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
  • 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
• • 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
  • B01J31/0201—Oxygen-containing compounds
  • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
  • B01J31/0212—Alkoxylates
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
• • 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
  • B01J31/122—Metal aryl or alkyl compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/28—Metal alcoholates
• • 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
  • 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
  • C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
• • 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
  • C08F210/02—Ethene

Definitions

• the present invention relates to a catalytic system based on rare earth and magnesium, a new neodymium alcoholate and their use for the polymerization of unsaturated compounds.
• the object of the invention is therefore the development of an efficient and simple preparation catalytic system
• the catalytic system according to the invention is characterized in that it comprises a compound constituted by the product of the reaction between
• the system of the invention is efficient and allows, according to preferred embodiments, to obtain unimodal polymers, if necessary homodispersed and with a high rate of syndiotacticity.
• the term “rare earth” is understood to mean the elements of the group constituted by ytt ⁇ um and the elements of the periodic classification with atomic number included inclusively between 57 and 71
• the catalytic system of the invention comprises a compound consisting of the product of the reaction of two reagents which will be described more precisely below
• the first reagent is a rare earth alcoholate.
• alcoholate is meant the products corresponding to the general formula (1) (TR) x (OR 1 ) y (X) z (S) t in which R 1 denotes an organic group, X a halogen and S a coordinating solvent and where x> 1, y> 1, z> 0 and t> 0.
• alcoholate also applies, in the context of the present invention, to alcoholates of formula (1) comprising several different radicals R 1 .
• the rare earth of the alcoholate can be more particularly yttrium, lanthanum, cerium, neodymium or samarium. Neodymium is preferred.
• the alcoholate is more particularly an alcoholate of an alcohol or of a polyol derived from an aliphatic or cyclic hydrocarbon and in particular from an aliphatic hydrocarbon, linear or branched, in more particularly in C 4 -C 8 . Mention may very particularly be made of tertiary alcoholates or polyalcoholates, for example tert-butylate or tertioamylate.
• the alcoholate can also be a phenate, that is to say a derivative of a compound of phenolic or polyphenolic type. According to a preferred embodiment of the invention, the alcoholate is prepared by specific methods which will be described more precisely below.
• a first method implements a reaction of a rare earth halide with an alkali or alkaline earth alcoholate.
• the halide can more particularly be a chloride and the alkali can be in particular sodium and potassium.
• the reaction is carried out in an anhydrous solvent medium and protected from air.
• the solvent medium is constituted by tetrahydrofuran (THF) or comprises tetrahydrofuran in mixture with another solvent.
• THF tetrahydrofuran
• solvent mention may be made of liquid hydrocarbons of 3 to 12 carbon atoms such as heptane, cyclohexane, cyclic or aromatic hydrocarbons such as benzene, toluene or even xylenes.
• ethers are examples of ethers.
• the reaction generally takes place at a temperature which can be between ambient (20 ° C.) and 100 ° C. over a period which can vary between approximately 12 hours and approximately 96 hours.
• a temperature which can be between ambient (20 ° C.) and 100 ° C. over a period which can vary between approximately 12 hours and approximately 96 hours.
• the reaction mixture is brought to reflux over a period of the same order of magnitude.
• the reaction medium is allowed to settle, the supernatant is evaporated and a solid product is thus obtained, in the form of a powder, which constitutes the rare earth alcoholate.
• a second specific process consists in reacting with an alkali or alkaline earth alcoholate an adduct of a rare earth halide and THF (TRX 3 , xTHF).
• the adduct can be obtained by heating a rare earth halide in THF, for example at 50 ° C., then evaporation of the solvent. This evaporation can be done under vacuum at 20 ° C.
• the reaction with the alcoholate also takes place in an anhydrous solvent medium and away from air. and under the same conditions as those described for the previous process
• the solvents are of the same type as those given above and mention may be made very particularly of toluene
• This process consists in reacting an alcohol with a rare earth amide.
• the alcohol can be an alcohol, a polyol or a phenolic or polyphenolic compound as defined above.
• the amide is a compound. of formula TR (N (S ⁇ R 2 3 ) 2 ) 3 , R 2 denoting an alkyl radical, for example methyl
• the reaction is also carried out in an anhydrous solvent medium and protected from air
• the solvent medium consists of tetrahydrofuran (THF) or comprises tetrahydrofuran in admixture with another solvent.
• liquid hydrocarbons of 3 to 12 carbon atoms such as heptane, cyclohexane, cyclic or aromatic hydrocarbons such as benzene, toluene or xylenes can also be mentioned ethers
• the reaction temperature can be between -20 ° C and 100 ° C, but generally one works at room temperature
• the reaction time can be short t vary between 15 minutes and 96 hours, it can be for example 24 hours
• the present invention also relates, as a new product, to a neodymium alcoholate.
• This neodymium alcoholate has as specific characteristic the fact that it does not contain chlorine in its structure.
• the known rare earth alcoholates by their mode of preparation, present either chlorine which belongs to their atomic structure even, or a liganded solvent, or both at the same time
• the alcoholate is a tert-butylate or a tertioamylate
• the neodymium alcoholate of the invention can correspond to the formula Nd 3 ( ⁇ 3-O t Bu) 2 ( ⁇ 2 -O t Bu) 3 ( ⁇ - O t Bu) 4 (THF) 2 nTHF or Nd 3 ( ⁇ 3 -O t Am ) 2 ( ⁇ 2 -O t Am) 3 ( ⁇ -O t Am) 4 (THF) 2 nTHF, where n can be 0 or 1
• the absence of chlorine can be demonstrated by X-ray analysis.
• the neodymium alcoholate of the invention can be prepared by implementing the specific methods which have been described above, in particular using tert-butylate or a tertioamylate or else the tertiobutanol or tertiobutyl alcohol
• the second reagent used in the reaction, the product of which constitutes the compound of the catalytic system of the invention, is an organomagnesium
• organo-magnesium is meant a product which is either a dialkyl-magnesian or a G ⁇ gnard reagent
• a dialkyl-magnesian that is to say the compounds of formula (2)
• R-Mg-R ' where R and R' denote alkyl radicals
• R and R ' may more particularly be n-hexyl Mention may also be made more particularly of the product of formula (2) in which R and R' are respectively butyl and ethyl
• the alkyl radicals R and / or R 'can also carry a heteroatom such as Si Mention may in particular be made of the radical -CH 2 -S ⁇ (CH 3 ) 3
• the organomagnesium can also be a G ⁇ gnard reagent, that is to say a compound of formula (3) R-Mg-X in which X denotes a halogen, the halogen can be bromine, chlorine or iodine, but use is more particularly made of those for which the halogen is bromine
• R may be any R may in particular be a saturated or non-ahcyclic or aromatic aliphatic radical R may more particularly be an alkyl radical, such as the ethyl radical, another phenyl radical
• the rare earth alcoholate and the magnesium compound can be reacted in respective variable proportions
• This proportion can be expressed by the ratio TR / Mg
• This ratio (molar ratio) is generally between 0.5 and 5 It can be more particularly equal to 1 It would not, however, depart from the scope of the present invention to use a ratio outside the above-mentioned range. This ratio may vary in particular as a function of the unsaturated compounds which it is desired to polymerize. It will be noted that the use of 'an organo-magnesian of formula (2) above in which R and R' are respectively butyl and ethyl makes it possible to work with TR / Mg ratios which can vary within a fairly wide range
• the product of the reaction of the two reactants which have just been described therefore constitutes the compound of the catalytic system of the invention.
• consists of the product of the reaction of the two reactants it is meant that there is no other compounds or elements which participate, as a reagent, in this reaction
• the catalytic system of the invention is usually in the form of a solution which is generally obtained by mixing and then reacting a first solution of the first reagent with a second solution of the second reagent then stirring These solutions are in solvents of the same type as those which were mentioned above.
• the mixture obtained from the two aforementioned solutions can be maintained and stirred, before its use, at a temperature which can be between -80 ° C and 110 ° C for a period of a few minutes a few hours, for example for an hour
• the system of the invention can be used for the polymerization or copolymerization of unsaturated compounds of the type of those described in the introduction to this description (olefins, dienes, (meth) acrylates) As compound of this type, mention may more particularly be made of ethylene, butadiene.
• the system of the invention is preferably used for the polymerization of ethylene. Mention may also be made of the polymerization of polar monomers of the (meth) acrylate type, iactone or lactide, preferably methyl methacrylate It will be noted that the system of the invention is suitable for block block copolymerization of ethylene with a polar monomer, in particular methyl methacrylate
• the polymerization is carried out under known conditions
• the polymerization temperature can be between -80 ° C. and 110 ° C. It is preferably worked at atmospheric pressure but it is also possible to work under pressure
• the reaction is usually carried out in the presence of a solvent which can be chosen in particular from aliphatic hydrocarbons or their mixtures such as butane, hexane, cyclohexane, aromatic hydrocarbons such as toluene
• Example 1 This example relates to the preparation of tert-butylates of different rare earths
• neodymium In a glove box, are weighed and placed in two Schlenk tubes of 100 ml, on the one hand sodium tertiobutylate (30mmol) and on the other hand anhydrous neodymium (III) (10mmol) These are then placed under argon and 40mL of THF are added to them respectively (distilled over K and degassed according to the freezing point technique) A solution of sodium tertiobutylate and a suspension are thus obtained of neodymium chloride The suspension of NdCI3 is transferred to a Schlenk tube with a minimum capacity of 300mL then the tBuONa solution is added to it.
• the two small Schlenk tubes are rinsed with 20mL of THF which will be added to the previous 80mL
• the mixture is maintained for 72 hours at room temperature with vigorous stirring and then the residual NaCl is left to settle overnight before filtering the solution which allows a clear blue solution to be obtained.
• the solvent for this solution is then evacuated under vacuum (10 2 mmHg) at room temperature for 5 to 6 hours.
• a light blue granular powder very soluble in toluene, is obtained with a yield of between 80 and 90%.
• the powdery product obtained can be re-installed in a solvent such as toluene or a toluene / pentane mixture (1/1) at -5 ° C.
• a solvent such as toluene or a toluene / pentane mixture (1/1) at -5 ° C.
• the X-ray diffraction analysis correlated by NMR analysis of the proton establishes that the compound has a formula like Nd 3 ( ⁇ 3-O t Bu) 2 ( ⁇ 2 -O t Bu) 3 ( ⁇ -O t Bu) 4 (THF) 2 THF
• the compound therefore does not contain chlorine
• the light blue powdery product and the crystallized product have the same catalytic properties
• Tm melting temperature of the polymer (determined by ATD)
• IP polymolecularity index (determined by GPC)
• the procedure is carried out using the same method as that described for Examples 2 to 10, but by injecting the mixture of rare earth tert-butoxide and the magnesium compound in 80 ml of toluene under 1 bar of ethylene placed at the desired reaction temperature. The consumption of ethylene is monitored by an instantaneous flowmeter and a totalizer. The polymer is precipitated in an acidified methanol solution (5% HCl). It is then filtered on a frit and dried in an oven at 60 ° C for 24 hours.
• polyethylenes prepared in the examples in the presence of Nd at low temperature (0 ° C) advantageously have a higher melting temperature than those of the polymers usually obtained.
• Physico-chemical analyzes show that the polymers obtained in these conditions are highly linear polymers with high molecular weights.
• the GPC analysis of the sample of example 11 reveals an Mn of 390000 and an IP of 2.1
• Neodymium tertiobutylate and d ⁇ (n-hexyl) magnesium are used in an Nd / Mg ratio of 1.
• the procedure is as described for Examples 2 to 10 with, however, the following modifications
• the mixing of the solutions which has been maintained for 1 hour at a temperature of 0 ° C. is injected into another Schlenk tube containing 80 ml of toluene saturated with ethylene (1 bar) at the polymerization temperature (0 ° C.)
• the polymerization of ethylene is carried out for 12 minutes
• the medium is purged with argon and the MAM is injected (50 mmol)
• the mixture is left stirring for one hour at 0 ° C.
• the reaction is stopped by adding a small amount of ethanol (1 to 2 ml ) and the polymer is precipitated in heptane
• the copolymer obtained is then filtered on filter and dried in an oven at 60 ° C for 24 hours 6.0g of the latter undergo extraction with acetone (at its point of boiling) for 48 hours in a Ku agawa apparatus.
• HomoPMMA is thus separated from homoPE and from the copolymer. Only 1.0 gram was dissolved in acetone, which amounts to saying that there is only 17%. homoPMMA in the polymer obtained
• the organomagnesium used is Mg (n-Hex) and the temperature at which the reaction between the alcoholate and the organo-magnesian is 0 ° C
• This example relates to the preparation of the tr ⁇ s (phenate) of neodymium Nd (O (2,6-'Bu-4- Me-C 6 H 2 ) 3 ) and its use in the polymerization of ethylene
• the neodymium t ⁇ s (phenate) is prepared as in Example 1 using sodium phenate in place of sodium tertiobutylate The other difference is that the reaction mixture is maintained for 72 hours at THF reflux. A fine powder is obtained purplish with a yield of 80-90%
• Example 2 For the polymerization, the procedure is as in Example 2 The mixing temperature of neodymium tr ⁇ s (phenate) and the magnesium compound is 20 ° C. The polymerization temperature is also 20 ° C. and the reaction time is d 'one o'clock

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• 1999
  • 1999-07-05 FR FR9908648A patent/FR2795976B1/fr not_active Expired - Fee Related
• 2000
  • 2000-06-30 BR BR0012165-7A patent/BR0012165A/pt not_active Application Discontinuation
  • 2000-06-30 KR KR1020027000118A patent/KR20020037328A/ko not_active Application Discontinuation
  • 2000-06-30 JP JP2001508233A patent/JP2003504429A/ja active Pending
  • 2000-06-30 EP EP00949599A patent/EP1200490A1/fr not_active Withdrawn
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