Classifications

• • 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
  • C08F10/02—Ethene
• • 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
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
  • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
  • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

• the present invention relates to a process for the polymerization of ethylene.
• Patent applications WO 99/61486 and WO 96/11960 describe methods of polymerizing ethylene using a supported metallocene, an aluminoxane, a trialkylaluminum and a nonionic antistatic agent chosen from diethoxylated tertiary alkylamines, which do not give crusting.
• Patent application EP 0 803 514 describes a process for (co) polymerization of propylene using a supported metallocene catalyst, an aluminoxane, a trialkylaluminium and an ionic antistatic agent, which does not give crusting or formation of d agglomerates.
• the present invention relates to a process for the manufacture of homo- or copolymers of ethylene comprising at least 90 mole% of units derived from ethylene in which is brought into contact, under polymerizing conditions, ethylene and, optionally, the other monomers with a catalytic system comprising
• a catalytic solid comprising a metallocene of a transition metal from groups 4 to 6 of the Periodic Table containing at least one cyclopentadienic ligand which can be substituted, deposited on a support,
• T is a hydrocarbon group containing from 1 to 30 carbon atoms
• - Y ' is a group chosen from -OR', -SR 'and NR'R "with R' and R" representing, independently, a hydrocarbon group containing from 1 to 30 carbon atoms, - X 'is an atom halogen,
• - x is a number satisfying the condition 0 ⁇ x ⁇ 3,
• - y is a number satisfying the condition 0 ⁇ y ⁇ 3,
• ethylene polymerization process is intended to denote a process for the manufacture of homo- and ethylene copolymers comprising at least 90 mole% of units derived from ethylene.
• the preferred copolymers are those of ethylene and another alpha-olefin comprising from 3 to 8 carbon atoms. Particularly preferred are the copolymers of ethylene and 1-butene and / or 1-hexene.
• the metallocene used in the process according to the present invention is most often chosen from the compounds corresponding to the formula
• R ⁇ and R ⁇ each represent hydrocarbon groups containing from 1 to 20 carbon atoms which can be linked to the cyclopentadienic ring in the form of a monovalent group or which can be linked to each other so as to form a ring adjacent to the cyclopentadienic ring, halogen atoms, alkoxy groups having 1 to 12 carbon atoms, silicon-containing hydrocarbon groups of the formula
• R ⁇ phosphorous hydrocarbon groups of formula -P (R) (R5), nitrogenous hydrocarbon groups of formula -N (R4) (R5) OR hydrocarbon groups containing boron of formula -B (R4) (R5) in which R ⁇ , R5 and R ⁇ represent hydrocarbon groups containing from 1 to 24 carbon atoms, provided that when b, c or d is 2 or plus and / or that there is a plurality of groups R ⁇ or R ⁇ , the latter may be identical or different,
• Me represents a transition metal from groups 4 to 6 of the Periodic Table, and - X and Y, identical or different, each represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group , a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms.
• the preferred transition metal compounds of formula (2) are generally such that
• Q represents an alkylene group containing 1 or 2 carbon atoms which may be substituted by alkyl or aryl groups containing from 1 to 10 carbon atoms, or a dialkylgermanium or dialkylsilicon group containing from 1 to 6 carbon atoms, a is 0 or i ,
• Ri and R ⁇ represent alkyl, alkenyl, aryl, alkylaryl, alkenylaryl or arylalkyl groups containing from 1 to 20 carbon atoms, several R ⁇ groups and / or several R2 groups which can be linked one to the other so as to form a ring containing from 4 to 8 carbon atoms,
• - Me is zirconium, hafhiurn or titanium
• - X and Y represent halogen atoms or hydrocarbon groups chosen from alkyls, aryls and alkenyls containing from 1 to 10 carbon atoms.
• metallocenes of formula (2) in which Q is a linking group chosen from dimethyl- and diphenyl silyl, ethylene and the methylenes and ethylenes substituted by alkyl or aryl groups containing from 1 to 8 atoms of carbon.
• Q is a linking group chosen from dimethyl- and diphenyl silyl, ethylene and the methylenes and ethylenes substituted by alkyl or aryl groups containing from 1 to 8 atoms of carbon.
• Compounds of formula (2) which are particularly suitable are the compounds in which the ligands (C5H5_ a _bRlb) and (C5H5_ a _ c R2 c ) are chosen from cyclopentadienyls, indenyls and fluorenyls which can be substituted.
• the catalytic solid (a) most often also includes an activator.
• the activator is generally chosen from aluminoxanes and ionizing agents.
• aluminoxanes is meant the compounds corresponding to the formula R ⁇ - (Al R ⁇ - O) m - A1R? 2 and the cyclic compounds corresponding to the formula (-A1 R? - O -) m +2 in which m is a number from 1 to 40 and R is an alkyl or aryl group containing from 1 to 12 carbon atoms.
• the preferred compounds are chosen from methyl-, ethyl-, isobutylaluminoxanes and their mixtures, and more particularly those in which m is a number from 2 to 20. Very particularly preferred is methylaluminoxane (MAO) in which m is a number from 10 to 18.
• ionizing agents is intended to denote the compounds comprising a first part which has the properties of a Lewis acid and which is capable of ionizing the metallocene and a second part which is inert with respect to the ionized metallocene and which is able to stabilize it.
• triphenylcarbenium tetrakis (pentafluorophenyl) borate N, N-dimethylanilium tetrakis (pentafluorophenyl) borate, tri (n-butyl) tetrakis (pentafluorophenyl) borate - ammonium, tri (pentafluorophenyl) boron, triphenyl boron, trimethyl boron, tri (trimethylsilyl) boron and organoboroxins.
• the amount of activator in the catalytic solid depends on the type of activator used.
• the activator is an aluminoxane
• the amount of aluminoxane is most often such that the atomic ratio of aluminum from the aluminoxane to the transition metal from the metallocene is from 2 to 5000. Preferably, this ratio is at least 5, more particularly at least 10. Good results are obtained when this ratio is at least 20.
• the aluminoxane is used in quantities such as the aluminum / metal atomic ratio of transition is at most 2000, more particularly at most 1500. Atomic ratios of aluminum from the aluminoxane of the transition metal of at most 1000 are most particularly preferred. Reports of up to 300 give good results.
• the quantity of ionizing agent is most often such that the molar ratio between the ionizing agent and the metallocene is from 0.05 to 50. Preferably this ratio is at least 0 , 1 and more particularly at most 20.
• the catalytic solid (a) contains a support.
• the support can be any known organic or inorganic support making it possible to support the metallocene and optionally the activator.
• inorganic supports mention may be made of talc or inorganic oxides such as silicas, aluminas, oxides of titanium, zirconium, magnesium or mixtures thereof. Such supports have in particular been described in patent application EP 0 206 794.
• the organic supports are most often chosen from porous polymeric supports, and more particularly from polyolefin supports as described in patent application EP 1 038 883.
• Inorganic supports are preferred in the context of the present invention. Silica is particularly preferred.
• the catalytic solid (a) used in the process according to the invention can be obtained by different methods. In general, carrier particles are contacted with a solution containing the activator to obtain a suspension which is then evaporated. The metallocene can be introduced into the suspension described above. It may also have been incorporated into the support before it came into contact with the activator. Finally, it can be brought into contact with the support particles comprising the activator.
• the catalytic solid (a) used in the process according to the present invention generally contains from 0.001 to 5 g of metallocene per gram of support. Preferably the metallocene concentration is at least 0.005 g and more particularly at least 0.01 g per gram of support. Amounts of metallocene less than or equal to 3 and preferably less than or equal to 1 g per gram of support give good results.
• a catalytic solid (a) which has been subjected to a preliminary polymerization during which it is brought into contact with an alpha-olefin, under polymerizing conditions so as to form 0.01 to 50 g of polyolefin per g of catalytic solid.
• the alpha-olefin used during the preliminary polymerization step is advantageously chosen from alpha-olefins containing from 2 to 4 carbon atoms.
• the catalytic system also comprises at least one organoaluminum compound (b) corresponding to the general formula (1).
• the organoaluminum compound is preferably chosen from trialkylaluminiums of formula AIT3, and more particularly from those in which each T independently represents an alkyl group containing from 1 to 20 carbon atoms. Particularly preferred is a trialkylaluminium in which T is an alkyl group containing from 1 to 6 carbon atoms, such as trimethylaluminium (TMA), triethylaluminium and tri-isobutylaluminium (TL3AL).
• TMA trimethylaluminium
• T3AL triethylaluminium
• TL3AL tri-isobutylaluminium
• the amount of organoaluminum compound (b) used in the process according to the invention is generally such that the atomic ratio of aluminum originating from the organoalumimum compound (b) to the transition metal originating from the metallocene is from 10 to 50,000. Preferably this ratio is at least 20, more particularly at least 30. Good results are obtained when this ratio is at least 40. Most often, the organoaluminum compound (b) is used in amounts such that the aluminum atomic ratio originating from the organoaluminum / transition metal compound originating from the metallocene is at most 20,000 and more particularly at most 17,000. Reports of at most 15,000 give good results.
• the catalytic system used in the process according to the invention also comprises at least one ionic antistatic agent (c).
• the ionic antistatic agents are generally chosen from those containing a long hydrophobic chain.
• ionic antistatic agents are used comprising at least one hydrocarbon group containing from 6 to 35 carbon atoms, optionally substituted.
• the antistatic agent is chosen from cationic antistatic agents and more particularly from the quaternary ammonium salts represented by the general formula A1A2A3A ⁇ NX1 in which A, A ⁇ , A- 3 and A4 independently represent a hydrocarbon group containing from 1 to 35 carbon atoms and at least one of A, A ⁇ , A ⁇ and A ⁇ is a hydrocarbon group containing from 6 to 35 carbon atoms, and ⁇ l is an atom halogen.
• Quaternary alkylammonium salts containing at least one alkyl group containing from 6 to 35 carbon atoms are preferred.
• Quaternary alkylammonium salts containing at least one alkyl group containing from 6 to 35 carbon atoms derived from a fatty acid give good results.
• quaternary ammonium salt mention may be made of dicocoalkyl-dimethylammonium chloride.
• the product commercially available under the name CHEMAX® X-997 is particularly preferred.
• the antistatic agent is chosen from anionic antistatic agents and more particularly from sulfonic acids comprising at least one hydrocarbon group containing from 6 to 35 carbon atoms, optionally substituted.
• Sulfonic acids comprising a hydrocarbon group, preferably an aryl group, containing from 6 to 18 carbon atoms and substituted with at least one alkyl group containing 6 to 16 carbon atoms give good results.
• sulfonic acid mention may be made of dinonylnaphthalene sulfonic acid.
• the product marketed by OCTEL under the name STADIS® 450 is particularly preferred.
• the amount of antistatic agent used in the process according to the invention is generally such that the molar ratio of the antistatic agent (c) to the organoaluminum compound (b) is less than 0.5.
• the molar ratio of the antistatic agent to the organoaluminum compound is less than 0.2. Molar ratios of less than 0.1 are particularly preferred.
• the amount of antistatic agent is such that the molar ratio of the antistatic agent (c) to the organoaluminum compound (b) is generally at least 0.001.
• this molar ratio is at least 0.002, more particularly at least 0.003.
• a premix comprising advantageously at least the organoaluminum compound (b) and the antistatic agent (c) is advantageously prepared, before adding the catalytic solid (a) to it.
• the polymerization process according to the invention can be carried out continuously or batchwise, according to any known process.
• the polymerization process is preferably carried out in suspension in a hydrocarbon diluent.
• the hydrocarbon diluent is generally chosen from aliphatic hydrocarbons containing from 3 to 10 carbon atoms.
• the diluent is chosen from propane, isobutane, hexane or their mixtures.
• the temperature at which the polymerization process according to the invention is carried out is generally from -20 ° C to +150 ° C, most often from 20 to 130 ° C.
• the polymerization temperature is preferably at least 60 ° C. Preferably, it does not exceed 115 ° C.
• the total pressure at which the process according to the invention is carried out is generally chosen between atmospheric pressure and 100 10 ⁇ Pa, more particularly between 10 10-> and 55 10-> Pa.
• the molecular mass of the polymers produced according to the process of the invention can be adjusted by adding one or more agents for adjusting the molecular weight of polyolefins such as more particularly hydrogen.
• the process comprises a first polymerization step, distinct from the preliminary polymerization step (described above in relation to the catalytic solid) and called prepolymerization step, during which 1 to 1000 g of polymer is formed per g of catalytic solid.
• the amount of prepolymer formed in this prepolymerization step is advantageously at least 3 g per g of catalytic solid. Good results are obtained when the amount of prepolymer is at most 700 g per g of catalytic solid.
• the prepolymerization step is carried out at a temperature of 0 to 60 ° C.
• the process according to the invention makes it possible to obtain significantly higher catalytic activities compared to the process free of ionic antistatic agent, without soiling the walls of the reactor and while giving polyethylenes having a higher apparent specific gravity (PSA).
• PSA apparent specific gravity
• Obtaining polymers with high PSAs has the advantage of increasing the production capacities of the polymerization, storage and transport facilities.
• the catalytic activity is characterized by the amount of polyethylene formed during the polymerization tests and is expressed in kg of polyethylene per mmol of transition metal originating from the metallocene used, per hour of polymerization and per 10 ⁇ Pa.
• the catalytic activity is assessed indirectly from the determination by vapor phase chromatography of the residual ethylene in the gas leaving the reactor.
• the PSA of the polyethylene obtained is expressed in kg / m ⁇ .
• the polyethylene PSA is measured by free flow according to the following procedure: into a cylindrical container of 50 cm ⁇ capacity, pour the polyethylene from the polymerization process, avoiding packing it, from a hopper whose lower edge is disposed 20 mm above the upper edge of the container. The container filled with the powder is then weighed, the tare is deducted from the recorded weight and the result obtained, expressed in kg, is multiplied by 20,000, so as to express the PSA in kg / m ⁇ .
• the antistatic agent (dicocoalkyldimethylarnmonium chloride sold under the name CHEMAX®) was introduced into a dry 5-liter autoclave equipped with a stirrer with dry nitrogen sweeping X-997 or dinonylnaphthalene sulfonic acid sold under the name STADIS® 450 by the company OCTEL) (in solution in hexane) and 1800 ml of isobutane.
• the temperature was increased to 80 ° C and ethylene was added so as to obtain a partial ethylene pressure of 10 10 ⁇ Pa.
• the polymerization was started by sending the catalytic solid, comprising 6% by weight of ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and 47.5% by weight of MAO (corresponding to 22.1% by weight of aluminum) on a silica support with 200 ml of isobutane.
• the temperature and the partial ethylene pressure were kept constant during the polymerization period (1 hour). The reaction was stopped by degassing and cooling the reactor. The polyethylene was recovered by draining the reactor and was dried.
• Example 1 The operations of Example 1 were repeated, but without the addition of antistatic agent. The results obtained are also found in Table 1.
• the temperature was increased to 80 ° C. and hydrogen was added so as to obtain the desired H 2 / ethylene molar ratio in the gas phase. Then ethylene was introduced until a partial ethylene pressure of 10 10 ⁇ Pa was obtained.
• the antistatic agent (CHEMAX® X-997 or STADIS® 450 from the firm OCTEL) (in solution in hexane) was sent to the reactor with 100 ml of isobutane, and the polymerization was started by sending the catalytic solid as described in Example 1, with 100 ml of isobutane.
• the temperature, the partial ethylene pressure and the H 2 / ethylene ratio were kept constant during the polymerization time (1 hour).
• the reaction was stopped by cooling and degassing the reactor.
• the polyethylene was recovered by draining the reactor and was dried.
• Example 6 The operations of Example 6 were repeated, but without the addition of antistatic agent. The results obtained are found in Table 2. Table 2 shows that the addition of an antistatic agent makes it possible to considerably increase the catalytic activity.
• the polymerization conditions are listed in Table 3.
• the suspension comprising the polyethylene was removed continuously from the reactor and was subjected to a pressure reduction, so as to evaporate the isobutane, hydrogen and ethylene in order to recovering the polyethylene in the form of a powder, which was then dried.
• the ethylene content in the gas leaving the reactor was
• Example 11R The operations of Example 10 were repeated but without the supply of CHEMAX® X-997 and with unchanged supply of catalyst and hydrogen.
• the ethylene content in the gas leaving the reactor was 16.7 mole%.
• Example 10 The comparison of Example 10 with Example 11R demonstrates that the addition of an antistatic agent allows better conversion of the ethylene to be obtained.
• Example 10 The operations of Example 10 were repeated but using the STADIS® 450 from the firm OCTEL at a rate of 0.33 g / h instead of the
• Example 12 The operations of Example 12 were repeated but without the supply of STADIS® 450 and the supply of catalyst and unchanged hydrogen.
• the ethylene content in the gas leaving the reactor was 12.6 mol%.
• Example 12 The comparison of Example 12 with Example 13R demonstrates that the addition of an antistatic agent makes it possible to obtain a better conversion of ethylene (less ethylene in the gas leaving the reactor), resulting in a higher catalytic yield.

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• 2001
  • 2001-02-28 IT IT2001MI000405A patent/ITMI20010405A1/it unknown
• 2002
  • 2002-02-27 EP EP02702378A patent/EP1268577A1/de not_active Withdrawn
  • 2002-02-27 CA CA002407367A patent/CA2407367A1/en not_active Abandoned
  • 2002-02-27 WO PCT/EP2002/002140 patent/WO2002068483A1/fr not_active Application Discontinuation
  • 2002-02-27 JP JP2002567992A patent/JP2004518804A/ja not_active Withdrawn
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