tai about 1.1, c _n g fficativamente _itself with the amount of hydroxy or a residue _iiwe not score. The active catalytic species source generated during pre methods
-— ^p ° ^da - - ^OXÍ9êni ° ;; ^de ; rZca ^and Ldo the teaching of this specification. for experts _f . of oxygen can be _{: 2} -—; - XXJ · »in the form of water Irvre, both in the phase of g, q
- "> * · -" x "" - "" XXX -... · - - - "™ ··" hydroxy groups Standing _onl the _{θθ | JGA} containing carbonyl or hydroxy, in which the atom dlmente both , a tertiary carbon and a hydrogen, for example, BuOH, Ph COH and the like, or a tertiary carbon and an Al after reacting with trialkyl aluminum, for example, PhC (O) Me, PhCOOH, and the like. Depending on the organoaluminium compound in use, the amount of oxygen source can be adjusted so that each of the majority (at least about 50%, and volume) of the oxygen atoms in the same contact at least. θό — mos aluminum The AI: O ratio can be about 100: 1, about · ₁₀ · 1, about 1: 1, about 1: 1.2 or it can be a ratio of such a quantity hydroxy or alkoxy residue does not significantly interact with the active catalytic species generated during the methods of the present invention.
_C ) Organo aluminum compound (Component l-ç).
the organoaluminium compound useful in the present invention can comprise AlR „(YRW where Al is aluminum; each R is hydrogen or a hydrocarbyl group, having up to about 20 carbon atoms, and each R can
15/44 __ j_ vr ⁶ Y is a heteroatom and butyl, isobutyl, n-pentyl, neopentyl and - Non-limiting examples of AIR _n (YR) (3-0). ^ Kii + ii aluminum trioctyl-aluminum, include trimethyl-aluminum, fdetyl-a.ummium, - 1-aum.n. _{di -} aluminum hydride, diethyl hydride -. θ, · „(2 6 di-tert-butyl-4-methyl-phenoxy) _d i-isobutyl-aluminum>, bis ^ .e-dt-tert aluminum, (2,6- _di -tert-butyl-4-methyl -phenoxy) diethyl-aluminum, ^IM * “,.« „«>
_d and oxygen phosphorous atom, sulfur atom and the like.
The organoaluminium compounds of the present invention can be prepared by any suitable method, including currently known methods, as will be familiar to those skilled in the art, or those that may become known.
Precursor of carhocation R ¹ (X) „l.Componenteja _One of the components in the activator composition is a precursor agent of carbocation. Essentially, a carbocatron precursor and a compound containing at least one carbon atom directly attached to a starting group X rich in unstable electrons, which easily forms a pair when placed in contact with aluminoxane supported in a ve. starting u X attaching to the aluminoxane main chain to form anion and the carbon directly attaching to the carbocation group. As a silicon atom has chemical properties similar to that of a carbon atom (Component I), with the leaving group X to ^{become a}
16/44 nature of cation formation, although the derived siiiia cation is less stable than the carbocation precursor, consequently, also a silicon cation precursor that contains a silicon atom directly annealed to the starting X-group, rich in electrons unstable, which tactically makes a pair of ₅ Z containing a silicon cation when co-placed in contact with aluminoxane. The compounds that can be used as a precursor carbocarbon are those having the formula RW in which each X can be anywhere in R 'and is, independently, halogen (fluorine or bromine, preferably fluorine), -OSiiRU, -SR · Λ (*) - ^C _"wherein each R ² is independently bidrogénio or h.drocarb.ia group having from about 1 to about 20 carbon atoms, the CA independently a hydrocarbyl having 1 to 20 atoms of which when at least one R ² is a hydrocarbyl group; R 'and R or R and R can be linked together to form a cyclic group; R is a hydrocarbyl group having about t (when X is halogen) or about 3 (when X is not halogen) to about 20 carbon atoms; ne from 1 to the number of possible substitutions of the hydrocarbyl group; with the proviso that at least one X is not directly attached to an aryan group, and with the proviso that when X is not halogen, X is attached to a secondary or tertane carbon, or a —CHa-aryl group in R .
The condition in relation to the “ariia group mentioned above is for a Situation when the starting group“ X, rich in unstable electrons is attached directly to an aryan group. It was observed that X in this situation is non-reactive, that is, such groups remain linked to the aria group when placed in contact with the supported or unsupported aluminum and / or organoalumin compounds. Preferably, when R ¹ comprises an ring group, R and an aralkyl group such that at least one X is attached to the alkyl group (i.e., aryl-alkyl-X, for example, PhCH ₂ -X), thereby containing way, at least one unstable starting group. In addition, the condition regarding “secondary or tertiary carbon mentioned above is for a situation when the group
17/44 starting 'X, rich in unstable electrons is not a halogen and is attached to a primary alkyl group. It was also observed that X in this situation is non-stable, that is, such groups remain attached to the primary alkyl group when placed in contact with the supported or unsupported aluminoxane and / or organoaluminium compounds. For example, when X contains oxygen and R 'is primary alkyl, such as diethyl ether (R1 = Et and X = OEt), or tetrahydrofuran (THF) (R = -CH2CH2-, and X = OR ³ = - OCH2CH2-), and R ¹ and R ³ are linked to form a cyclic group), they remain as a solvent when mixed with a supported or unsupported MAO. _{1 ή} o In one embodiment, n is 1, 2, 3, 4, 5 or 6. In another embodiment, R is C, -C ₈ alkyl or C ₇ -C ₁₅ aralkyl. In another embodiment, X is -OR ² , and R ² is C1-C4 alkyl or Ce-Cis aralkyl. In one embodiment, R ¹ (X) n is (R ⁴ ) 3C-OR ⁵ or (R ⁴ ) 3C-N (R ⁵ ) 2; wherein each R ⁴ is, independently, a hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms; R ⁵ is a hydrocarbyl group having from about 1 to about 20 carbon atoms; or R ⁴ and R ⁵ can be linked together to form a cyclic group. Preferably. R ⁴ is, independently, a C, -C1B group, and more preferably (R ⁴ ) 3C is, independently, tert-butyl or trityl, and R ⁵ is a C-C6 alkyl group.
When X is halogen in R ¹ (X) „, R ¹ can be a primary, secondary or tertiary hydrocarbyl group; and when X is a non-halogen group, R ¹ is preferably a tertiary hydrocarbyl group or a separate aromatic group from saturated carbon, and less preferably a secondary hydrocarbyl group, but not a primary hydrocarbyl group. The definitions of primary, secondary and tertiary hydrocarbyl groups are as follows; a human hydrocarbyl group represents a -CH _Z R group (for example, ethyl -CH ₂ CH ₃ or propyl CH ₂ CH2CH ₃ ), a secondary hydrocarbyl group represents a -CH (R) _{2 group} (for example, isopropyl -CH ( Me) ₂ or sec-butyl -CH (Me) CH2CH ₃ ) and a tertiary hydrocarbyl group represents a -C (R) _{3 group} (for example, tert-butyl -CMe ₃ or CPh ₃ trityl), where R is a hydrocarbyl that contains at least one carbon.
18/44
A separate aromatic group from saturated carbon represents a -CHjAr group, where Ar is an aromatic group (for example, benzyl -CH ₂ Ph).
Non-limiting examples of R, (X) „are: when X = F, fluorine-methane CH ₃ F, fluorine-ethane CH ₃ CH ₂ F, tert-butyl fluoride Me ₃ CF, trityl fluoride Ph ₃ CF fluoride trimethyl silyl Me ₃ SIF, α-fluoro-toluene C ₆ H ₅ CH ₂ F, α, α-drfluortoluene C ₆ H ₈ CHF ₂ , «, α, α-trifluoro-toluene CF ₃ Ph, 1,3-bis (trifluoromethyl) benzene 1,3 (CF ₃ ) ₂ Ph, and the like; when X = O, isopropyl-methyl-ether Me ₂ CHOMe, tert-butyl-methyl-ether Me ₃ COMe, trityl-methyl-ether Ph ₃ COMe, butenoxide CH ₂ OCHCH ₂ CH ₃ , 1,2di-tert-butyl-benzene 1 , 2 - (* BuO) ₂ C ₆ H ₄ , 1,3-di-tert-butyl-benzene-1,3 - ('BuO) ₂ C ₆ H4, 1,4 - (' BuO) ₂ CeH4; * BuO-CH ₂ -CH ₂ -O-'Bu, isobutene oxide CH ₂ OCMe ₂ , 2,3d'imethoxy-2,3-dimethyl-butane Me ₂ C (OMe) C (OMe) Me ₂ , 2, 3-dimethoxy-butane MeCH (OMe) CH (OMe) Me; tert-butyl-trimethyl-silyl ^ ter Me ₃ COSIMe ₃ , 1-methyl-tetrahydrofuran, 1,2-dimethyl-tetrahydrofuran and the like, and when X = N, tri-isopropylamine (Me ₂ CH) ₃ N, tert -butyl-dimethyl-amine Me ₃ CNMe ₂ , trityl-methyl-dimethyl-amma Ph ₃ CNMe ₂ 2,3-bis (dimethyl-amino) -2,3-dimethyl-butane Me ₂ C (NMe ₂ ) C (NMe ₂ ) Me ₂ , 2,3-bis (dimethyl-amino) butane MeCH (NMe ₂ ) CH (NMe ₂ ) Me; tert-butyl-trimethyl-silyl ether Me ₃ COSiMe ₃ , N, N-dimethyl-benzyl-amine and the like, and when X = O and N in a separate aromatic group of saturated carbon, benzyl-methyl-ether MeOCH.Ph, benzyl-dimethyl-amine Me ₂ NCH ₂ Ph and the like, where Wt is a group of phenylene
I and ^l Bu is a tertiary butyl group.
Non-limiting examples of R ¹ (X) „are: Me ₃ CF, Me ₃ SIF, C ₆ H ₅ CH ₂ F, CeHsCFs, 1,3-C ₆ H ₄ (CF ₃ ) ₂ , 1, 2- (' BuO) ₂ C ₆ H4; 1, 3 - (* BuO) ₂ C ₆ H4; 1.4 - ('BuO) ₂ C ₅ H4; 'BuO-CH ₂ -CH ₂ -O'Bu; or mixtures thereof, where C ₆ H ₄ is a femen group and 'Bu is a tertiary butyl group.
Other non-limiting examples of R '(X) „are tertiary methyl butyl ether, tertiary ethyl butyl ether, tertiary butyl butyl ether, tertiary butyl butyl ether, l-tert-butoxy-2,6-di- tert-butyl-benzene, 1-trimethyl-siloxy-2,6-di-tert-butyl-benzene, trimethyl-siloxy-benzene, trimethyl-methoxy-silane, benzyl-methyl ether, benzyl-ethyl ether, benzyl ether- propyl, benzyl-butyl ether or mixtures thereof.
19/44 ‘BuOMe mixtures, based on the formula Al is aluminum and each R is, independently, a group
Still, other non-limiting examples of RW propylene oxide, isobutene oxide, t-butene oxide, styrene oxide 4J, -styrene, trimethylene oxide, 2,2-dimethyl trimethylene oxide, ox.do and 2,2diphenyl-trimethylene, 1-methyl-tetrahydrofuran, ₅ -ethylene-imine, 1,1,2-trimethyl-ethyl-imine, t-d-phenyl-methyl-methylene-mma. 1-metHhydro-pyrrole, tt-dimethyl-tetrahydro-pyrrole, tl-diphenyl-2-methyl-tetrahydro-p.rrol, 1methyl-piperidine, tt-dimethyl-piperidine, lt-dphenyl-2-methyl- pipendin, or the same.
Preferred examples of R ¹ (X) n are: CFsCeHs, and isobutene _3- oxide, and N, N-dimethyl-benzyl-amine.
trihydrocarbyl aluminum taste (Component J1U One of the components in the supported aluminum activator composition is a trihydrocarbumin aluminum compound having C-C ₂₀ hydrocarb. Non-limiting examples of R include alkyl groups having about tO carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, n-pentyl, neopentyl, benzyl, substituted benzyl and s.mHares. Preferably, the trihydrocarbyl aluminum compound is free of beta-proton Non-limiting examples of AIR ₃ useful in the present invention include, but are not limited to: trimethyl-aluminum, triethyl-aluminum, tripropyl-aluminum, aluminum, tri-isobutyl-aluminum, tri-n-octyl -aluminum, trineopentyl-aluminum, tnbenz, aluminum, tris (2,6-dimethyl-benzyl) aluminum or mixtures thereof and preferably, trimethyl-aluminum (AIMes), trineopentyl-aluminum (AI (CH ₂ C (Me ₃ ) ₃ ) ₃ ) and tribenyl aluminum (AI (CH2C ₆ H ₅ ) 3) ·
The trihydrocarbyl aluminum compounds of the present invention can be prepared by any suitable method, including currently known methods, as will be familiar to those skilled in the art, or the methods which may become known.
Preparation of compositions of this invention supported activator compositions according to the present
20/44. _{They can be} prepared by combining the compound of the invention, P, _carbocation θ θ daily _intermediary of organoaluminium, the ag combined in three components poaem · ——rz:
z = - r: by combining at least a portion of the .ntermedran ₁₅ supported with the trihydrocarbylaluminium compound (Component rmm the carbocationic agent (Component II).
More preferably, the intermediate of a — o supports (Component 1) can be formed in situ by the addition of an organoaluminium compound (Component 1-0 in the support (Component> -a) containing aon and deoxygen (Component ib) , such as water physically — the supported activator composition of the present invention can then be formed by combining at least a portion of the supported intermediate with the trihydrocarbii-aluminum compound (Component III) and then with the carbocationic agent ( Component It): The oxygen source that originally was on the support can be supplemented with additional oxygen sources to allow the reaction with more organoalum compound to increase the charges of Ai in the supported aiuminoxane intermediates. , a non-calcined silica with 5 "of water can be saturated with _more water to reach 10-12" /. to increase A. loads from about 7 /. to about 14 "/ .. Another example is adding an amount desired and wait
21/44 silica free from physically absorbed water (eg silica calcined at 600 ° C) to control the desired Al loads.
An alternative route to form the supported aluminoxane intermediate (Component I) "in situ" is to add excess 5 organoaluminium compound to the support (Component la) containing the oxygen source (Component lb) when a trihydrocarbyl aluminum compound it is used as the organoaluminium compound. The excess organoaluminium compound now serves as both Component 1-c and Component III. The activator composition of the present invention is then formed by combining at least a portion 10 of the intermediate composition with the carbocationic agent (Component II).
Yet another alternative route to form the supported aluminoxane intermediate (Component I) when a trihydrocarbyl aluminum compound is used as the organoaluminium compound is to add an aluminoxane containing high trihydrocarbyl aluminum to the support (Component I15 a). Aluminoxane containing high trihydrocarbyl aluminum is prepared from a low content oxygen source (Component l-b) that allows a desired amount of free trihydrocarbumin aluminum compound as Component III present in aluminoxane. In the following, at least a portion of the intermediate composition with the trihydrocarbyl aluminum present as Component III can be combined with the carbocationic agent (Component II) to form the activator composition of this invention.
The combination can be conducted in an inert gas atmosphere, at a temperature of about -80 ° C to about 200 ° C, or from about 0 C to about 150 ° C; the combination time can be from about 1 minute to about 25 of 36 hours, or from about 10 minutes to about 24 hours. Exemplary treatments after the completion of the combining operation include filtration of supernatant, followed by washing with inert solvent and solvent evaporation under reduced pressure or in an inert gas flow, however these treatments are not required. The resulting activator composition can be used for polymerization in any appropriate state, including fluid,
22/44 dry, or semi-dry powder, and can be used for polymerization in the state of being suspended in an inert solvent. The combination of the components can be carried out at room temperature and in a combination time of about 15 minutes to about 48 hours, or about 15 minutes to about 6 hours; the resulting combination can be used as is or subsequently heated to a temperature of about 80 ° C to about 150 C.
In the supported aluminoxane situation, the molar ratio of the carbocationic agent compound of the formula R ¹ (X) n to the AIR3 trihydrocarbyl aluminum compound is about 0.01: 1 to 2: 1 or about 0.1: 1 to about 1.5: 1 or 10 to about 0.9: 1 to 1.1: 1, and ideally, 1: 1, the molar ratio of X to Al to the compound of formula R ¹ (X) n θ the supported aluminoxane is about 0.01: 1 to 0.8: 1 or about 0.03: 1 to 0.5: 1 or about 0.1: 1. The molar ratio of Al to trihydrocarbyl-aluminum to aluminoxane supported is about 0.01: 1 to 0.8: 1 or about 0.03: 1 to 0.5: 1 or about 0.1: 1 . If the AO is generated “in situ on a support by reacting the organoaluminium compound with the oxygen source on the vehicle, for example, the water absorbed or added to the silica, the organoaluminium compound can be charged as the sum of two portions, a portion such as the trihydrocarbyl aluminum component (Component III), a stoichiometric portion for reaction with R ¹ (X) _n described above, plus the other portion such as the organoaluminium compound (Component lc) for internal formation situ ”of aluminoxane on the support.
In the situation of having aluminoxane in unsupported solution, the molar ratio of the carbocationic agent compound of the formula R ¹ (X) n to the AIR3 trihydrocarbyl aluminum compound is about 0.01: 1 to 0, 1: 1 or about 25 from 0.05: 1 to about 0.08: 1 or about 1: 1. The molar ratio of X to Al to the compound of the formula R ¹ (X) n θ aluminoxane in unsupported solution is about 0.01: 1 to 0.15: 1 or about 0.03: 1 to 0.08: 1 or ideally 0.04: 1. The molar ratio of Al to trihydrocarbil-aluminum to aluminoxane in unsupported solution is about 0.01: to 0.15: 1 or about 0.03: 1 to 0.08: 1 or about 0.04: 1.
23/44
The amount of aluminum atom in the product activator composition when a catalyst precursor is present, for example, solid component, obtained by combining the support with the aluminum components cannot be less than about 0.1 mmol of atom of aluminum, or not less than about 1 mmol of aluminum atom, in 1 g of the solid component in the dry state.
Catalysts for olefin polymerization
The activator compositions of the present invention are useful in catalysts for olefin polymerization. The activator composition according to this invention and the transition metal component can be individually added independently, and substantially, also simultaneously, to the monomer to catalyze the polymerization. The activator composition and the transition metal component can be combined to form the product and at least a portion of the product can be added to the monomer to catalyze the polymerization. The ratio of ALmetal transition can be from about 1: 1 to about 1000: 1, for example, it can be from about 100: 1 to about 500: 1 or from about 200: 1 to 300: 1 .
Catalysts for olefin polymerization - transition metal component
The transition metal component can comprise any transition metal component having a potential for the polymerization of olefins. For example, without limitation, the transition metal component may comprise one or more transition metal-metal components.
The transition metal component may comprise a catalyst precursor ML _to Q _q . _a (wherein M represents a transition metal atom of the 4th Group or lanthanide series of the Periodic Table of the Elements (1993, IUPAC), and examples thereof include transition metals 4 ^of the Periodic Table of Elements such as Group atom titanium, zirconium atom and hafnium atom and transition metals of the Lanthanide Series, such as samarium; L represents a group having a group or structure of cyclopentadienyl, having
At least one heteroatom, at least one L, a group having the structure of cyclopentadienyl, and a plurality of L can be the same or different and can be cross-linked; Q represents halide radicals, alkoxide radicals, amide radicals, and hydrocarbyl radicals having from 1 to about 20 carbon atoms; “A” represents a number that satisfies the expression 0 <a <q; and q represents the valence of the transition metal atom M).
In L in the transition metal component, the group having the cyclopentadienyl structure can comprise, for example, a cyclopentadienyl group, a substituted cyclopentadienyl group or a polycyclic group having the cyclopentadienyl structure. Exemplary substituted cyclopentadienyl groups include hydrocarbon group having from 1 to about 20 carbon atoms, halogenated hydrocarbon group having from 1 to about 20 carbon atoms, silyl group having from 1 to about 20 carbon atoms and the like. The silyl group according to the present invention can include SiMes and the like. Examples of a polycyclic group having the structure of cyclopentadienyl include indenyl group, fluorenyl group and the like. Examples of the heteroatom of the group having at least one heteroatom include nitrogen atom, oxygen atom, phosphorus atom, sulfur atom and the like.
Exemplary substituted cyclopentadienyl groups include the methyl-cyclopentadienyl group, the ethyl-cyclopentadienyl group, the n-propylcyclopentadienyl group, the n-butyl-cyclopentadienyl group, the isopropylcyclopentadienyl group, the isobutyl-cyclopentadienyl group, the sec group tert-butyl-cyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3-dimethyl-cyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethyl-cyclopentadienyl group, tetramethylcyclopentadienyl group , the pentamethyl-cyclopentadienyl group and similar groups.
Exemplary polycyclic groups having the cyclopentadienyl group include the indenyl group, the 4,5,6,7-tetrahydroindenyl group, the fluorenyl group and similar groups.
25/44
Exemplary groups having at least one heteroatom include the methyl-amino group, tert-butyl-amino group, benzyl-amino group, methoxy group, tert-butoxy group, phenoxy group, pyrrolyl group, thiomethoxy group and similar groups.
One or more groups having the cyclopentadienyl structure, or one or more groups having the cyclopentadienyl structure and one or more group having at least one heteroatom, can be cross-linked with (i) an alkylene group, such as ethylene, propylene and the like; (ii) a substituted alkylene group, such as isopropylidene, diphenylmethylene and the like; or (iii) a silylene group or substituted silylene group, such as the dimethyl-silylene group, diphenyl-silylene group, methyl-silyl-silylene group and the like.
Q in the transition metal component comprises halide radicals, alkoxide radicals, amide radicals, hydrogen radicals, or hydrocarbyl radicals having from 1 to about 20 carbon atoms. Examples of Q include Cl, F, Br, MeO, EtO, PhO, CeF ₅ O, BHT, Me2N, EÍ2N, Ph ₂ N, (Me ₃ Si) 2N, alkyl group having from 1 to about 20 carbon atoms , such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, benzyl group, silyl groups, such as Me ₃ Si, Ph ₃ Si and the like.
Examples of transition metal component ML _to Q _q . _a , where M comprises zirconium, include bis (cyclopentadienyl) zirconium dichloride, bis (methyl-cyclopentadienyl) zirconium dichloride, bis (pentamethyl-cyclopentadienyl) zirconium-dimethyl, bis (indenyl) zirconium dichloride, bis (4 , 5,6,7-tetrahydro-indenyl) zirconium, bis (fluorenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, dimethyl-silylene dichloride (cyclopentadienyl-fluorenyl) zirconium, diphenyl-silylene dichloride bis (indenyl) ) zirconium, cyclopentadienyldimethyl-amino zirconium dichloride, cyclopentadienyl-phenoxy zirconium dichloride, dimethyl dichloride (tert-butyl-amino) (zirconium tetramethyl-cyclopentadienyl) zirconium-isopropylidene-3-cyclopentyl (3-cyclopentyl) dichloride methyl-2-phenoxy) zirconium, dimethyl-silylene dichloride (tetramethyl-cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) zirconium, bis (cyclopentadienyl) zirconium dimethyl, bis (methyl-cyclopentadienyl) zirconium dimethyl ,
26/44 bis (pentamethyl-cyclopentadienyl) dimethyl zirconium, bis (indenyl) dimethyl zirconium, bis (4,5,6,7-tetrahydro-indenyl) dimethyl zirconium, bis (fluorenyl) dimethyl zirconium, bis (1-butyl) -3-methyl-cyclopentadienyl) zirconium dimethyl, ethylene bis (indenyl) zirconium dimethyl, dimethyl-silylene (cyclopentadienyl-fluorenyl) zirconium dimethyl, diphenyl-silylenebis (indenyl) zirconium dimethyl, cyclopentadienyl-dimethyl-amino-zirconium dimethyl, dimethyl (tert-butyl-amino) (tetramethylcyclopentadienyl) zirconium silane dimethyl, isopropylidene (cyclopentadienyl) (3-tercbutil-5-methyl-2-phenoxy) dimethyl zirconium, dimethyl-silylene (tetramethyl-cyclopentadienyl) butyl-5-methyl-2-phenoxy) zirconium dimethyl and the like.
Additional exemplary transition metal components, Ml_a Qq-a, include components in which zirconium is replaced by titanium or hafnium in the above zirconium components.
Additional exemplary transition metal components, ML _to Qq-a include components where Q can be the same or different in a molecule.
Other catalyst precursors useful in the present invention are: rac-dimethyl-silyl-bis (2-methyl-4-phenyl-indenyl) zirconium dimethyl; rac-dimethylsilyl-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride (M3); rac-dimethyl-silyl-bis (2-methyl-1-indenyl) zirconium dimethyl; rac-dimethyl-silyl-bis (2-methyl-4,5-benzo-indenyl) zirconium dimethyl; rac-ethylene bis (tetrahydro-indenyl) zirconium dimethyl; rac-ethylene bis (tetrahydro-indenyl) zirconium dichloride (M4); rac-ethylene bis (indenyl) zirconium dimethyl (M2), rac-ethylene-bis (indenyl) zirconium dichloride, bis (1-butyl-3-methyl-cyclopentadienyl) dimethyl zirconium and bis (1-butyl-3- dichloride methyl-cyclopentadienyl) zirconium (M1).
Polymerization using Activator Compositions of this Invention
When using activator compositions of the present invention in polymerization, any olefin or diolefin having from 2 to 20 carbon atoms can be used as a monomer for polymerization. Specific examples of the same include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, hexadecene-1, eicocene-1,4,4-methyl-pentene -1, 5-methyl-2-pentene-1, vinyl-cyclohexane, styrene, dicyclopentadiene, norbornene, 5
27/44 ethylidene-2-norbornene and similar, but are not limited to them. In the present invention, copolymerization can be carried out using two or more monomers, simultaneously. Specific examples of the monomers constituting the copolymer include ethylene / an α-olefin, such as ethylene / propylene, ethylene / butene-1, ethylene / hexene-1, ethylene / propylene / butene-1, ethylene / propylene / 5-ethylidene-2 -norbornene and the like, propylene / butene-1, and the like, but are not limited to them.
The polymerization method is not limited, and both the liquid phase polymerization method and the gas phase polymerization method can be used. Examples of solvents used for liquid phase polymerization include aliphatic hydrocarbons, such as butane, pentane, heptane, octane and the like; aromatic hydrocarbons, such as benzene, toluene and the like; and hydrocarbon halides, such as methylene chloride and the like. It is also possible to use at least a portion of the olefin to be polymerized as a solvent. Polymerization can be carried out in a batch, semi-batch or continuous regime, and the polymerization can be conducted in two or more stages that differ in their reaction conditions. The polymerization temperature can be from about -50 ° C to about 200 ° C, or from 0 ° C to about 100 ° C. The polymerization pressure can be from atmospheric pressure to about 100 kg / cm ² or from atmospheric pressure to about 50 kg / cm ² . The appropriate polymerization time can be determined by means known to those skilled in the art according to the reaction apparatus and the desired olefin polymer, and is typically in the range of about 1 minute to about 20 hours. In the present invention, a chain transfer agent, such as hydrogen, can be added to adjust the molecular weight of the olefin polymer to be obtained in the polymerization.
The invention also relates to a polymer produced from the process described above, such as polyolefin copolymers and polyolefin copolymers using the monomers described above.
28/44
EXAMPLES
The following examples are illustrative of the principles of the present invention. It should be understood that the present invention is not limited to any specific modality exemplified herein, either in the examples or in the remainder of that description.
Example 1
0 mol% of C ₆ H ₅ CF ₃ - without carbocation precursor (Comparative) Preparation of MAO supported on regular silica (sMAO)
In a desiccant container, 24.2 g of silica (G952, 200 ° C, 4 h) and 125 g of toluene are loaded into a round bottom flask with three 300 mL necks, equipped with a mechanical stirrer and an oil bath with heating device. The agitator is turned on at 400 rpm. The MAO solution (MAO 30% in commercial toluene, from Albemarle, Al = 13.6% by weight), 50.0 g (252 mmol of Al, based on 10.4 mmol of Al / g of silica filler ) is added to the silica paste in ambient condition. After the addition, the resulting mixture is left under stirring at room condition for 30 min. The heating device is switched on and set to 110 ° C. After the oil bath reaches 110 ° C, the mixture is left under stirring at that temperature for 4 h. The oil bath is then removed and the feed mixture is allowed to cool to room temperature. The paste is then filtered, washed with 1x 100 g of toluene and 2x 100 g of isohexane and then dried under vacuum overnight. Yield: 39.3 g, ICP: Al = 14.8%. In ambient conditions, the obtained sMAO is used to re-form a paste in 160 g of toluene.
Preparation of the final catalyst with sMAO
The solid metallocene M2 (rac-ethylene-bis (indenyl) zirconium dimethyl) in an amount of 0.58 g (based on 0.35% Zr) is added at once while the paste is stirred at 400 rpm. After two hours, the resulting orange paste is filtered, washed with 1x 100 g of toluene and 2x 100 g of isohexane, and dried under vacuum overnight. Yield: 40.0 g, ICP: Al = 14.5%; Zr = 0.36%. Ethylene polymerization test: 5,700 g / g cat./h (minor encrustation in the
29/44 reactor (autoclave 4 L, 50 mg of cat., 80 ° C, 2.206 MPa (320 psi), 40 mL of 1hexene, without hydrogen, 2 mL 10% TIBA, 60 min, in isobutane).
Example 2
C ₆ H ₅ CF2 at 10 mol% (Comparative)
Preparation of MAO treated with carbocation agent (CAT-MAQ)
In a desiccant container, 50.0 g (252 mmol Al) of a solution of MAO (30% MAO in commercial toluene, from Albemarle, Al = 13.6% in) are loaded into a 2.37 L bottle (80 oz). Under ambient conditions, 15.1 g (25.2 mmol Al) of a TMA solution (12.0%) were mixed with the MAO solution, following the slow addition of a toluene solution Ο ₆ Η ₅ ΟΡ ₃ (9 , 9%) in an amount of 12.4 g (25.2 mmol F). The resulting mixture becomes a dark blue color and begins to form dark blue solids. The dark blue mixture is left under stirring at room temperature for 1 h and then heated to 70 ° C for 20 min. The dark blue solid remains insoluble and the dark blue color becomes dark green. The mixture is left to sediment. A small amount of solids is isolated by filtration / washing / drying (difficult to filter) and sent for analysis ICP: Al = 41% by weight.
Preparation of supported CAT-MAQ (sCAT-MAO)
Before the 10 mol% CAT-MAO is placed on silica, the green solid is removed by filtration to obtain a green solution. The solution is sampled for both ICP and for quantitative H ¹ -NMR analysis: ICP: Al = 7.43%; H ¹ -NMR (25 ° C, 400 mHz, in THF-d8 for MAO and TMA analysis and in ΟθΟ ₆ for DMAF analysis): Al = 7.33% of Al, of which 2.70% is TMA, 0 , 69% are AIMe ₂ F (DMAF), and 3.94% are modified MAO. The total aluminum lost to solid precipitation is about 2.9 g of 7.48 g (of MAO + TMA) or 39%. The molar ratio of MAO to TMA is now 100: 68.5, compared to the normal ratio of MAO: TMA at 100: 15. This abnormal modified MAO solution is placed in a holder anyway.
In a desiccant container, 12.1 g of silica (G948, 200 ° C, 4 h), and 63
30/44 g of toluene are loaded into a round bottom flask with three 300 mL necks equipped with a mechanical stirrer and a heating device bath. The agitator is turned on at 400 rpm. The green solution (7.33% Al), in an amount of 46.4 g (3.4 g Al, based on 10.4 mmol of 5 Al / g silica), prepared as above, is slowly added to the paste silica under ambient conditions. After the addition, the resulting mixture is left under stirring at room condition for 30 min. The heating device is switched on and set to 110 ° C. After the oil bath reaches 110 ° C, the mixture is left under stirring at that temperature for 4 h. The oil bath is then removed and the reaction mixture is allowed to cool to room temperature.
After sedimentation of the solids, the supernatant is sampled for PCI analysis: Al = 3.6%. The paste is filtered, washed with 1x 50 g of toluene and 2x 50 g of isohexane, and then vacuum dried overnight. Yield: 15.10 g. ICP: Al = 9.3% (Total Al = 1.4 g, only 41% of Al out of 3.4 g of loaded Al are placed in the holder).
Final catalytic converter with sCAT-MAO
In ambient conditions, the supported CAT-MAO obtained above is repulped again in 60 g of toluene. The solid metallocene M2 in an amount of 0.31 g is added at once, while the slurry is stirred at 400 20 rpm. After two hours, the resulting yellow-orange paste is filtered, washed with 1x 100 g of toluene and 2x 100 g of isohexane, and dried under vacuum overnight. Yield: 15.5. ICP: Al = 9.1%; Zr = 0.38%. PE test: 2,800 g / g cat./h (serious scale in the reactor) (4 L autoclave, 50 mg cat., 80 ° C, 2.206 MPa (320 psi), 40 ml 1-hexene, without hydrogen , 2 mL of 10% TIBA, 60 mm, in isobutane).
Example 3
C ₆ H ₅ CF ₃ to 10 mol% (Invention)
Preparation of MAO supported on silica (sMAQ)
3Q In a desiccant container, silica (G952, 200 ° C, 4 h) in a
31/44 quantity of 24.3 g and toluene in a quantity of 125 g are loaded in a round bottom flask with three 300 mL necks, equipped with a mechanical stirrer and an oil bath with heating device. The agitator is turned on at 400 rpm. The MAO solution (commercial MAO 30% in toluene 5, Al = 13.6% by weight, from Albemarle), in an amount of 50.0 g (252 mmol Al, based on the 10.4 mmol Al / g of silica), is added to the silica paste under ambient conditions. After the addition, the resulting mixture is left under stirring at room condition for 30 min. The heating device is switched on and set to 110 »C. After the oil bath reaches 110 ° C, the mixture is left under stirring at that temperature for 4 h. The oil bath is then removed and the reaction mixture is allowed to cool to room temperature. The paste is then filtered, washed with 1x 100 g of toluene and 2x 100 g of isohexane and then dried under vacuum overnight. Yield: 39.3 g. ICP:
Al = 14.9%.
₁₅ Preparation of sMAO treated with carbocationic agent (CAT-sMAQ)
In ambient condition, the solid sMAO obtained above is repulped again in 125 g of toluene. The TMA solution in toluene (12.0%), in an amount of 15.0 g (25.0 mmol of Al) is mixed with the sMAO slurry, following the slow addition of C ₆ H ₅ CF _{3 solution} ( 9.9%) in toluene, in an amount of 12.3 g (25.0 mmol F). The resulting mixture becomes a dark blue color.
The mixture is left under stirring in room for 2 h and then it is heated to 70 ° C for 20 min to obtain a paste consisting of a light yellow and almost colorless solid supernatant. A small portion of the supernatant sample was taken for H ¹ -NMR analysis to quantify F. absorption.
The result shows that 7 mol% of the 10 mol% of charge F was placed in the sMAO, a conversion of 70%.
Preparation of final catalyst based on CAT-sMAO
The solid metallocene M2, in an amount of 0.58 g, is added at once, while the paste is stirred at 400 rpm. After two hours, the resulting orange paste 30 is filtered, washed with 1x 100 g of toluene and 2x 100 g of iso
32/44 hexane, and dried under vacuum overnight. Yield: 39.5 g. ICP: Al = 15.2%; Zr = 0.36%. PE test: 10,900 g / g cat./h (small scale in the reactor) (4 L autoclave, 25 mg cat., 80 «C, 2.206 MPa (320 psi), 40 ml 1-hexene, without hydrogen , 2 mL of 10% TIBA, 60 min, in isobutane).
₅ Example 4
10 mol% C6H5CF3 (Invention)
Preparation of MAO supported on silica (sMAQ)
In a desiccant container, silica (G952, 200 ° C, 4 h), in an amount of 24.1 g, and toluene, in an amount of 125 g, are loaded into a 300 ml autoclave. The agitator is turned on at 400 rpm. The MAO solution (MAO 30% in commercial toluene, Al = 13.6% by weight, from Albemarle), in an amount of 50.0 g (252 mmol of Al, based on a load of 10.4 mmol of Al / g silica) is added to the silica paste under ambient conditions. After the addition, the resulting mixture is left under stirring at room condition for 30 min. The autoclave is assembled and removed from the desiccant container and connected to the controller that monitors the temperature, the speed in rpm of the agitator, and the internal pressure of the reactor. The stirrer is turned on and set at 500 rpm and the heating device is turned on and set at 130 ° C. After reaching 130 ° C, the mixture is left under stirring at that temperature for 4 h. The heater is then removed and the reaction mixture is allowed to cool to room temperature. The autoclave is then placed in the desiccant container. The reaction mixture was then transferred to a round bottom flask with three 300 ml necks equipped with a mechanical stirrer. The paste is left to settle.
A small amount of sample is taken for ICP analysis: Al = 3,600 ppm. Preparation of sMAO treated with carbocationic agent (CAT-sMAO)
The TMA solution in toluene (12.0%), in an amount of 15.0 g (25.0 mmol of Al), is mixed with the sMAO paste, under stirring, following the slow addition of C6H5CF3 solution (9 , 9%) in toluene, in an amount of 12.3 30 g (25.0 mmol of F). The resulting mixture becomes a dark blue color. The mixture is
33/44 left under stirring at room temperature for 2 h and then heated to 70 ° C for 20 min to obtain a paste consisting of a very light yellow supernatant and an almost colorless solid. A small portion of the supernatant sample was taken for H'-NMR analysis to quantify the absorption 5 of F and shows 8 mol% of the 10 mol% is placed on silica, a conversion of
80%.
Final catalyst pre-catalysis based on CAT-sMAO
The solid metallocene M2, in an amount of 0.58 g, is added at once, while the paste is stirred at 400 rpm. After two hours, the resulting yellow-orange paste 10 is filtered, washed with 1x 100 g of toluene and 2x 100 g of isohexane, and vacuum dried overnight. Yield: 39.8 g. ICP: Al = 17.0%; Zr = 0.34%. Ethylene polymerization test: 13,600 g / g cat./h (without fouling in the reactor) (4 L autoclave, 25 mg cat., 80 “C, 2, 206 MPa (320 psi), 40 mL of 1 -hexene, without hydrogen, 2 mL of 10% TIBA, 60 min, in isobutane).
EXAMPLE 5
Metallocene without M1 connection for PE applications
C ₆ H ₅ CF ₃ to 10 mol% (Invention)
MAO pressing supported on silica (sMAQl ₂₀ In a desiccant container, silica (G948, 200 ° C, 4 h), in an amount of 9.1 g and toluene, in an amount of 45 g, are loaded into a 300 ml autoclave. The stirrer is turned on at 400 rpm The MAO solution (MAO 30% in commercial toluene, Al = 13.6% by weight, from Albemarle), in an amount of 21.5 g (108 mmol of Al, based on a load of 11.9 mmol of Al / g of silica) is added to the silica paste in room condition After addition, the resulting mixture is left under stirring in room condition for 30 mm. The autoclave is assembled and removed from the desiccant container and connected to the controller that monitors the temperature, the speed in rpm of the stirrer, and the internal pressure of the reactor.The stirrer is turned on and set to 500 rpm and the heating device is turned on and set to 130 ° C. After reaching 130 ° C, a
The mixture is left under stirring at that temperature for 4 h. The heater is then removed and the reaction mixture is allowed to cool to room temperature. The autoclave is then placed in the desiccant container. The reaction mixture was then transferred to a round bottom flask with three 300 ml necks 5 equipped with a mechanical stirrer. The paste is left to settle. A small amount of sample is taken for ICP analysis:
AI = 1200ppm.
Prenuation of sMAO treated with carbocationic agent (CAT-sMAQl
The TMA solution in toluene (12.0%), in an amount of 6.0 g 10 (10.0 mmol of Al) is mixed with the sMAO paste under stirring, following the slow addition of C ₆ H _{5 solution} CF ₃ (9.9%) in toluene, in an amount of 4.91 g (10.0 mmol of F). The resulting mixture becomes a dark blue color. The mixture is left under stirring at room temperature for 2 h, and then it is heated to 70 ° C for 20 min to obtain a paste consisting of a very light yellow and almost colorless solid supernatant. A small portion of the supernatant sample was taken for H'-NMR analysis to quantify the absorption of F and shows that 8 mol% of the 10 mol% was placed on silica, an 80% conversion.
Preparation of final catalyst based on CAT-sMAO ₂₀ the solution of metallocene M1 (bis- (1-butyl-3-methylcyclopentadienyl) zirconium dichloride) in toluene (19.6%), in an amount of 1.73 g at once, while the paste is stirred at 400 rpm. After two hours, the resulting yellow-orange paste is filtered, washed with 1x 50 g of toluene and 2x 50 g of isohexane, and vacuum dried overnight. Yield. 15.6 g. ICP.
Al = 18.1%; Zr = 0.45%. Ethylene polymerization test: 5,700 g / g cat./h (without fouling in the reactor) (4 L autoclave, 50 mg cat., 85 ° C, 2.206 MPa (320 psi), 50 ml 1-hexene , without hydrogen, 1 mL of 10% TIBA, 60 mm, in isobutane).
Example 6
0 mol% of C ₆ H ₅ CF3
35/44 (Comparative)
Preparation of MAO supported on silica (sMAO)
In a desiccant container, silica (G948, 200 ° C, 4 h), in an amount of 24.1 g, and toluene, in an amount of 125 g, are loaded in 5 in a 300 ml three-necked round-bottom flask, equipped with a mechanical stirrer and an oil bath with heating device. The agitator is turned on at 400 rpm. The MAO solution (MAO 30% in toluene, Al 13.6% by weight, from Albemarle), in an amount of 56.9 g (287 mmol of Al, based on a load of 11.9 mmol of Al / g silica) is added to the 10 silica slurry in ambient condition. After the addition, the resulting mixture is left under stirring at room condition for 30 min. The heating device is switched on and set at 130 ° C. After the oil bath reaches 130 ° C, the mixture is left under stirring at that temperature for 4 h. The oil bath is then removed and the reaction mixture is allowed to cool to room temperature. The paste is then filtered, washed with 1 x 100 g of toluene and 2x 100 g of isohexane, and then vacuum dried overnight. Yield: 39.1 g. ICP: Al 17.9%. In ambient conditions, the obtained sMAO is repulped again in 160 g of toluene.
Preparation of final catalyst based on CAT-sMAO
The solution of metallocene M1 in toluene (19.6%), in an amount of 4.33 g (based on 0.45% Zr) is added at once, while the paste is stirred at 400 rpm. After two hours, the resulting orange paste is filtered, washed with 1x 100 g of toluene and 2x 100 g of isohexane, and vacuum dried overnight. Yield: 39.8 g. ICP: Al = 17.5%; Zr = 0.46%. Ethylene polymerization test: 3,500 g / g cat./h (without fouling in the reactor) (4 L autoclave, 50 mg cat., 85 ° C, 2.206 MPa (320 psi), 50 mL 1-hexene , without hydrogen, 2 mL of 10% TIBA, 60 min, in isobutane).
Example 7
Metallocene bonded to silicon M3 for applications of PP C ₆ H ₅ CF ₃ to 10 mol% (Invention)
36/44
Propararan from MAO supported on silica (sMAO)
In a desiccant container, silica (Fuji P-10, 100 »C, 8 h), in an amount of 20.3 g, and the totuene, in an amount of 70 g, are loaded into a 300 ml autoclave. The agitator is turned on at 400 rpm. The solution of 5 (MAO 30% in commercial toluene, Al = 13.6% by weight, from Albemarle), in an amount of 48.5 g (244 mmol of Ai, based on 12.0 mmol of Al / g of silica paste) and added to the silica paste in ambient condition. After the addition, the resulting mixture is left under stirring at room condition for 30 mm. The autoclave is assembled and removed from the desiccant container and connected to the controller that monitors the temperature, the speed in rpm of the fertilizer, and the internal pressure of the reactor. The stirrer is turned on and set at 500 rpm and the heating device is liver and set at 130 ° C. After reaching 130-C, the mixture is left under stirring at that temperature for 4 h. The heater is then removed and the reaction mixture is allowed to cool to room temperature. The autoclave is then placed in the desiccant container. The reaction mixture was then transferred to a 300 ml three-necked round-bottom flask, equipped with a mechanical stirrer. The paste is left to settle. A small amount of sample is taken for 1CP analysis: Al = 900 ppm.
The slurry is quite agitated, and 4.0 g of slurry is removed and filtered, washed with 3x 10 g of isohexane and dried under vacuum until constant weight. The yield is 1.04 g. which indicates that the paste has a percentage of sMAO of 26.0%. The solid was sampled for ICP: Al = 18.44%. The sMAO paste is divided into two portions; one for the modified version with carbocationic agent and the other for a regular supported MAO version for comparisons (Example
8).
Preparation of sMAO treated with carbocationic agent (CAT-sMAO)
An amount of 82.7 g of sMAO paste (Al = 147 mmol) is loaded into a round bottom flask with three 300 ml necks, equipped with a mechanical stirrer. The paste is heated to 70 ° C in an oil bath with stirring. The solution of TMA in toluene (20.0%), in an amount of
37/44
,. . . the sMAO cream, following the slow addition of r 4 a (17 mmol of Al) is added to the sivimu paste, and solution of CsHsCFs (9.9%) in toluene, in an amount of 7.3 g (14.8 mm) of _{F) The} resulting mixture changes to a dark blue color. The mixture is left> stirred at 70 ° C for 15 min and then the temperature is reduced to 35 ° C for 1 h and 45 min, to obtain a paste consisting of a light greenish-yellow supernatant and a green solid. A small portion of masters r supernatant was removed for analysis N'-NMR to quantify the absorption shows that F and 8 mol% 10 mol% silica are placed in a 80% conve.
Prenaracão of catalisadorfina ^^ M3 solid metallocene _(c-ra dichloride dimethyl silyl bis (2-methyl-
4-phenyl-indenyl) zirconium), in an amount of 0.25 g, is added at once while the paste is stirred at 400 rpm. After two hours, the resulting worm paste is filtered, washed with 1 x 100 g of toluene and 2 x 100 g of sodium hexane, and vacuum dried for 4 h. Yield: 21.3 g. ICP: Ai = 18.5%; Zr = 0.18%. Propylene polymerization test: 34,000 g / g cat./h (without fouling in the reactor (4 L autoclave, 14 mg cat., 70 »C, 2200 ml propylene, 50 ml x 1.24 MPa (180 psi) of H ₂ , 1 mL of 5% TIBA, 60 min)
Example 8
0 mol% of C6H5CF3 (Comparative M3)
MAO pressing supported on silica (sMAO)
A quantity of 44.2 g of sMAO paste (Al = 78.5 mmol) from Example 7 was loaded into a round bottom flask with three 300 ml necks, equipped with a mechanical stirrer. The metallocene solid M3, in an amount of 0.080 g, is added at once, while the paste is added at 400 rpm. After two hours, the resulting red paste is filtered, washed with 1x 50 g of toluene and 2x 50 g of isohexane, and dried under vacuum for 4 h. Yield:
11.3 g. ICP: Al = 18.3%; Zr = 0.19%. Propylene polymerization test: 10,800 g / g cat./h (without fouling in the reactor) (4 L autoclave, 14 mg cat., 70 »C,
38/44
2200 ml propylene, 50 ml x 1.24 MPa (180 psi) H ₂ , 1 ml 5% TIBA min).
Carbocationic agent of 3 mol% butene oxide ₅ (Invention)
MAO (30% in toluene, Albemarle's product), in an amount of 12.67 g (Al = 64.5 mmol), was placed in a 20 mL bottle. Pure butene oxide (or 1.2 epoxy-butane, 99% from Aldrich), in an amount of 0.14 g (1.9 mmol), was then slowly added to the MAO solution in the 1st ambient condition. The resulting solution was left under stirring, on a stirrer overnight.
The above solution was tested for M2-catalyzed 1-hexene polymerization, using a simple calorimetry method to quantify the reaction heat released by the polymerization process that forms two simple DC bonds (releasing 2x heat approximately 83 = 166 kcal / mol) while breaking a C = C double bond (absorbing heat of approximately 146 kcal / mol, which provides a net heat release of about 20 kcal / mol of 1hexene. Under the same conditions, the higher the heat of reaction, the catalytic system was more active. The calorimetric measurement was made in a 50 ml double-bottomed round 20 reactor equipped with a stir bar and a thermocouple for temperature measurement. Dry toluene, in an amount of 17,115 g, and solution of M2 in toluene, in an amount of 0.5482 g, prepared from the stock solution of 0.111 g of solid M2 in 10.0 g of toluene was loaded into the reactor. The stirrer was turned on. naked ma 25 amount of 0.326 g, based on AI: Zr = 100: 1, was loaded into the reactor and a timer was started to measure the activation time. After 15 min (lap 1), the temperature of the solution was recorded as 28.0 ° C, and 0.60 g of 1-hexene was injected into the solution while the timer was turned on (lap 2). The temperature started to rise and after 5 min (lap 2), a temperature of 41.9 ° C was recorded. The reaction heat was calculated to be 18.66 kcal / g of cat./5 min.
39/44 a reference run based on untreated MAO was also performed to verify the difference in relation to the treated MAO To.ueno se ^ in an amount of 17.11 g, and a solution of M2, in a quantity 0 _g from the same stock solution M2 were loaded into the reactor The agitator was turned on. Then the untreated MAO (0.328 g) based on. r ₁₀ 0-1 was loaded into the reactor and a timer was started to count the activation time. After 15 min (lap 1), the temperature of the solution was recorded as 28.3 ° C, and 0.60 g of 1-hexene was injected into the solution while the timer was turned on (lap 2). The temperature started to rise and after 5 mm (lap 2). a temperature of 37.0 »C was recorded. The heat of reaction is calculated to be 12.8 kcal / g cat / 5 min.
The reference run for AI: Zr = 200: 1 was also performed and a reaction heat of 22.4 kcal / g of cat./5 min. It was obtained. Therefore, it can be seen _that the increase is very significant through the treatment of MAO with 3 ”/ butene oxide. molar. It can be seen that with MAO treated for AI: Zr = 100: 1, the performance is closer to the performance of an MAO untreated for AI: Zr = 200: 1.
Example 10
6 mol%% methyl tert-butyl ether carbocationic agent (Invention)
SMAO is prepared using the same procedures as in example 7. The sMAO slurry is determined and contains 19.6% sMAO and the amount of Al in the sMAO solid is 18.0%. The sMAO paste is divided into two portions; one for the modified version with carbocationic agent and another for a regular supported MAO version for comparisons (Example
11).
A quantity of 12.5 g of sMAO paste (Al - 16.0 mmol) is loaded into a 20 mL bottle. A solution of TMA in toluene (12.0%), in an amount of 0.9 g (1.5 mmol Al) is added to the sMAO paste, following the slow addition of the toluene solution having 0.085 g of methyl tert- butyl ether (MTBE,
40/44 added at once, from Aldrich) in 1 g of toluene (0.96 mmol) with manual stirring for _ The mixture is left under stirring on a shaker for 1 h. A small portion of the supernatant sample was taken for H ¹ -NMR analysis. - _is detected, and the MTBE tBu has been converted to neopentane or rsobutene, MTBE methoxy air is not detectable.
_S6l metallocene oxide M4 (rac-ethylene-blsdetrahydroindenyl) zirconium), in an amount of 0.035 g, and while the paste is stirred at 400 rpm. After two hours, the resulting θ Red slurry is filtered, washed 1x with 10 g of toluene and 10 g of iso 2x exa, IPP. Δΐ = 17 5% · Zr = 0.41%. Vacuum dry test for 4 h. Yield: 2.45 g. ICP. Al 1..
x ·. «Ann n / n of cat / h (without incrustation in the reactor) polymerization of ethylene: 13,900 g / g ae falls./n <
80 ° C 2 206 MPa (320 psi), 40 ml 1-hexene, (4 L autoclave, 25 mg cat., 80 C, ζ, ζυο ivira _k mL 10% TIBA, 60 min , in isobutane).
Example 11
0 mol% of methyl-tert-butyl-ether (Comparative)
An amount of 13.5 g of sMAO paste (from example 10) was loaded into a 20 ml bottle. Metallocene solid M4, in an amount of 0 037 g is added at once. while the paste is stirred at 400 rpm. After two hours, the resulting red paste is filtered, washed with 1x 10 g of toluene and 2x 10 g of isohexane, and dried under vacuum for 4 h. Yield. 2.65 g. _ICP . Al = 17.8%; Zr = 0.40%. Ethylene polymerization test: 8,400 g / g and cat / h (without fouling in the reactor) (4 L autoclave, 25 mg cat., 80 »C, 2,206 _MPa (320 psi), 40 ml 1-hexene, 2 mL of 10% TIBA, 60 min, in isobutane).
Example 12
Ν, Ν-dimethyl-benzyl-amine at 10 mol% (Invention)
Preparation of MAO supported on silica (sMAQl
An amount of 8.8 kg (19.4 lb) of Fuji P-10 silica (26 microns), calcined at 150 ° C for 7.5 h with an LOD of 0.84% (300-C, 4 h under N ₂ ) fol
41/44 loaded in a 37.85 liter (10 gallon) reactor with toluene, in an amount of 48.7 kg (107.4 Ib), to form a paste. In ambient conditions (about 25 ° C), a 30% MAO solution (Al = 15.58%, Albemarle product), in an amount of 20.18 kg (44.5 Ib), based on 11.5 mmol of Al / g of silica, was added slowly with internal temperature control not exceeding 30 ° C.
An amount of 3.18 kg (7.0 Ib) of toluene was used to rinse the residual MAO. The mixture was left under stirring at room condition for 30 min. The temperature was then raised to 130 ° C and maintained for 4 h. A small sample was filtered, washed, and dried to obtain the solid and determined that the solid in the paste is 21.38% and the Al in the pure solid is 18.5%.
Preparation of sMAO treated with carbocationic agent (CAT-sMAO)
An amount of 16.8 g of supported MAO paste (containing 3.59 g of solid) from the above procedure was loaded into a 20 ml flask. At once, a solution of AIMe ₃ in 15 toluene (15.5%, as Component III - AIR3) was added, in an amount of 1.14 g containing 2.45 mmol of pure AIMe ₃ , based on 10 mol% Al in the sMAO solid. While the flask was vigorously shaken, 0.33 g of pure Me ₂ NCH ₂ C ₆ H5 (Ν, Ν-dimethyl-benzyl-amine), as Component II, was slowly added to the mixture of sMAO and AIMe ₃ . The reaction mixture was left under stirring on a shaker for 2 h.
Preparation of final catalyst based on CAT-sMAO
To the mixture of sMAO treated with amine carbocation, prepared according to the above procedure, 0.052 g of Rac-ethylene was then added; bis (indenyl) zirconium dimethyl (M2), following stirring in a mixer for 25 1 h. The mixture was then filtered, washed with 2x 10 g of toluene and 2x 15 g of isohexane, and dried in vacuo for 2 h. Yield: 3.56 g. (ICP Al = 18.7%; Zr = 0.35%). The ethylene polymerization tests were carried out under conditions similar to Example 1 (4 L autoclave, 30 mg of cat., 80 ° C, 2.206 MPa (320 psi), 40 mL of 1-hexene, without hydrogen, 1 mL of 10% TIBA, 60 min, in 30 isobutane) and the results are listed in Table 1, as Example 12.
42/44
Example 13
0 mol% of N, N-dimethyl-benzyl-amine (Comparative)
An amount of 15.2 g of supported MAO paste (containing 5 3.25 g of solid) from Example 12 was loaded into a 20 ml vial. Metallocene M2 (0.054 g) was added to the supported MAO, followed by stirring in a mixer for 1 h. The mixture was then filtered, washed with 2x 10 g of toluene and 2x 15 g of isohexane, and dried in vacuo for 2 h. Yield: 3.18 g (ICP Al = 18.8%; Zr = 0.39%). The ethylene polymerization tests were carried out under 10 conditions similar to Ex. 1 (4 L autoclave, 30 mg of cat., 80 ° C, 2.206 MPa (320 psi), 40 mL of 1-hexene, without hydrogen, 1 mL of 10% TIBA, 60 mm, in isobutane) and the results are listed in Table 1 as Entry 13.
43/44
TABLE 1 - Summary of Examples
Example Carbocátion Comp. II TMAComp.III Intermediate AOComp. I Metallocene PE / PP test g / g of cat./h Inlay in the reactor 1Comparative - No Yes M2 5,700(PE) Minimum 2Comparative 10 mol% c ₆ h ₅ cf ₃ Yes No M2 2,800(PE) Would be
Minimum
10,900
M2
Yes
Yes
10 mol%
Inventive
Invention
Invention
Comparative
Invention
Invention
CeHgCF 3
10 mol%
CeHsCF 3
10 mol%
CeHsCF 3
No
10 mol%
C ₆ H ₅ CF ₃
Comparative
3 mol%
Butene oxide
6 mol%
Yes
Yes
Yes
No
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
M2
M1
M1
M3
M3 (PE)
13,600 (PE)
5,700 (PE)
3,500 (PE)
34,000 (PP)
10,800
No
No
No
No
No (PP)
No
13,900
M4
Comparative
Methyl t-butyl (PE) ether
C ₆ H ₅ CF ₃
44/44
11How to - No Yes M4 8,400(PE) No 12Invention 10 mol% Me ₂ NCH ₂ - c ₆ h ₅ Yes Yes M2 11,000(PE) NoNo Yes M2 7,400(PE) No 13rnmnorativn l - t— rj -----------'---------- „
uomparauvo __________________________ * Example 4 - sMAO prepared at 130-C versus 110 ° C for Example 3.
Comparative Example 2 and Invention Example 3 show that when aluminoxane is first reacted with the carbocation precursor, the catalyst activation is about 3 times less than the example of the invention, where the supported AO intermediate is first formed, and then reacted with the carbocation precursor.

权利要求:
Claims (22)
[1]
1. Composition, characterized by the fact that it comprises:
i) a supported aluminoxane intermediate composition comprising:
a) a support; b) an organo-aluminum compound; and c) an oxygen source;
ii) a compound having the formula R ¹ (X) ri, wherein R ¹ is a hydrocarbyl group having from about 1 to about 20 carbon atoms; n varies from 1 to the number of possible substitutions of the hydrocarbyl group and each X can be substituted anywhere in R ¹ and is, independently, halogen, OSi (R ² ) 3, -N (Sí (R ² ) 3) ₂ , -N (R ² ) 2; -SR ² ; -P (R ² ) 2; -CN or -OR ³ ; wherein each R ² is, independently, hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms; each R ³ is, independently, a hydrocarbyl having from 1 to 20 carbon atoms, where when at least one R ² is a hydrocarbyl group; R ¹ and R ² or R ¹ and R ³ can be linked together to form a cyclic group; with the proviso that at least one X is not directly linked to an aryl group, and with the proviso that when X is not halogen, X is linked to a secondary or tertiary carbon, or a CH ₂ -aryl group; and iii) a trihydrocarbyl aluminum compound, having the formula AIR ₃ , where each R is, independently, a C1-C20 hydrocarbyl group.
[2]
2. Composition according to claim 1, characterized in that R is Ci-C ₈ alkyl, R ¹ is a C ₃ -C ₈ alkyl or C7 -C15 aralkyl, n is from 1 to 3, X is halogen, or -OR ² , and R ² is C-1-C4 alkyl or C6-C15 aralkyl.
[3]
Composition according to claim 1, characterized by the fact that R ¹ X is (R ⁴ ) 3C-OR ⁵ or (R ⁴ ) 3C-N (R ⁵ ) ₂ ; wherein each R ⁴ is, independently, a hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms and at least one R ⁴ is a hydrocarbyl group; R ⁵ is a hydrocarbyl group having from about 1 to about 20 carbon atoms; or R ⁴ and R ⁵ can be linked together to form a cyclic group.
2/4
[4]
Composition according to claim 1, characterized in that R ¹ (X) n is: Me3CF, Me3SiF, C6H5CH2F, C6H5CF3 1,3-C6H4 (CF3) 2, 'BuOMe, 1,2- ( ^ι ΒυΟ ) 20 ₆ Η ₄ ; 1,3- ( ⁴ ΒυΟ) 206Η4ι 1,4- ( ^ι ΒυΟ) 20 ₆ Η ₄ ; 'ΒυΟ-ΟΗ ₂ -ΟΗ ₂ - O'Bu; 1methyl-tetrahydrofuran, 1,2-dimethyl-tetrahydrofuran or mixtures thereof, with C ₆ H ₄ being a phenylene group and 'Bu being a tertiary butyl group.
[5]
5. Composition according to claim 1, characterized in that R ¹ (X) _n is tertiary methyl-butyl ether, tertiary ethyl-butyl ether, tertiary propyl-butyl ether, tertiary butyl-butyl ether, 1-tert-butoxy-2,6-di-tert-butylbenzene, 1-trimethyl-siloxy-2,6-di-tert-butyl-benzene, trimethyl-siloxy-benzene, trimethylmethoxy-silane, benzyl-methyl ether, benzyl-ethyl ether, benzyl-propyl ether, benzyl-butyl ether or mixtures thereof.
[6]
6. Composition according to claim 1, characterized by the fact that R ¹ (X) _n is ethylene oxide, propylene oxide, isobutene oxide, 1-butene oxide, styrene oxide, 4-methyl oxide styrene, 2,2-dimethyl-trimethylene oxide, 2,2-diphenyl-trimethylene oxide, 1-methyl-ethylene-imine, 1,1,2-trimethyl-ethylene-imine, 1,1-diphenyl-2-methyl-ethylene- imine, 1-methyl-tetrahydro-pyrrole, 1,1,2-trimethyl-tetrahydro-pyrrole, 1,1-diphenyl-2-methyl-tetrahydro-pyrrole, 1-methylpiperidine, 1,1, 2-trimethyl-piperidine, 1,1-diphenyl-2-methyl-piperidine or mixtures thereof.
[7]
Composition according to claim 1, characterized in that the aluminoxane on a support comprises methyl aluminoxane, neopentylaluminoxane, benzylaluminoxane, ethylaluminoxane, n-butylalumininox or isobutylalumininoxane.
[8]
8. Composition according to claim 1, characterized by the fact that the trihydrocarbyl aluminum compound is trimethyl aluminum, trineopentyl aluminum, tribenyl aluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum, tri isobutyl -aluminum, tri-n-octyl-aluminum or mixtures thereof.
[9]
Composition according to claim 1, characterized in that the support is silica, alumina, silica-alumina, clay, a modified clay composition, or any combination thereof.
3/4
[10]
10. Composition according to claim 1, characterized in that the molar ratio of the compound of formula R ¹ (X) n to the trihydrocarbyl aluminum compound is about 0.01: 1 to 2: 1 and the molar ratio of X in the compound of formula R ¹ (X) n to Al in the supported aluminoxane is about 0.01: 1 to 0.8: 1.
[11]
11. Composition according to claim 1, characterized by the fact that it also comprises a transition metal component.
[12]
12. Polymerization process of a monomer, characterized by the fact that it comprises carrying out the polymerization in the presence of a composition as defined in claim 1.
[13]
13. Composition, characterized by the fact that it comprises:
i) a trihydrocarbyl aluminum compound having the formula AIR ₃ , wherein each R is, independently, a C1-C20 alkyl;
ii) a compound having the formula R ¹ (X) n; wherein R ¹ is a hydrocarbyl group having from about 3 to about 20 carbon atoms; n varies from 1 to the number of possible substitutions of the hydrocarbyl group and each X can be substituted anywhere in R ¹ and is, independently, -OSi (R ² ) 3, N (Si (R ² ) ₃ ) ₂ , - N (R ² ) 2; -SR ² ; -P (R ² ) 2; -CN or -OR ³ ; each R ² being, independently, hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms; each R ³ is, independently, a hydrocarbyl having from 1 to 20 carbon atoms, where when at least one R ² is a hydrocarbyl group; R ¹ and R ² or R ¹ and R ³ can be linked together to form a cyclic group; with the proviso that at least one X is not directly linked to an aryl group, and with the proviso that X is linked to a secondary or tertiary carbon, or a -CH ₂ -aryl group; and iii) an aluminoxane.
[14]
Composition according to claim 13, characterized in that R is CrC ₈ alkyl, R ¹ is C 3 -C 8 alkyl or C 7 -C 15 aralkyl, n ranges from 1 to 3, X is -OR ² , and R ² is a C1 -C4 alkyl or aralkyl C6-Ci _5.
[15]
Composition according to Claim 13, characterized in that R ¹ X is (R ⁴ ) 3C-OR ⁵ or (R ⁴ ) 3C-N (R ⁵ ) ₂ ; where each R ⁴ is,
4/4 independently, a hydrogen or a hydrocarbyl group having from about 1 to about 20 carbon atoms and at least one R ⁴ is a hydrocarbyl group; R ⁵ is a hydrocarbyl group having from about 1 to about 20 carbon atoms; or R ⁴ and R ⁵ can be linked together to form a cyclic group.
[16]
16. Composition according to claim 13, characterized in that R ¹ (X) n is: 'Bu-OMe, 1,2- ( ^{ ΒυΟ) 2ΰ ₆ Η ₄ ; 1,3- ( ^{ ΒυΟ) ₂ ΰ ₆ Η ₄ , 1,4 ('BuO) 2C ₆ H ₄ ; 'BuO-Chfe-Chfe-CyBu; 1-methyl-tetrahydrofuran, 1,2-dimethyl-tetrahydrofuran or mixtures thereof, with C ₆ H ₄ being a phenylene group and ¹ Bu being a tertiary butyl group.
[17]
17. Composition according to claim 13, characterized in that the molar ratio of the compound of formula R ¹ (X) n to the trihydrocarbyl aluminum compound is about 0.01: 1 to 0.1 : 1 and the molar ratio of X in the compound of formula R ¹ (X) n to Al in the unsupported aluminoxane solution is about 0.01: 1 to 0.8: 1.
[18]
18. Composition according to claim 13, characterized by the fact that it also comprises a vehicle.
[19]
19. Composition according to claim 13, characterized in that it further comprises a transition metal component.
[20]
20. Process for the polymerization of a monomer, characterized by the fact that it comprises carrying out a polymerization in the presence of a composition as defined in claim 13.
[21]
21. Polymer, characterized by the fact that it is formed by the process as defined in claim 12.
[22]
22. Polymer, characterized by the fact that it is formed by the method as defined in claim 20.

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TW201244821A|2012-11-16|

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KR20140007450A|2014-01-17|

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CN103534278B|2016-10-05|

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MX2013010313A|2014-02-11|

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WO2012122332A1|2012-09-13|

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CA2828936A1|2012-09-13|

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SG193257A1|2013-10-30|

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2020-06-02| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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优先权:

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申请号 | 申请日 | 专利标题

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US201161450696P| true| 2011-03-09|2011-03-09|

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PCT/US2012/028188|WO2012122332A1|2011-03-09|2012-03-08|Aluminoxane catalyst activators containing carbocation agents, and use thereof in polyolefin catalysts|

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