CA2365718A1 - High temperature ziegler-natta solution catalysts - Google Patents

High temperature ziegler-natta solution catalysts Download PDF

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CA2365718A1
CA2365718A1 CA002365718A CA2365718A CA2365718A1 CA 2365718 A1 CA2365718 A1 CA 2365718A1 CA 002365718 A CA002365718 A CA 002365718A CA 2365718 A CA2365718 A CA 2365718A CA 2365718 A1 CA2365718 A1 CA 2365718A1
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radicals
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Isam Jaber
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Nova Chemicals Corp
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Nova Chemicals Corp
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Priority to CA002365718A priority Critical patent/CA2365718A1/en
Priority to US10/314,796 priority patent/US6878658B2/en
Priority to KR1020020080361A priority patent/KR20030051346A/en
Priority to EP02258638A priority patent/EP1321479B1/en
Priority to BR0205303-9A priority patent/BR0205303A/en
Priority to AT02258638T priority patent/ATE277089T1/en
Priority to DE60201328T priority patent/DE60201328T2/en
Priority to CNB021563853A priority patent/CN1247621C/en
Priority to EA200201225A priority patent/EA005891B1/en
Publication of CA2365718A1 publication Critical patent/CA2365718A1/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

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  • Engineering & Computer Science (AREA)
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Catalysts (AREA)

Abstract

The present invention provides a Ziegler-Natta catalyst useful in solution processes for the polymerization of olefins having a low amount of aluminum and magnesium. The catalysts of the present invention contain an alkyl silanol and have a molar ratio of Si: Ti from 0.25:1 to 4:1. The catalysts are effective for the solution polymerization of olefins at high temperatures.

Description

FIELD OF THE INVENTION
The present invention relates to new catalyst systems for the polymerization of olefins. The catalyst system comprises a mixture of (i) a dialkyl magnesium compound; (ii) an aluminum alkyl compound and; (iii) a silanol; (iv) an alkyl halide; (v) a transition metal halide; and optionally (vi) either a dialkyl aluminum alkoxide or a trialkyl aluminum compound. The to catalyst systems are particularly useful as catalysts systems used in the solution polymerization of olefins and particularly for the polymerization of co- and homopolymers of ethylene.
BACKGROUND OF THE INVENTION
United States Patent 6,130,300 issued Oct. 10, 2000 to Jaber discloses a low aluminum and magnesium Ziegler Natta system. The catalyst comprises a mixture of an aluminum alkyl compound and a dialkyl magnesium compound, an alkyl halide, a titanium halide and a dialkyl aluminum alkoxide. The patent does not suggest that a silanol could be used in the catalyst. Additionally, the present invention contemplates some cases where the dialkyl aluminum alkoxide is absent.
United States Patent 4,295,992 issued Oct. 20, 1981 to Gibbs teaches preparing a catalyst support by reacting an alcohol, an organo 3o magnesium compound and a silicon halide. The present invention has eliminated the essential alcohol from the teaching of U.S. patent 4,295,992.
United States Patent 4,612,300 issued Sept 16, 1986 to Coleman, III teaches a Ziegler Natta catalyst in which one component is a soluble organomagnesium component of the formula MgR"2.xMR"y in which M may M:\Trevor\TT Specs\9235-Cda.doc
2 be AI, Zn, Si, Sn, B or P. There is no significant teaching regarding the possible use of silicon containing compounds. Further the catalyst requires the presence of a vanadium compound which has been eliminated from the catalysts of the present invention.
The present invention seeks to provide a catalyst useful in high temperature solution polymerization.
io SUMMARY OF THE INVENTION
Accordingly, the present invention seeks to provide a catalyst consisting essentially of a mixture of (i) a magnesium compound of the formula (R2)2Mg wherein R2 is a C,-~o alkyl radical (ii) an alkyl aluminum compound of the formula (R')~AI'(OR5)a and, wherein R' and R5 are independently selected from the group consisting of C~_,o alkyl radicals and a is 0 or 1;
(iii) a silicon containing compound of the formula:

(A)-( Ri O-)W-Bx-(SRO)y-D
wherein each A is independently selected from the group consisting of C~_2o alkyl radicals; G~_2o alkoxide radicals; C&~a 3o aryl radicals; C~.~4 aryl oxide radicals; and a hydroxy radical, B is selected from the group consisting of divalent C~_~o alkyl radicals and divalent C~.~4 aryl radicals which is unsubstituted or up to fully substituted by one or more C~_~o alkyl radicals, D is selected from the group consisting of a hydrogen atom, C~_2o alkyl radicals; C~_2o alkoxide radicals;
M:\Trevo~TT Specs19235-Cda.doc
3 Cs_~a aryl radicals; Cs_~a aryl oxide radicals; an amine radical or the formula NR9R'° where R9 and R'° are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C~.~° alkyl radical; a radical of the formula S02CF3; a radical of the formula SO2C6F5; a radical of the formula S-R9 where R9 is as defined above; a radical of the formula OS02R" wherein R" is selected from the group consisting of C~.2° alkyl radicals, and Cs_~a aryl radicals, a hydrogen atom; or a group 1, 2 or 3 metal, each R8 is selected from the group consisting of a hydrogen atom, a C~_ a alkyl radical, a C~~ alkoxide radical, a Cs_~a aryl radical; a Cs.~a aryl oxide radical; w is an integer from 1 to 5, x is 0 or 1, and y is 0 or 1, provided the silicon compound contains a functional group or atom which reacts with the above aluminum compound;
(iv) a halide of the formula R3X, wherein R3 is a C~.s alkyl radical and x is a halide selected from the group consisting of chlorine and bromine;
(v) transition metal halide, preferably titanium tetrachloride;
3o to provide a molar ratio of Mg to AI' from 2.0:1 to 12:1; Mg:
transition metal (e.g.Ti) from 3 to 8; a molar ratio of AI' to transition metal (e.g.Ti) from 0.25:1 to 4:1; a molar ratio of halide to Mg from 1.6:1 to 2.7:1; a molar ratio of Si:Ti from 0.25:1 to 4:1 and a molar ratio of AI' : Si from 0.25:1 to 4:1; and (vi) optionally an alkyl aluminum compound of the formula M:\Trevo~lTT Specs\9235-Cda.doc
4 (R4)~-eAl2(OR')b wherein R4 and R' are independently selected from the group consisting of C,_,o alkyl radicals and b is 1 or 0 to provide: a molar ratio of AI2 to transition metal (e.g.Ti) from 0:1 to 5:1 In a further embodiment, the present invention provides a process for the polymerization of a mixture consisting of at least 40 weight % of ethylene and up to 60 weight % of one or more C~,2 olefins comprising contacting said monomer mixture in a hydrocarbon solvent at a temperature from 105°C to 320°C and a pressure from 4 to 20 mPa with a catalyst consisting essentially of a mixture of (i) a magnesium compound of the formula (R2)2Mg wherein R2 is a C,_,o alkyl radical (ii) an alkyl aluminum compound of the formula (R')3_aAI'(OR5)a and, wherein R~ and R5 are independently selected from the group consisting of C,_,o alkyl radicals and a is 0 or 1;
(iii) a silicon containing compound of the formula:

(A)-(SI-O-),H-Bx-(SI-O)y-D
Ra Ra wherein each A is independently selected from the group so consisting of C,_2o alkyl radicals; C,_2o alkoxide radicals; C~,a aryl radicals; C~.,4 aryl oxide radicals; and a hydroxy radical, B is selected from the group consisting of divalent C,_,o alkyl radicals and divalent Cs_,4 aryl radicals which is unsubstituted or up to fully substituted by one or more C,_,o alkyl radicals, D is selected from the group consisting of a M:\Trevor\TT Specs\9235-Cda.doc
5 hydrogen atom, C~_2o alkyl radicals; C~_2o alkoxide radicals;
C~~4 aryl radicals; Cg_,4 aryl oxide radicals; an amine radical or the formula NR9R'°where R9 and R'° are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C~.~o alkyl radical; a radical of the formula S02CF3; a radical of the formula S02CsF5; a radical of the 1o formula S-R9 where R9 is as defined above; a radical of the formula OS02R" wherein R" is selected from the group consisting of C~_2o alkyl radicals, and C~~4 aryl radicals, a hydrogen atom; or a group 1, 2 or 3 metal, each R8 is selected from the group consisting of a hydrogen atom, a C~_ a alkyl radical and a C» alkoxide radical, a C~.~4 aryl radical;
and a C~~4 aryl oxide radical, w is an integer from 1 to 5, x is 0 or 1, and y is 0 or 1, provided the silicon compound contains a functional group or atom which reacts with the above aluminum compound;
(iv) a halide of the formula R3X, wherein R3 is a C~$ alkyl radical and x is a halide selected from the group consisting of chlorine and bromine;
(v) transition metal halide, preferably titanium tetrachloride;
to provide a molar ratio of Mg to AI' from 2.0:1 to 12:1; Mg:
transition metal (e.g.Ti) from 3 to 8; a molar ratio of AI' to transition metal (e.g.Ti) from 0.25:1 to 4:1; a molar ratio of halide to Mg from 1.6:1 to 2.7:1; a molar ratio of Si:Ti from 0.25:1 to 4:1 and a molar ratio of AI':Si from 0.25:1 to 4:1; and M:lTrevorlTT Specs19235-Cda.doC
6 (vi) optionally an alkyl aluminum compound of the formula (R4)3_bAl2(~R')b wherein R4 and R' are independently selected from the group consisting of C~_~o alkyl radicals and b is 1 or 0 to provide: a molar ratio of AI2 to transition metal (e.g.Ti) from 0:1 to 5:1 (vii) optionally an alkyl aluminum compound of the formula to (R4)3-bAl2(OR')b wherein R4 and R' are independently selected from the group consisting of C,_~oalkyl radicals and b is 1 or 0 to provide: a molar ratio of AIZ to transition metal (e.g.Ti) from 0:1 to 5:1 BEST MODE
There are a number of types of polymers of alpha olefins which may be made. For example, the polymer may be a liquid polymer or a waxy polymer having a low molecular weight. On the other hand, the polymer may have a very high molecular weight and have excellent physical properties but may be difficult to process. The present invention is directed to "useful" polymers of alpha olefins. In practical terms the polymer should have a melt index as determined by ASTM D 1238 (190°C
2.16 kg) of up to 200 dglmin. ASTM means the American Standard Test so Method and the conditions of the test are at 190°C and under a load of 2.16 kg. While the melt index may be fractional the lowest melt index would be that useful for extrudable polymers. Typical ranges would include melt indexes from 0.1 to 150, most typically from 0.1 to 120 dg/min.
M:\TrevorlTT Specs19235-Cda.doc
7 The process of the present invention may be used to prepare homopolymers of ethylene and copolymers of ethylene and higher alpha-olefins having densities in the range of, for example, about 0.900-0.970 g/cm3 and especially 0.910-0.965 g/cm3; the polymers of higher density, e.g. about 0.960 and above, being homopolymers. Such polymers may have a melt index, as measured by the method of ASTM D-1238, condition 1o E, in the range of, for example, 0.1-200 dg/min, typically from about 0.1 to 150 dg/min., and especially in the range of about 0.1 to 120 dg/min. The polymers may be manufactured with narrow or broad molecular weight distribution. For example, the polymers may have a stress exponent, a measure of the molecular weight distribution, in the range of about 1.1-2.5 and especially in the range of about 1.3-2Ø Stress exponent is determined by measuring the throughput of a melt indexer at two stresses (2160 g and 6480 g loading) using the procedures of the ASTM melt index test method, and the following formula:
Stress Exponent = 1/(0.477) x (Log. wt extruded with 6480 g weight) / wt. extruded with 2160 g wt).
Stress exponent values of less than about 1.40 indicate narrow molecular weight distribution while values above about 1.70 indicate broad molecular 3o weight distribution.
The present invention is directed to a process for the preparation of useful polymers of alpha-olefins, such polymers being intended for fabrication into articles by extrusion, injection molding, thermoforming, rotational molding and the like. In particular, the polymers of alpha-olefins are homopolymers of ethylene and copolymers of ethylene and higher M:\Trevo~\TT Specs\9235-Cda.doC
8 alpha-olefins, i.e. alpha-olefins of the ethylene series, especially such higher alpha-olefins having 3 to 12 carbon atoms, i.e. C3_,2 alpha-olefins, examples of which include 1-butene, 1-hexane, and 1-octane. The preferred higher alpha-olefins have 4-10 carbon atoms. In addition, cyclic endomethylenic dienes may be fed to the process with the ethylene or mixtures of ethylene and C3.~2 alpha-olefin. The monomer feed typically 1o comprises at least 40, preferably 60, most preferably 80 weight % of ethylene and up to 60, typically up to 40, preferably up to 20 weight % of one or more comonomers selected from the group consisting of C3_~2 olefins. Such polymers are known per se.
In the process of the present invention, monomer, generally one or more hydrocarbyl monomers, a coordination catalyst and inert hydrocarbon solvent and optionally hydrogen are fed to a reactor. The monomer may be ethylene or mixtures of ethylene and at least one C3_~2 alpha-olefin, preferably ethylene or mixtures of ethylene and at feast one C~~o alpha-olefin.
The solvent used in the preparation of the coordination catalyst is an inert C~~o hydrocarbon which may be unsubstituted or substituted by a C~.~ alkyl radical such as a hydrocarbon that is inert with respect to the so coordination catalyst. Such solvents are known and include for example, hexane, heptane, octane, cyclohexane, methylcyclohexane, and hydrogenated naphtha. The solvent used in the preparation of the catalyst is preferably the same as that fed to the reactor for the polymerization process. Caution should be exercised in selecting a solvent as a M:\Trevo~\TT Specs\9235-cda.doc
9 saturated monomer is not desired as a solvent for the reaction (i.e. hexane would not be preferred solvent for a hexene containing monomer).
The process of the present invention may be practiced over a wide range of temperatures that may be used in an alpha-olefin polymerization process operated under solution conditions. For example, such polymerization temperatures may be in the range of 105°C to 320°C, 1o preferably in the range of 130°C to 260°C, most preferably in the range from 180°C to 250°C. However, one of the considerations in selecting the temperature is that the polymer should remain in solution.
The pressures used in the process of the present invention are those known for solution polymerization processes, for example, pressures in the range of about 4-20 mPa, preferably from 8 to 20 mPa.
2o In the process of the present invention, the alpha-olefin monomers are polymerized in the reactor in the presence of the catalyst. Pressure and temperature are controlled so that the polymer formed remains in solution.
Optionally, small amounts of hydrogen, for example 0-100 parts per million based on the total solution fed to the reactor, may be added to the feed in order to improve control of the melt index and/or molecular weight 3o and thus aid in the production of a more uniform product, as is disclosed in Canadian Patent 703,704.
The coordination catalyst is formed from five, or optionally six components. The first component is a dialkyl magnesium compound of the formula (R2)2Mg wherein each R2 is independently (i.e. each R2 may be the same or different) a C~_~o, preferably a CZ.~, alkyl radical. Some M:\Trevor\TT Specs\9235-cda.doc useful magnesium compounds include diethyl magnesium and ethyl butyl magnesium.
The second component is a first aluminum compound of the formula (R')3_aAl'(OR5)a and, wherein R' and R5 are independently selected from the group consisting of C~_~o, preferably C1~ alkyl radicals andais0or1.
1o In a particularly preferred embodiment of the present invention the aluminum compound is triethyl aluminum.
The third component in the catalyst is a silicon containing compound of the formula:
Ra R$
~A)U R 0-)w-Bx-(SR~)yD
wherein each A is independently selected from the group consisting of C~_ 20, preferably C~_~o alkyl radicals; C~_2o, preferably C~_~o alkoxide radicals;
C&14, preferably C~.~2, aryl radicals; C~~4, preferably C~~2, aryl oxide radicals; and a hydroxy radical, B is selected from the group consisting of divalent C~_~o, preferably C~.~, alkyl radicals and divalent C~,4, preferably Cg_~2, aryl radicals which are unsubstituted or up to fully substituted by one or more C,_~o, preferably C~~, alkyl radicals, D is selected from the group 3o consisting of C~_2o, preferably C~.~o, alkyl radicals; C,_2o, preferably C~_~o, alkoxide radicals; Cs_,4, preferably C6_~2, aryl radicals; C6_~a,preferably C6.
~2, aryl oxide radicals; an amine radical or the formula NReR'° where and R'° are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C~-~o, preferably C~.~, alkyl radical; a radical of the formula S02CF3; a radical of the formula S02CsF5; a radical M:\T~evorlTT Specs\9235-Cda.doc of the formula S-R9 where R9 is as defined above; a radical of the formula OS02R" wherein R" is selected from the group consisting of C,_2o, preferably C~_~o, alkyl radicals, and C~.~4, preferably Cs_~2 aryl radicals, a hydrogen atom; or a group 1, 2 or 3 metal, each R8 is selected from the group consisting of a hydrogen atom, a C,~ alkyl radical, a C~.~ alkoxide radical, a Cg_~4, preferably C6_~2, aryl radicals; and a C~.~4, preferably C6_ ~2, aryl oxide radical, w is an integer from 1 to 5, preferably 1 to 3, most preferably 1, x is 0 or 1, and y is 0 or 1, provided the silicon compound contains a functional group or atom which reacts with the first aluminum compound (i.e. component (ii)).
Preferably the silicon containing compound contains a functional group selected from the group consisting of a hydroxyl radical, a C~_~o alkoxy radical a C~.~4 aryloxide radical, a radical of the formula OS02 R"
wherein R" is selected from the group consisting of Ci_2o alkyl radicals, and C~~4 aryl radicals, a lithium, sodium or potassium atom, a radical of the formula NR9R'°where R9 and R'° are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C~_~o alkyl radical; a radical of the formula S-R9 where R9 is as defined above; a radical of the formula S02CF3; and a radical of the formula SO2C6F5.
3o In one embodiment of the invention each R8 is independently selected from the group consisting of methyl, ethyl, methoxy, ethoxy, and phenyl radicals and a hydrogen atom.
In one embodiment of the invention A is selected from the group consisting of a methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, M:lTrevor~TT Specs~9235-Cda.doC

propyoxy, iso-propoxy, tertiary butyl, hydroxy, phenyl, phenoxy, benzyl and benzyloxy radicals.
In a further embodiment of the invention B is selected from the group consisting of a divalent methyl, ethyl, propyl, isopropyl, tertiary -butyl, phenyl, and benzyl radicals.
In a still further embodiment of the invention D is selected from the group consisting of a methoxy, ethoxy, propyoxy, iso-propoxy, phenoxy, benzyloxy radicals, a radical of the formula S02CF3, a radical of the formula S02C~F5, and a hydrogen, lithium, sodium, or potassium atom.
The fourth component in the catalyst systems according to the present invention is a reactive alkyl halide (reactive halide) of the formula R3X wherein R3 is a C~_8, preferably a C», alkyl radical and X is a halide selected from the group consisting of chlorine and bromine. Preferably, the second component is t-butyl halide, most preferably t-butyl chloride.
The fifth component in the catalyst of the present invention is a transition metal halide of the formula MX4, wherein M is a transition metal such as titanium, zirconium or hafnium, preferably titanium and X is a halide, preferably chloride. Preferably the transition metal halide is TiCl4.
The optional sixth component in the catalyst of the present 3o invention is an alkyl aluminum alkoxide of the formula (R4)3.eA12(OR~)~
wherein R4 and R' are independently selected from the group consisting of C~_~o, preferably C~.~ alkyl radicals and a is 1 or 0. A useful dialkyl aluminum alkoxide is diethyl aluminum ethoxide.
The first four components of the catalyst system are mixed to provide a molar ratio of Mg: AI' from 2.0:1 to 12:1, preferably 4.:1 to 6:1, M:\Trevo~\TT Specs\9235-Cda.doc Mg:Ti from 3:1 to: 8,1 preferably 4:1 to 6:1, a molar ratio of AI'aransition metal from 0.25:1 to 4:1, preferably from 0.5:1 to 3:1; a molar ratio of (reactive) halide from component (iv) to Mg from 1.6:1 to 2.7:1, preferably from 1.8:1 to 2.4:1, and a molar ratio ofAl':Si from 0.25:1 to 4:1, preferably from 0.5:1 to 3:1 The fifth component is optional and may used in an amount to 1o provide a molar ratio of Al2aransition metal (preferably titanium) 0:1 to 5:1, if it is used preferably it is present in an amount from 0.5:1 to 3:1.
In one embodiment of the present invention R', R3, R4, R5 and R' are independently selected from the group consisting of C,~ alkyl radicals and preferably R', R4, R5 and R' are ethyl radicals.
While all of the components of the catalyst system may be mixed together at once, generally the first components are mixed together, optionally at room temperature to form a precursor which may be further activated by the sixth component.
In a further embodiment of the present invention all of the components of the catalyst or a preformed precursor which may be prepared by inline mixing (typically from one to two minutes) at a temperature from 20° C to 180° C, typically form about 20° C to 80° C, 3o preferably from 20° C to 60° C for a time upto three or four hours, preferably less than an hour, typically from 5 seconds to 30 minutes. After preparation the catalyst may be stored in inert conditions (i.e. under an inert atmosphere).
The catalyst system of the present invention is used in the process of the invention without separation of any of the components of the M:\Trevor\TT Specs19235-Cda.doc catalyst. In particular, neither liquid nor solid fractions are separated from the catalyst before it is fed to the reactor. In addition, the catalyst and its components are not slurries. All the components are easy-to-handle, storable stable liquids.
The solvent containing monomers, catalyst or catalyst components, and optionally hydrogen an: fed to the reactor and react under good io mixing conditions for a short period of time, preferably less than 10 minutes.
The solution passing from the polymerization reactor is normally treated to deactivate any catalyst remaining in the solution. A variety of catalyst deactivators are known, examples of which include fatty acids, alkaline earth metal salts of aliphatic carboxylic acids and alcohols. The hydrocarbon solvent used for the deactivator is preferably the same as the solvent used in the polymerization process. If a different solvent is used, it must be compatible with the solvent used in the polymerization mixture and not cause adverse effects on the solvent recovery system associated with the polymerization process. The solvent may then be flashed off from the polymer, which subsequently may be extruded into water and cut into pellets or other suitable comminuted shapes. The recovered polymer may 3o then be treated w~h saturated steam at atmospheric pressure to, for example, reduce the amount of volatile materials and improve polymer color. The treatment may be carried out for about 1 to 6 hours, following which the polymer may be dried and cooled with a stream of air for 1 to 4 hours.
M:\Trevo~\TT Specs\9235-Cda.doc Pigments, antioxidants, UV screeners, hindered amine light stabilizers and other additives may be added to the polymer either before or after the polymer is formed into pellets or other comminuted shapes.
The antioxidant incorporated into polymer obtained from the process of the present invention may, in embodiments, be a single antioxidant, e.g.
hindered phenolic antioxidant, or a mixture of antioxidants, e.g. a hindered 1o phenolic antioxidant combined with a secondary antioxidant, e.g.
phosphite. Both types of antioxidant are known in the art. For example, the ratio of phenolic antioxidant to secondary antioxidant may be in the range of 0.1:1 to 5:1 with the total amount of antioxidant being in the range of 200 to 3,000 ppm.
The present invention will now be illustrated by the following non-limiting examples. Unless otherwise indicated parts means part by weight and percent (%) is weight percent. In the following examples, unless indicated otherwise, the compound to give AI' was triethyl aluminum; the magnesium compound was butyl ethyl magnesium; the transition metal compound was TiCl4; the halide compound was t-butyl chloride; and the compound providing the AI2 was diethyl aluminum ethoxide.
Unless otherwise indicated the polymerizations were conducted 3o using a small scale continuous polymerization unit. The polymerization was a solution polymerization of ethylene and octane conducted at 230°
C.
In all the experiments the feed rates were controlled so that the ratio of octane to ethylene was 0.5 (weight e.g. glg). The feed rates of the catalyst components were controlled to provide a molar ratio of MglTi of 5.0 and a molar ratio of chlorine ftom component (iv) to Mg of 2.2. The hold up time M:\Trevo~lTT Specs\9235-Cda.doC

(HUT) in the reactor was 1 minute. The conversion (% Q) and the propagation rate constant (kp - liter of ethylene consumed per m mol of catalyst per minute of reaction time) were recorded together with the product properties of melt index (Mi - g of polymer per 10 min), density (D
g/cc), the molecular weight (weight average Mw) and poiydispersity (PD) of the polymer (Mw/AAn) were recorded.
to Example 1 A series of polymerizations were conducted using Ph3SiOH as the silicon containing compound (A and R8 are phenyl radicals , w is 1, x is 0 and D is a hydrogen atom). The first aluminum component was triethyl aluminum (R' is ethyl and a is 0) and the second aluminum compound was present and was diethyl aluminum ethoxide (R4 is ethyl, R' is ethyl and b is 1 ). In the experiment the mole ratio of AI2: Ti was 2. In the control no silicon compound was used. The results of the experiment are set forth in table 1.
Table 1.
Use of Ph3SiOH-AIEt3 and Et2AlOEt in the catalyst Run [Ti] Si/TiAIEt3/AIEt% Kp MI DensitMW PD
# (umol(mollSi 3lTiC2 (Ummol y o /L) mol)(moll(mollConv.Ti.min) (g/cc) mol) mol) 1 270 1.0 87.6626.3 16.50.937855800 4.16 2 270 2.0 0.5 1.0 92.5145.7 17.30.937745200 3.25 3 270 1.0 1.0 1.0 92.7047.0 15.90.935548500 3.13 4 270 0.5 2.0 1.0 93.5653.8 32.20.935738900 2.92 5 240 1.0 0.94 0.9488.6432.5 24.40.938644100 3.58 6 240 0.5 1.0 0.5 86.6527.0 12.00.935255600 3.07 M:lTrevor\TT Specs\9235-Cda.doc Run 1 is a control with no silanol. Runs 2, 3, and 4 show higher conversions than the control run. In runs 5 and 6 a lower amount of titanium was used in the catalyst and comparable conversions were obtained. The poliydispersity (Mw/Mn) of the polymers made using the catalyst of the present invention is narrower than the control.
to Example 2 Example 1 was repeated except that the silicon compound was t-butyl Me2SiUH ( i.e. A is t-butyl , R8 is methyl, w is 1, x is 0 and D is a hydrogen atom). The first aluminum component was diethyl aluminum ethoxide (R4 is ethyl, R' is ethyl and b is 1 ) and the second aluminum compound was present and was triethyl aluminum, combined with t-butyl Me2SiOH, (R' is ethyl and a is 0). In the control no silicon compound was used. The results of the experiment are set forth in table 2.
Table 2 Run [Ti) Sid AIEt3/AIEt3/k Kp MI DensityMW PD

# (umoUL)(mollSi Ti Conv(Ummol (glcc) mol) (moll(moll Ti.min) mol) mol) 1 270 1.0 87.6626.3 16.50.937855800 4.2 7 270 1.0 1.0 1.0 91.8341.6 32.70.937244600 3.6 8 270 1.5 1.0 1.5 91.7841.4 37.90.938839000 3.5 9* 270 1.0 1.0 1.0 90.6035.7 38.50.937939100 3.4 The results show that the second component may be an aluminum alkyl combined with silanol and the first component may be an alkyl aluminum alkoxide and still there is a higher conversion than the control. Again, the M:\T~evor\TT Specs\9235-Cda.doc polymers prepared in accordance with the present invention have a narrower polydispersity than the control.
Example 3 Example 2 was repeated except that the first aluminum compound was triethyl aluminum combined with t-butyl Me2SiOH and the second 1o aluminum compound was diethyl aluminum ethoxide. The results of the experiment are shown in table 3.
Table 3 Run [Ti] Si/TiAIEt3AIEt3/TirbC2 Kp MI DensityMW PD
# (umol/(mol//Si (mol/ Conv.(Ummol (g/cc) L) mol) (mol/mol) Ti.min) mol) 1 270 1.00 87.6626.3 16.5 0.9378558004.2 20 10 270 1.0 1.0 1.00 94.4663.2 48.0 0.9317372002.8 11 165 1.0 1.0 1.00 87.5942.8 24.5 0.9365453003.4 12 165 1.5 1.0 1.50 87.3441.8 26.4 0.9165453002.9 Runs 11 and 12 of table 3 show that when using the silicon containing catalyst of the present invention it is possible to reduce the titanium in the catalyst by up to about 40% and still maintain comparable ethylene conversion. Again the polymers prepared in accordance with the present invention have a narrower polydispersity than those prepared according to the prior art.
Example 4 Example 3 was repeated except that either the second aluminum compound was omitted or significantly reduced. The first aluminum alkyl M:\TrevorlTT Specs\9235-Cda.doc was triethyl aluminum combined with t-butyl Me2SiOH. The results are set forth in table 4.
Table 4.
Run [Ti] AIEt3/TiSi/AlEt3Et2AlOEtQ-FE Kp MI DensityMW PD
# (umol/l_)(moll (moll ffi 10 (Ummol (g/cc) mol) mol) (mol/mol) Ti.min) 13 317 1.1 2.0 87.6227.2 0.9389424003.5 14 317 1.1 0.9 71.758.0 317 1.6 0.9 88.7524.9 26.00.9341417003.3 16 317 2.2 0.9 95.1161.3 102Ø9318304003.1 17 317 2.7 0.9 95.2663.4 73.10.9326309003.2 18 317 2.2 0.9 0.5 95.0560.5 70.80.9344355003.5 19 317 2.2 0.9 1.0 95.2062.5 88.80.9345319003.4 Table 4 shows it is possible to eliminate the second aluminum component and still maintain a good ethylene conversion.

M:lTrevor~TT Specs19235-cda.doc

Claims (69)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A catalyst consisting essentially of a mixture of (i) a magnesium compound of the formula (R2)2Mg wherein R2 is a C1-10 alkyl radical (ii) an alkyl aluminum compound of the formula (R1)3-aAl1(OR5)a and, wherein R1 and R5 are independently selected from the group consisting of C1-10 alkyl radicals and a is 0 or 1;

(iii) a silicon containing compound of the formula:

wherein each A is independently selected from the group consisting of C1-20 alkyl radicals; C1-20 alkoxide radicals; C6-14 aryl radicals; C6-14 aryl oxide radicals; and a hydroxy radical, B
is selected from the group consisting of divalent C1-10 alkyl radicals and divalent C6-14 aryl radicals which is unsubstituted or up to fully substituted by one or more C1-10 alkyl radicals, D is selected from the group consisting of a hydrogen atom, C1-20 alkyl radicals; C1-20 alkoxide radicals;
C6-14 aryl radicals; C6-14 aryl oxide radicals; an amine radical or the formula NR9R10 where R9 and R10 are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C1-10 alkyl radical; a radical of the formula SO2CF3; a radical of the formula SO2C8F5; a radical of the formula S-R9 where R9 is as defined above; a radical of the formula OSO2R11 wherein R11 is selected from the group consisting of C1-20 alkyl radicals, and C6-14 aryl radicals, a hydrogen atom; or a group 1, 2 or 3 metal, each R8 is selected from the group consisting of a hydrogen atom, a C1-4 alkyl radical, a C1-4 alkoxide radical, a C6-14 aryl radical; a C6-14 aryl oxide radical; w is an integer from 1 to 5, x is 0 or 1, and y is 0 or 1, provided the silicon compound contains a functional group or atom which reacts with the above aluminum compound;

(iv) a halide of the formula R3X, wherein R3 is a C1-8 alkyl radical and x is a halide selected from the group consisting of chlorine and bromine;

(v) titanium tetrachloride;
to provide a molar ratio of Mg to Al1 from 2.0:1 to 12:1; Mg:Ti from 3 to 8; a molar ratio of Al1 to Ti 0.25:1 to 4:1; a motar ratio of halide to Mg from 1.6:1 to 2.7:1; a molar ratio of Si:Ti from 0.25:1 to 4:1 and a molar ratio of Al1: St from 0.25:1 to 4:1; and (vi) optionally an alkyl aluminum compound of the formula (R4)3-bAl2(OR7)b, wherein R4 and R7 are independently selected from the group consisting of C1-10 alkyl radicals and b is 1 or 0 to provide: a molar ratio of Al2 to Ti from 0:1 to 5:1
2. The catalyst according to claim 1, wherein R1, R3, R4, R5 and R7 are independently selected from the group consisting of C1-4 alkyl radicals.
3. The catalyst according to claim 2, wherein R1 is an ethyl radical.
4. The catalyst according to claim 3, wherein R2 is a C2-5 alkyl radical.
5. The catalyst according to claim 4, wherein R3 is a tertiary butyl radical.
6. The catalyst according to claim 5, wherein each R8 is independently selected from the group consisting of methyl, ethyl, methoxy, ethoxy and phenyl radicals and a hydrogen atom.
7. The catalyst according to claim 6, wherein in the silicon containing compound contains a functional group selected from the group consisting of a hydroxyl radical, a C1-10 alkoxy radical a C6-14 aryloxide radical, a radical of the formula OSO2 R11 wherein R11 is selected from the group consisting of C1-20 alkyl radicals, and C6-14 aryl radicals, a lithium, sodium or potassium atom, a radical of the formula NR9R10 where R9 and R10 are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C1-10 alkyl radical; a radical of the formula S-R9 where R9 is as defined above; a radical of the formula SO2CF3; and a radical of the formula SO2C6F5.
8. The catalyst according to claim 7, wherein R1, R4, R5 and R7 are ethyl radicals.
9. The catalyst according to claim 8, wherein the molar ratio of Mg:Al1 is from 4:1 to 6:1.
10. The catalyst according to claim 9, wherein the molar ratio of Mg:Ti is from 4:1 to 6:1.
11. The catalyst according to claim 10, wherein the molar ratio of Al1 to Ti is from 0.5:1 to 3:1.
12. The catalyst according to claim 11, wherein the molar ratio of halide to Mg is from 1.8:1 to 2.4:1.
13. The catalyst according to claim 12, wherein the molar ratio of Al1:Si is from 0.5:1 to 3:1.
14. The catalyst according to claim 13, wherein the molar ratio of Si:Ti is from 0.5:1 to 3:1.
15. The catalyst according to claim 14, wherein A is selected from the group consisting of a methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propyoxy, iso-propoxy, tertiary butyl, hydroxy, phenyl, phenoxy, benzyl and benzyloxy radicals.
16. The catalyst according to claim 15, wherein B is selected from the group consisting of a divalent methyl, ethyl, propyl, isopropyl, tertiary -butyl, phenyl, and benzyl radicals.
17. The catalyst according to claim 16, wherein D is selected from the group consisting of a methoxy, ethoxy, propyoxy, iso-propoxy, phenoxy, benzyloxy radicals, a radical of the formula SO2CF3, a radical of the formula SO2C6F5, and a hydrogen, lithium, sodium, or potassium atom,
18. The catalyst according to claim 17, wherein x is 1
19 The catalyst according to claim 17, wherein x is 0 and y is 1.
20. The catalyst according to claim 19 wherein w is 1.
21. The catalyst according to claim 17 wherein w is 1 and x is 0 and y is 0.
22. The catalyst according to claim 21, wherein the Al2 is absent
23. The catalyst according claim 22 wherein a is 1.
24. The catalyst according to claim 22 wherein a is 0.
25. The catalyst according to claim 21, wherein Al2 is present to provide a molar ratio of AI2 to Ti from 0.5:1 to 3:1
26. The catalyst according to claim 25, wherein a is 0 and b is 0.
27. The catalyst according to claim 25 wherein a is 1 and b is 0.
28. The catalyst according to claim 25 wherein a is 0 and b is 1.
29. The catalyst according to claim 25 wherein a is 1 and b is 1.
30. A process for preparing a catalyst according to claim 1, comprising mixing in components (i), (ii), (iii), (iv) (v) and optionally (vi) for a time from 5 seconds to 30 minutes.
31. The process according to claim 30 wherein the temperature for mixing is from 20° C to 180 ° C.
32. The process according to claim 31 wherein the components (ii) and (iii) are pre-mixed and added as a single component.
33. The process according to claim 32 wherein component (vi) is absent.
34. The process according to claim 33, wherein the components are mixed in a line feeding into an olefin polymerization reactor.
35. The process according to claim 32 wherein component (vi) is present.
36. The process according to claim 35 wherein component (vi) is mixed in a line feeding into an ethylene polymerization reactor.
37. The process according to claim 36 wherein component (vi) is added directly to the olefin polymerization reactor.
38. A process for the polymerization of a mixture consisting of at least 40 weight % of ethylene and up to 60 weight % of one or more C3-12 olefins comprising contacting said monomer mixture in a hydrocarbon solvent at a temperature from 105°C to 320°C and a pressure from 4 to 20 mPa with a catalyst consisting essentially of a mixture of (i) a magnesium compound of the formula (R2)2Mg wherein R2 is a C1-10 alkyl radical (ii) an alkyl aluminum compound of the formula (R1)3aAl1(OR5)a and, wherein R1 and R5 are independently selected from the group consisting of C1-10 alkyl radicals and a is 0 or 1;
(iii) a silicon containing compound of the formula:
wherein each A is independently selected from the group consisting of C1-20 alkyl radicals; C1-20 alkoxide radicals; C6-144 aryl radicals; C6-14 aryl oxide radicals; and a hydroxy radical, B is selected from the group consisting of divalent C1-10 alkyl radicals and divalent C6-14 aryl radicals which is unsubstituted or up to fully substituted by one or more C1-10 alkyl radicals, D is selected from the group consisting of a hydrogen atom, C1-20 alkyl radicals; C1-20 alkoxide radicals;
C6-14 aryl radicals; C6-14 aryl oxide radicals; an amine radical or the formula NR9R10 where R9 and R10 are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C1-10 alkyl radical; a radical of the formula SO2CF3; a radical of the formula S02C6F5; a radical of the formula S-R9 where R9 is as defined above; a radical of the formula OSO2R11 wherein R11 is selected from the group consisting of C1-20 alkyl radicals, and C6-14 aryl radicals, a hydrogen atom; or a group 1, 2 or 3 metal, each R8 is selected from the group consisting of a hydrogen atom, a C1-4 alkyl radical and a C1-4 alkoxide radical, a C6-14 aryl radical;
and a C6-14 aryl oxide radical, w is an integer from 1 to 5, x is 0 or 1, and y is 0 or 1, provided the silicon compound contains a functional group or atom which reacts with the above aluminum compound;

(iv) a halide of the formula R3X, wherein R3 is a C1-8 alkyl radical and x is a halide selected from the group consisting of chlorine and bromine;
(v) titanium tetrachloride;
to provide a molar ratio of Mg to Al1 from 2.0:1 to 12:1; Mg:Ti from 3 to 8; a molar ratio of Al1 to Ti 0.25:1 to 4:1; a molar ratio of halide to Mg from 1.6:1 to 2.7:1; a molar ratio of Si:Ti from 0.25:1 to 4:1 and a molar ratio of Al1:Si from 0.25:1 to 4:1; and (vi) optionally an alkyl aluminum compound of the formula (R4)3-bAl2(OR7)b, wherein R4 and R7 are independently selected from the group consisting of C1-10 alkyl radicals and b is 1 or 0 to provide a molar ratio of Al2 to Ti from 0:1 to 5:1.
39. The process according to claim 38, wherein the temperature is from 180°C to 250°C.
40. The process according to claim 39, wherein the said monomer mixture comprises at least 60 weight % of ethylene and up to 40 weight %
of one or more C3-12 olefins.
41 The process according to claim 40, wherein the said monomer mixture comprises at least 80 weight % of ethylene and up to 20 weight %
of one or more C3-12 olefins.
42. The process according to claim 41, wherein R1, R3, R4, R5 and R7 are independently selected from the group consisting of C1-4 alkyl radicals.
43. The process according to claim 42, wherein R1 is an ethyl radical.
44. The process t according to claim 43, wherein R2 is a C2-6 alkyl radical.
45. The process according to claim 44, wherein R3 is a tertiary butyl radical.
46. The process according to claim 45, wherein each R8 is independently selected from the group consisting of methyl, ethyl, methoxy, ethoxy and phenyl radicals and a hydrogen atom.
47. The process according to claim 46, wherein in the silicon containing compound contains a functional group selected from the group consisting of a hydroxyl radical, a C1-10 alkoxy radical a C6-14 aryloxide radical, a radical of the formula OSO2 R11 wherein R11 is selected from the group consisting of C1-20 alkyl radicals, and C6-14 aryl radicals, a lithium, sodium or potassium atom, a radical of the formula NR9R10 where R9 and R10 are independently selected from the group consisting of a hydrogen atom, a hydroxyl radical, a C1-10 alkyl radical; a radical of the formula S-R9 where R9 is as defined above; a radical of the formula SO2CF3; and a radical of the formula SO2C6F5.
48. The process according to claim 47, wherein R1, R4, R5 and R7 are ethyl radicals.
49. The process according to claim 48, wherein the molar ratio of Mg:Al1 is from 4:1 to 6:1.
50. The process according to claim 49, wherein the molar ratio of Mg:Ti is from 4:1 to 6:1.
51. The process according to claim 50, wherein the molar ratio of Al1 to Ti is from 0.5:1 to 3:1.
52. The process according to claim 51, wherein the molar ratio of halide to Mg is from 1.8:1 to.2.4:1.
53. The process according to claim 52, wherein the molar ratio of Al1:Si is from 0.5:1 to 3:1.
54. The process according to claim 53, wherein the molar ratio of Si:Ti is from 0.5:1 to 3:1.
55. The process according to claim 54, wherein A is selected from the group consisting of a methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propyoxy, iso-propoxy, tertiary butyl, hydroxy, phenyl, phenoxy, benzyl and benzyloxy radicals.
56. The process according to claim 55, wherein B is selected from the group consisting of a divalent methyl, ethyl, propyl, isopropyl, tertiary -butyl, phenyl, and benzyl radicals.
57. The process according to claim 56, wherein D is selected from the group consisting of a methoxy, ethoxy, propyoxy, iso-propoxy, phenoxy, benzyloxy radicals, a radical of the formula SO2CF3, a radical of the formula SO2C6F5, and a hydrogen, lithium, sodium, or potassium atom.
58. The process according to claim 57, wherein x is 1.
59 The process according to claim 57, wherein x is 0 and y is 1.
60. The process according to claim 59, wherein w is 1.
61. The process according to claim 57, wherein w is 1 and x is 0 and y is 0.
62. The process according to claim 61, wherein the Al2 is absent.
63. The process according claim 62, wherein a is 1.
64. The process according to claim 62, wherein a is 0.
65. The process according to claim 61, wherein AIZ is present to provide a molar ratio of AI2 to Ti from 0.5:1 to 3:1
66. The process according to claim 65, wherein a is 0 and b is 0.
67. The process according to claim 65, wherein a is 1 and b is 0.
68. The process according to claim 65, wherein a is 0 and b is 1.
69. The process according to claim 65, wherein a is 1 and b is 1.
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