WO2002088195A1 - Composante catalytique supporte de type metallocene et son procede d'obtention - Google Patents
Composante catalytique supporte de type metallocene et son procede d'obtention Download PDFInfo
- Publication number
- WO2002088195A1 WO2002088195A1 PCT/FR2002/001463 FR0201463W WO02088195A1 WO 2002088195 A1 WO2002088195 A1 WO 2002088195A1 FR 0201463 W FR0201463 W FR 0201463W WO 02088195 A1 WO02088195 A1 WO 02088195A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalytic component
- group
- support
- catalyst
- component according
- Prior art date
Links
- 0 *C1C(*)=C(*)C(*)=C1* Chemical compound *C1C(*)=C(*)C(*)=C1* 0.000 description 4
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
-
- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08F4/65925—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 non-bridged
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- the invention relates to new metallocene catalysts, in particular for heterogeneous catalysis and their preparation process.
- the polymerization of olefins in the presence of metallocene catalysts has mainly been described in the homogeneous phase.
- the catalyst, the olefin to be polymerized and the synthesized polyolefin are present in the same liquid phase, which generally involves a solvent.
- One way consists of elementary construction on an inorganic support: the catalyst is built 0 step by step on a support. The grafting on the support is done either via the cene ligands, or via a substituent of the bridge of the metallocene complex.
- EP 0 821 009 proposes the construction of a metallocene on a support treated with butyl lithium by means of an ethyl cyclopentadienyl as anchoring chain.
- the cyclopentadienyl ligand (Cp) is always linked to the silane before being grafted onto the support.
- the activity of the catalyst remains however much lower than that of the equivalent homogeneous catalyst.
- a second way consists in grafting a presynthesized catalyst: a metallocene catalyst already synthesized is reacted on an inorganic support via a substituent present on one of its cene ligands. The grafting is done in a single step.
- This route has a number of advantages including that of a good definition of the structure of the metallocene.
- the support is generally treated beforehand chemically to increase its reactivity with respect to the substituent of the ligand supper, which will make it possible to increase the efficiency of the grafting.
- this process comprises only one step, it remains necessary to carry out the numerous steps of synthesis and of purification of the presynthesized catalyst.
- US Patents 5,202,398 and US 5,824,620 describe a supported catalyst obtained by direct reaction of a functionalized metallocene with the support.
- a third way of obtaining solid catalytic components finally constitutes the elementary construction on an organic support: the synthesis of the catalyst is done either on a polymer already synthesized, polystyrene for example, or on a polysiloxane which contains cene ligands.
- a first object of the invention is a solid catalytic component of metallocene type comprising a cyclopentadienyl group chemically linked by a methyl group to a support consisting of a porous inorganic compound.
- the porous inorganic compound is a silica.
- the metallocene comprises a metal chosen from titanium, vanadium, hafnium, zirconium and chromium, preferably zirconium.
- the methyl group chemically linking the first ligand comprising a cyclopentadienyl group to the support is substituted by two methyl or phenyl groups.
- the metallocene further comprises a second ligand.
- this second ligand comprises a cyclopentadiene group. According to another embodiment, the second ligand comprises a substituted or unsubstituted amide group or an alcoholate group.
- the first and the second ligand are linked together by a bridging group.
- the bridging group is a dimethylsilane group. ii-.
- Another object of the invention relates to a process for the preparation of a metallocene: chemically bound to a solid, comprising the steps of: • , ⁇ •• - ..;
- RI to R6 may be a hydrogen atom or different, or identical, C1 to C1, alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals which may form one or more saturated or unsaturated rings; (c) for obtaining a cyclopentadienyl derivative linked to the solid support by a methyl bridge, reaction of the product obtained in step (c) with a transition metal compound according to the formula MLx, in which M is a metal of transition selected from the elements of groups 3, 4, 5, 6, 7, 8, 9 and 10 of the periodic table of the elements and the lanthanides, L is a halogen, a hydrogen, an alkyl, an aryl, an alkoxy or an amide and x is an integer corresponding to the valence of the metal M.
- the method further comprises the step of: (d) reacting the product of step (c) with a compound according to formula (4):
- the method further comprises the step of activating the product of step (d) with a cocatalyst.
- the cocatalyst is chosen from methylalumiumoxane or systems B. (C 6 F 5 ) 3 / triisobutylalumim ' um and [HNMe 2 Ph] [B, ( ⁇ 6 F 5 ) 4] / trijsobutylalurninium.
- stage (c) the product of stage (b) is reacted with a compound carrying a difunctional group then the product thus obtained is subjected to deprotonation.
- the compound carrying a bridging group A corresponds to the formula (6):
- A is a difunctional group
- X is a halogen
- R7 to RIO represent a hydrogen atom or different or identical C1, C1, 6 alkyl, alkenyl, aryl, alkylaryl or arylalkyl groups which may form one or more saturated or unsaturated rings.
- the subject of the invention is also a solid catalytic component capable of being obtained by this process.
- the subject of the invention is a process for the polymerization or copolymerization in suspension or in the gas phase of at least one olefin in the presence of the catalytic component according to the invention.
- the solid catalytic component according to the invention has a strong activity in polymerization or copolymerization of at least one olefin such as ethylene or propylene.
- the solid catalytic component according to the invention can lead to polymers or copolymers of high molar mass, for example whose average molar mass by weight is greater than 100,000 and whose polymolecularity is low, for example less than 2.5.
- Diagram 1 Preparation process according to a preferred embodiment
- the support used for the preparation of the solid catalytic component according to the invention is finely divided and has functions having a high reactivity with respect to the reagents used.
- An inorganic support carrying hydroxyl function is preferably chosen. Among these, mention may be made of mineral oxides such as alumina, silica or their mixtures.
- the support preferably comprises pores with a diameter ranging from 7.5 to 30 nm. Its porosity is preferably 1 to 4 cm 3 / g.
- the support has a surface ranging from 100 to 600 m 2 / g.
- the support has an average particle size diameter ranging from 10 to 100 ⁇ m.
- the support preferably has at its surface from 0.5 to 10, and more preferably 1 to 8 hydroxyl groups per nm 2 .
- This support can be of various nature. Depending on its nature, its state of hydration and its ability to retain water, it may be necessary to subject it to dehydration treatments until the desired content of hydroxyl groups is obtained on the surface.
- the silica can be heated between 100 and 1000 ° C and preferably between 140 and 800 ° C under the sweeping of an inert gas such as nitrogen or argon, at atmospheric pressure or preferably under vacuum , for example of absolute pressure 1.10 "2 mbar, for for example at least 60 minutes.
- an inert gas such as nitrogen or argon
- the silica can be mixed for example with NH C1 so as to accelerate the dehydration.
- the support is also preferably activated before its implementation.
- R is a C2 to C6 alkyl, even more preferred R is butyl.
- chemical grafting is carried out on the support by reaction of the reactive function with a fulvene substituted according to formula (1),
- RI to R6 may be a hydrogen atom or C1 to C6 alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals, different or identical, which can form one or more saturated or unsaturated rings.
- R5 and R6 are methyl or phenyl.
- the activated support is suspended in an inert solvent as chosen from aliphatic hydrocarbons such as hexane or heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, alicyclic hydrocarbons such as cyclopentane, cyclooctane, methylcyclopentane, methylcyclohexane, ethers such as diethyl ether, tetrahydrofuran, under an atmosphere of an inert gas such as nitrogen or argon.
- the derivative of fulvene (1 ) is added in an amount between 0.01 and 100, and preferably ranges from 0.5 to 2.
- the suspension obtained is then stirred at a temperature between room temperature and boiling point of the solvent used, preferably at a temperature between 40 and 10 ° C.
- a cyclopentadienyl derivative is then obtained grafted onto the support by a bridge - [C (R5, R6) J- according to formula (2):
- G is the reactive functional group of the support, preferably a deprotonated hydroxyl
- X is an alkali, preferably lithium
- R1 to R6 have the same meaning as in formula (1).
- pathway a there is an unbridged compound (5), while pathway b gives access to the bridged compound (5 ').
- M is a transition metal chosen from the elements of groups 3, 4, 5, 6, 7, 8, 9 and 10 and the lanthanides of the periodic table of the elements, preferably chosen from titanium, vanadium, hafhium, zirconium and chromium;
- L is halogen, hydrogen, alkyl, aryl, alkoxy or amide;
- x is an integer corresponding to the valence of the metal M; and
- RI to R6 have the same meaning as in formula (1).
- transition metal derivatives As examples of transition metal derivatives, mention may be made of TiCl 4 , TiBr, Til4, ZrCl 4 , ZrBr 4 , ZrLj, HfCl 4 , HfBr 4 , Hfl 4 , NC1 4 , ⁇ bCl 5 , TaCl 5 , M0CI 5 , WC1 5 , NdCl 3 .
- the transition metal derivative can also be a complex between one of the compounds described and an electron donor compound such as tetrahydrofuran.
- an inert solvent is preferably used, which can for example be chosen from aliphatic hydrocarbons such as hexane or heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, alicyclic hydrocarbons such as cyclopentane, cyclooctane, methylcyclopentane, methylcyclohexane, ethers such as diethyl ether, tetrahydrofuran, under a gas atmosphere inert like nitrogen or argon.
- aliphatic hydrocarbons such as hexane or heptane
- aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene
- alicyclic hydrocarbons such as cyclopentane, cyclooctane, methylcyclopentane, methylcyclohexane
- ethers such as die
- the molar ratio of the halogen derivative to the hydroxyl groups on the surface of the support is generally between 0.5 and 30, and preferably ranges from 1 to 20. Preferably, 5 to 100 ml are used and more preferably from 10 to 50ml of inert solvent per gram of support.
- This contacting can be carried out between 80 and 150 ° C., with stirring, if necessary under pressure if the nature of the solvent so requires.
- the solid should be washed with an inert solvent of the type proposed for carrying out this step. The solid can then be recovered by siphoning or filtration.
- RI 'to R5' represent a hydrogen atom or alkyl, alkenyl, aryl, alkylaryl or arylalkyl C1 to Cl 6, different or identical, which can form one or more saturated or unsaturated rings
- X is an alkali , preferably lithium.
- the derivative (4) is preferably a cyclopentadienyl, an indenyl, a substituted or unsubstituted and optionally hydrogenated fluorenyl, such as tetrahydroindenyl or octahydrofluorenyl.
- the precatalyst (5) obtained following the reaction of (3) and (4) has the following general formula:
- noisy b Compound (2) is reacted with a ligand carrying a bridging group A.
- the ligand can be a cyclopentadienyl group, but also any other compound capable of acting as a ligand, for example NR 2 , NHR or OR, c that is to say amide or alcoholate.
- the ligand is a compound according to formula 6:
- A is a difunctional group such as Si (CH 3 ) 2 , SiPh 2 , CH 2 CH 2 ;
- X is halogen; and
- R7 to RIO may be a hydrogen atom or C1 to C6 alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals, different or identical, which may form one or more saturated or unsaturated rings.
- (6) is FluorenylSi (CH 3 ) 2 Cl.
- the compound (7) is transformed into a precatalyst (5 ′) carrying a ligand bridged by the deprotonation of the ligands followed by metallation by MLx.
- the solid catalytic components according to the invention then constitute heterogeneous catalytic components compatible with polymerization processes in heterogeneous phase.
- the organometallic species are chemically linked to the surface of a solid support, which makes it possible to avoid the phenomena of desorption of catalytic species during the subsequent implementation steps of the component: activation, polymerization.
- the component is heterogeneous and therefore compatible with heterogeneous polymerization processes, in particular the gas phase process is very active in the polymerization of olefins.
- grafting as described makes it possible to avoid the deprotonation step of the ligands of the cyclopentadienyl type chemically bound to the surface. This step may be incomplete and / or give rise to secondary reactions such as the detachment of the grafted species or the opening of siloxane bridges on the support.
- the method described has, compared to the grafting of a presynthesized catalyst, the advantage of being easily generalized to a large number of structures. In addition, it does not require the delicate synthesis of molecular complexes. In other words, one can emphasize the ease and the reduced number of synthesis steps.
- the invention will be described in more detail by means of the following examples, which are given by way of illustration and not limitation.
- the manipulations are carried out under argon with conventional schlenk techniques.
- the heptane and toluene used as solvents are dried over a 3 ⁇ molecular sieve.
- the THF used as solvent and reagent is dried over sodium / benzophenone.
- 6 g of this support are subjected to a heat treatment under vacuum, which successively comprises a temperature rise from 20 ° C to 100 ° C in thirty minutes, from 100 ° C to 130 ° C in thirty minutes, from 130 ° C to 550 ° C in one hour and thirty minutes, a step of 5 hours at 550 ° C and a descent to room temperature.
- a heat treatment under vacuum which successively comprises a temperature rise from 20 ° C to 100 ° C in thirty minutes, from 100 ° C to 130 ° C in thirty minutes, from 130 ° C to 550 ° C in one hour and thirty minutes, a step of 5 hours at 550 ° C and a descent to room temperature.
- the levels of hydroxyl groups on the surface of the various silicas are as follows:
- the support is brought to ambient temperature before being dried under vacuum.
- the support which then has a brown coloring, is suspended in 20 ml of toluene.
- a solution containing 0.086 g of cyclopentadienyl lithium (1.2 mmol) suspended in 30 ml of toluene is then introduced therein at room temperature.
- the mixture is brought to reflux for 24 hours.
- the catalyst is washed with three times 40 ml of toluene at 100 ° C.
- the catalyst is then dried under vacuum. Elemental analysis of this catalyst gives us a zirconium content equal to 7.4% by weight (0.811 mmol / g).
- Catalyst B is prepared in the same way as catalyst A except that in this case, the silica used corresponds to said silica B heat treated.
- the amounts introduced for the synthesis are as follows: 0.996 g of said silica B (1.1 mmol of hydroxyl group), 0.66 ml of the 1.6 M BuLi solution in heptane (1.1 mmol), 0.13 ml of 6-6- dimethylfulven (1.1 mmol), 1.190 g of ZrCl 4 (5.1 mmol), 0.83 ml of freshly distilled THF (10.2 mmol), 0.078 g of LiCp (1 , 1 mmol).
- Catalyst C is prepared in the same way as catalyst A except that in this case, 0.777 g (0.85 mmol of hydroxyl group) of the strain S is taken.
- the amounts introduced for the synthesis are the following 1.353 g of ZrCl 4 (5.8 mmol), 0.94 ml of freshly distilled THF (11.6 mmol), 0.020 g of LiCp (0.3 mmol).
- 0.56 ml of a BuLi 1 solution is introduced at room temperature into a 150 ml schlenk containing 1.287 g of said heat-treated silica C (0.9 mmol of hydroxyl groups) suspended in 50 ml of toluene .6 M in heptane (0.9 mmol). The suspension is stirred for 4 hours at room temperature. The support is washed with 3 times 40 ml of toluene then the solvent is evaporated under a stream of argon. The solid recovered is suspended in 50 ml of toluene. Then 0.13 ml of 6-6-dimethylfulvene (1.0 mmol) is introduced therein at room temperature and under an argon atmosphere.
- the suspension is agitated for 30 minutes at room temperature and then at reflux for 2 hours. During the reaction, the support takes on an orange color. After returning to ambient temperature, the support is washed with three times 40 ml of toluene and then washed with three times 40 ml of heptane. The solvent is then evaporated by scanning argon. We then recover an orange solid. This solid is suspended in 20 ml of toluene. In a 100 ml schlenk containing 1.040 g of zirconium tetrachloride (4.4 mmol) suspended in 50 ml of toluene, 0.72 ml of freshly distilled THF (ie 8.8 mmol) is introduced at room temperature.
- the solution containing the ZrCl .2THF complex is introduced at 100 ° C. into the schlenk containing the support.
- the mixture obtained is brought to reflux for 24 hours.
- the support is washed with three times 40 ml of toluene.
- the support is brought to room temperature then the solvent is evaporated by argon sweeping.
- the support which then has a brown coloring, is suspended in 20 ml of toluene.
- a solution containing 0.061 g of cyclopentadienyl lithium (0.8 mmol) suspended in 30 ml of toluene is then introduced therein at room temperature.
- the mixture is brought to reflux for 24 hours.
- the catalyst Before being brought to room temperature, the catalyst is washed with three times 40 ml of toluene at 100 ° C. The solvent is then evaporated by scanning argon. Elemental analysis of the catalyst obtained gives us a zirconium content equal to 6.9% by weight (0.757 mmol / g).
- the support After returning to 80 ° C., the support is washed with three times 40 ml of toluene. The support is brought to room temperature then the solvent is evaporated under a stream of argon. The solid recovered is suspended in 50 ml of toluene. 0.05 ml of 6-6-dimethylfulvene (0.5 mmol) is then introduced therein at room temperature and under an argon atmosphere. The suspension is stirred for 30 minutes at room temperature and then at reflux for 24 hours. During the reaction, the support takes on an orange color. After returning to 100 ° C., the support is washed with three times 40 ml of toluene. The solvent is then evaporated by scanning argon. We then recover an orange solid.
- This solid is suspended in 20 ml of toluene.
- 0.41 ml of freshly distilled THF (5.0 mmol) is introduced at room temperature into a 100 ml schlenk containing 0.594 g of zirconium tetrachloride (2.5 mmol) suspended in 50 ml of toluene.
- the solution containing the ZrCl .2THF complex is introduced at room temperature into the schlenk containing the support.
- the mixture obtained is brought to reflux for 24 hours.
- the support is washed with three times 40 ml of toluene.
- the support is brought to room temperature then the solvent is evaporated under a stream of argon.
- the support which then has a brown coloring, is suspended in 20 ml of toluene.
- a solution containing 0.016 g of cyclopentadienyl lithium (0.2 mmol) suspended in 30 ml of toluene is then introduced therein at room temperature.
- the mixture is brought to reflux for 24 hours.
- the catalyst is washed with three times 40 ml of toluene at 100 ° C. then the solvent is evaporated under a stream of argon. Elemental analysis of the catalyst obtained gives us a zirconium level equal to
- silica D 0.191 g of silica D is introduced into a 50 ml schlenk containing 0.046 g of catalyst A. A solid / solid dilution to 20% of catalyst A is thus obtained in silica D.
- silica D 0.095 g is introduced into a 50 ml schlenk containing 0.027 g of catalyst D. This gives a solid / solid dilution to 22% of catalyst D in silica D.
- Example 2 2.5 ml of a 0.9 M tributylaluminum solution in heptane (2.2 mmol) and then 0.028 g of catalyst A are introduced into a 500 ml two-necked flask containing 300 ml of heptane. i.e. 22.7 ⁇ mol of Zr). Then introduced 7.9 ml of a solution of tris (pentafluorophenyl) borane 3, lmM in petroleum ether (24.5 ⁇ mol). The suspension thus obtained is introduced under a stream of argon into a 0.5 liter glass reactor. After degassing the reactor, the pressure is raised to 4 bars absolute of ethylene and the temperature to 80 ° C.
- the pressure and the temperature are kept constant during the polymerization. After 4 hours of polymerization, the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 4.0 g of polyethylene are recovered, which corresponds to a productivity of 143 g PE / g catalyst.
- acid methanol MeOH / HCl
- 0.45 ml of a 0.9 M tributylaluminum solution in heptane (0.4 mmol) is then introduced into a 500 ml two-necked flask containing 300 ml of heptane followed by 0.005 g of catalyst A (i.e. 4 , 1 ⁇ mol of Zr). Then introduced 0.005 g of N, N-dimethylaluminium tetra (pentafluorophenyl) borate (ie 6.2 ⁇ mol).
- the suspension thus obtained is introduced under a stream of argon into a 0.5 liter glass reactor. After degassing the reactor, the pressure is raised to 4 bars absolute of ethylene and the temperature to 80 ° C.
- the pressure and the temperature are kept constant during the polymerization.
- the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH HCl). After filtration, washing with methanol and drying, 17.9 g of polyethylene are recovered, which corresponds to a productivity of 3580 g PE / g catalyst.
- the melt index of the polymer, at 190 ° C. under 21.6 kg, is 10.2 g / 10 minutes.
- 0.1 ml of a 0.9 M tributylaluminum solution in heptane (0.11 mmol) is then introduced into a 500 ml two-necked flask containing 300 ml of heptane and then 0.006 g of catalyst F (i.e. , 2 mg of catalyst A, i.e. 1.0 ⁇ mol of Zr). Then 0.001 g of N, N-dimethylaluminum tetra (pentafluorophenyl) borate (i.e. 1.2 ⁇ mol) is introduced. The suspension thus obtained is introduced under a stream of argon into a 0.5 liter glass reactor.
- the pressure is raised to 4 bars absolute of ethylene and the temperature to 80 ° C.
- the pressure and the temperature are kept constant during the polymerization.
- the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 4.4 g of polyethylene are recovered, which corresponds to a productivity of 3,384 g PE / g of catalyst A.
- the melt index of the polymer, at 190 ° C. under 21.6 kg, is 0.8 g / 10 minutes.
- Example 5 1.96 ml of a 1.53 M methylamminoxane solution in toluene (2.9 mmol) and then 0.005 g of catalyst B (3.8 ⁇ mol) are introduced into a 500 ml two-necked flask containing 300 ml of heptane of Zr). The suspension thus obtained is introduced under a stream of argon into a 0.5 liter glass reactor. After degassing the reactor, the pressure is raised to 4 bars absolute of ethylene and the temperature to 80 ° C. The pressure and the temperature are kept constant during the polymerization. After 20 minutes of polymerization, the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 9.5 g of polyethylene are recovered, which corresponds to a productivity of 1900 g PE / g catalyst.
- MeOH / HCl acid methanol
- the pressure and the temperature are kept constant during the polymerization.
- the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 5.5 g of polyethylene are recovered, which corresponds to a productivity of 1100 g PE / g catalyst.
- the melt index of the polymer, at 190 ° C under 2.16 kg, is 0.1 g / 10 minutes.
- the gas is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 6.8 g of polyethylene are recovered, which corresponds to a productivity of 971 g PE / g catalyst.
- the melt index of the polymer, at 190 ° C. under 2.16 kg, is 0.8 g / 10 minutes.
- the gas is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 6.5 g of polyethylene are recovered, which corresponds to a productivity of 812 g PE / g catalyst.
- the melt index of the polymer, at 190 ° C. under 2.16 kg, is 1.5 g / 10 minutes.
- the pressure and the temperature are kept constant during the polymerization.
- the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 7.1 g of polyethylene are recovered, which corresponds to a productivity of 887 g PE / g catalyst.
- the melt index of the polymer, at 190 ° C. under 2.16 kg, is 1.2 g / 10 minutes.
- Example 11 0.42 ml of a 1.3 M solution of tributylaluminum in heptane (0.5 mmol) is then introduced into a 500 ml two-necked flask containing 300 ml of heptane followed by 0.007 g of catalyst D ( 5.3 ⁇ mol of Zr). Then introduced 0.007 g of N, N-dimethylaluminium tetra (pentafluorophény ⁇ ) borate (8.7 ⁇ mol). The suspension thus obtained is introduced under a stream of argon into a 0.5 liter glass reactor.
- the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 6.9 g of polyethylene are recovered, which corresponds to a productivity of 985 g PE / g catalyst.
- the melt index of the polymer, at 190 ° C. under 2.16 kg, is 1.5 g / 10 minutes.
- the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 5.7 g of polyethylene are recovered, which corresponds to a productivity of 814 g PE / g catalyst.
- the melt index of the polymer, at 190 ° C. under 2.16 kg, is 2.0 g / 10 minutes.
- the pressure and the temperature are kept constant during the polymerization. After 20 minutes of polymerization, the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 5.7 g of polyethylene are recovered, which corresponds to a productivity of 4750 g PE / g catalyst D.
- acid methanol MeOH / HCl
- the pressure and the temperature are kept constant during the polymerization. After 25 minutes of polymerization, the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 8.4 g of polyethylene are recovered, which corresponds to a productivity of 10,500 g PE / g catalyst D.
- acid methanol MeOH / HCl
- Example 16 0.2 ml of a 1.3 M solution of tributylaluminum in heptane (0.3 mmol) is then introduced into a 500 ml two-necked flask containing 300 ml of heptane followed by 0.006 g of catalyst G ( 1.3 mg of catalyst D, 1.0 ⁇ mol of Zr). 0.014 g of N, N- are then introduced dimethylaluminum tetra (pentafluorophenyl) borate (17.5 ⁇ mol). The suspension thus obtained is introduced under a stream of argon into a 0.5 liter glass reactor. After degassing the reactor, the pressure is raised to 4 bars absolute of ethylene and the temperature to 80 ° C.
- the pressure and the temperature are kept constant during the polymerization. After 10 minutes of polymerization, the reactor is degassed and the polymer is precipitated in a dilute solution of acid methanol (MeOH / HCl). After filtration, washing with methanol and drying, 8.7 g of polyethylene are recovered, which corresponds to a productivity of 7,250 g PE / g catalyst D.
- acid methanol MeOH / HCl
- 0.011 g of catalyst D (7.2 ⁇ mol of Zr) are successively introduced into a 50 ml flask containing 2.772 g of HDPE (the HDPE was drawn off under dynamic vacuum for 2 hours at 200 ° C. before its use) ), 0.009 g of N, N- dimethylaluminium tetra (pentafluorophenyl) borate (11.2 ⁇ mol), 1.4 ml of a solution of tributylaluminum 1.3 M in heptane (1.6 mmol) and 20 ml of toluene . After 15 minutes of stirring, the solvent is evaporated under dynamic vacuum.
- the solid obtained is introduced under a stream of argon into a gas phase reactor containing 20 HDPE feedstock (the reactor and the feedstock have previously been conditioned by a series of three times vacuum / argon at 80 ° C., then 1, 2 ml of a solution of tributylaluminum 1.3 M in heptane (1.6 mmol) was introduced before drawing the reactor under vacuum at 80 ° C).
- 0.5 bar of butene is introduced before raising the pressure to 12 bar with ethylene and the temperature to 70 ° C.
- the total pressure of the reactor is maintained at 12 bar (by adding ethylene) and the temperature at 70 ° C during the polymerization.
- the reactor is degassed and 26.0 g of polyethylene is recovered (plus the 20 g of feed), which corresponds to a productivity of 2,363 g of PE / g of catalyst D.
- the melt index of the polymer, at 190 ° C under 21.6 kg, is 1.6 g / 10 minutes.
- 0.012 g of catalyst D (9.1 ⁇ mol of Zr) are successively introduced into a 50 ml flask containing 0.828 g of HDPE (the HDPE was drawn off under dynamic vacuum for 2 hours at 200 ° C. before its use) ), 0.030 g of N, N- dimethylaluminium tetra (pentafluorophenyl) borate (37.4 ⁇ mol), 1.5 ml of a solution of tributylaluminum 1.3 M in heptane (2.0 mmol) and 20 ml toluene. After 15 minutes of stirring, the solvent is evaporated under dynamic vacuum.
- the solid obtained is introduced under a stream of argon into a gas phase reactor containing 20 HDPE feedstock (the reactor and the feedstock have previously been conditioned by a series of three times vacuum / argon at 80 ° C., then 1.5 ml of a 1.3 M solution of tributylaluminum in heptane (2.0 mmol) was introduced before drawing the reactor under vacuum at 80 ° C.).
- 0.5 bar of butene is introduced before raising the pressure to 12 bar with ethylene and the temperature to 70 ° C.
- the total pressure of the reactor is maintained at 12 bar (by adding ethylene) and the temperature at 70 ° C during the polymerization.
- the reactor is degassed and 43 g of polyethylene are recovered (plus the 20 g of feed), which corresponds to a productivity of 3,583 g PE / g catalyst D.
- the pressure and the temperature are kept constant during the polymerization. After 15 hours of polymerization, the reactor is degassed and the polymer is precipitated in a dilute acid methanol solution (MeOH / HCl). After filtration, washing with methanol and drying, 15 g of polypropylene are recovered, which corresponds to a productivity of 1500 g PP / g catalyst E.
- a dilute acid methanol solution MeOH / HCl
- Atactic polypropylene Mn 3820 g / mol; Mw 5930 (GPC in Tetrahydrofuran at 45 ° C - Polystyrene standards) -
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/476,152 US7060767B2 (en) | 2001-04-30 | 2002-04-26 | Supported metallocene catalytic component and method for obtaining same |
EP02735509A EP1397399A1 (fr) | 2001-04-30 | 2002-04-26 | Composante catalytique supporte de type metallocene et son procede d'obtention |
JP2002585492A JP2004534869A (ja) | 2001-04-30 | 2002-04-26 | 支持されたメタロセン触媒成分及びそれを得る方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0105805A FR2824066B1 (fr) | 2001-04-30 | 2001-04-30 | Composante catalytique solide de type metallocene et son procede d'obtention |
FR01/05805 | 2001-04-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002088195A1 true WO2002088195A1 (fr) | 2002-11-07 |
Family
ID=8862850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/001463 WO2002088195A1 (fr) | 2001-04-30 | 2002-04-26 | Composante catalytique supporte de type metallocene et son procede d'obtention |
Country Status (5)
Country | Link |
---|---|
US (1) | US7060767B2 (fr) |
EP (1) | EP1397399A1 (fr) |
JP (1) | JP2004534869A (fr) |
FR (1) | FR2824066B1 (fr) |
WO (1) | WO2002088195A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7060767B2 (en) | 2001-04-30 | 2006-06-13 | Bortolussi Frederic | Supported metallocene catalytic component and method for obtaining same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104334590B (zh) * | 2012-02-08 | 2016-08-31 | 信实工业公司 | 用于制备uhmwpe的单中心催化剂在无机氧化物载体上的固定化 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5202398A (en) * | 1987-06-05 | 1993-04-13 | Hoechst Aktiengesellschaft | Process for the preparation of a 1-olefin polymer |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4147664A (en) * | 1975-10-24 | 1979-04-03 | Pomogailo Anatoly D | Catalyst of polymerization, copolymerization and oligomerization of olefins and drolefins |
DE2727245C3 (de) * | 1977-06-16 | 1980-06-26 | Brintzinger, Hans, Prof. Dr., 7750 Konstanz | Polymergebundene CyclopentadienylÜbergangsmetall-Verbindungen und ihre Ligand-Substitutions-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren |
CA1268754A (fr) | 1985-06-21 | 1990-05-08 | Howard Curtis Welborn, Jr. | Catalyseur de polymerisation sur support |
US5312938A (en) * | 1990-09-20 | 1994-05-17 | The Dow Chemical Company | Homogeneous catalysts and olefin polymerization process |
US5587439A (en) * | 1995-05-12 | 1996-12-24 | Quantum Chemical Corporation | Polymer supported catalyst for olefin polymerization |
ES2120868B1 (es) * | 1995-08-03 | 2000-09-16 | Repsol Quimica Sa | Sistema de catalizadores hetereogeneos tipo metalogeno, para procesos de obtencion de poliolefinas. |
FI961511A (fi) * | 1996-04-03 | 1997-10-04 | Mikrokemia Oy | Menetelmä olefiinien polymerointikatalyyttien valmistamiseksi |
IT1283010B1 (it) * | 1996-05-15 | 1998-04-03 | Enichem Spa | Complesso metallocenico supportato e procedimento per la sua prepa- razione |
KR100205738B1 (ko) | 1996-07-26 | 1999-07-01 | 이정국 | 담지체 계류 담지 촉매 및 그 제조 방법 |
PT839836E (pt) | 1996-10-31 | 2001-06-29 | Repsol Quimica Sa | Sistemas cataliticos para a polimerizacao e copolimerizacao de alfa-olefinas |
KR100367463B1 (ko) * | 1999-03-03 | 2003-01-14 | 주식회사 엘지화학 | 메탈로센 화합물 및 이를 이용한 올레핀 중합 |
FR2824066B1 (fr) | 2001-04-30 | 2004-02-06 | Atofina | Composante catalytique solide de type metallocene et son procede d'obtention |
-
2001
- 2001-04-30 FR FR0105805A patent/FR2824066B1/fr not_active Expired - Fee Related
-
2002
- 2002-04-26 WO PCT/FR2002/001463 patent/WO2002088195A1/fr not_active Application Discontinuation
- 2002-04-26 JP JP2002585492A patent/JP2004534869A/ja not_active Withdrawn
- 2002-04-26 EP EP02735509A patent/EP1397399A1/fr not_active Withdrawn
- 2002-04-26 US US10/476,152 patent/US7060767B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5202398A (en) * | 1987-06-05 | 1993-04-13 | Hoechst Aktiengesellschaft | Process for the preparation of a 1-olefin polymer |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7060767B2 (en) | 2001-04-30 | 2006-06-13 | Bortolussi Frederic | Supported metallocene catalytic component and method for obtaining same |
Also Published As
Publication number | Publication date |
---|---|
US20040147692A1 (en) | 2004-07-29 |
FR2824066A1 (fr) | 2002-10-31 |
US7060767B2 (en) | 2006-06-13 |
EP1397399A1 (fr) | 2004-03-17 |
FR2824066B1 (fr) | 2004-02-06 |
JP2004534869A (ja) | 2004-11-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2097777C (fr) | Procede de preparation d'un systeme catalytique, procede de (co)polymerisation d'olefines et (co)polymeres d'au moins une olefine | |
JP4951351B2 (ja) | メタロセン触媒用の活性化担体 | |
CN1113070C (zh) | 烯烃聚合 | |
CA2246003C (fr) | Support solide activateur des catalyseurs metallocenes en polymerisation des olefines, son procede de preparation, systeme catalytique et procede de polymerisation correspondants | |
JP6458050B2 (ja) | ポリオレフィンの製造方法およびこれから製造されたポリオレフィン | |
EP0127530B1 (fr) | Procédé de préparation d'une composante de métal de transition pour un système catalytique de polymérisation d'oléfines | |
EP0742226B1 (fr) | Procédé de préparation de catalyseurs dérivés de borane pour la préparation de polymères vinyl aromatiques syndiotactiques | |
KR20040085650A (ko) | 혼성 담지 메탈로센 촉매 및 그의 제조방법과 이를 이용한폴리올레핀의 제조방법 | |
FR2500457A1 (fr) | Nouveau catalyseur a base d'un alkylmagnesium, d'un organosilane et d'un compose de titane, son procede de production et son application a la polymerisation d'olefines | |
US20020019504A1 (en) | Novel metallocene compound, and process for preparing polyolefin by using it | |
US6075103A (en) | Silyl-terminated polymer and method for preparing silyl-terminated polyolefins | |
EP0889065B1 (fr) | Composante catalytique solide pour la polymérisation des oléfines | |
EP1397399A1 (fr) | Composante catalytique supporte de type metallocene et son procede d'obtention | |
WO2002012357A2 (fr) | Procédé de préparation d'un support de catalyseur pour la polymérisation d'alpha olefines | |
EP0574067B1 (fr) | Procédé de fabrication d'un solide catalytique, solide catalytique et procédé de (co)polymérisation d'oléfines au moyen de ce solide catalytique | |
US20040002420A1 (en) | Stable catalysts and co-catalyst compositions formed from hydroxyaluminoxane and their use | |
EP0992515B1 (fr) | Catalyseur destiné à la polymérisation des oléfines, procédé pour sa fabrication et utilisation | |
EP0206893A1 (fr) | Procédé de préparation d'une composante de métal de transition pour un système catalytique de polymérisation d'oléfines | |
JP2004511562A (ja) | 非メタロセン、その製造法及びそのオレフィンの重合への使用法 | |
CN111471074A (zh) | 一种取代茚基金属配合物、其制备方法和应用 | |
BE1012363A3 (fr) | Procede pour la preparation d'un catalyseur pour la polymerisation des alpha-olefines, catalyseur obtenu et procede de polymerisation utilisant un tel catalyseur. | |
KR20010024060A (ko) | 오르가노폴리실록산 마이크로겔 입자상에서 고정화시킨오르가노 알루미늄 화합물 | |
WO2000068276A1 (fr) | Procede de production de polymere d'olefine vivant | |
AU652363B2 (en) | Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution | |
EP1038883A1 (fr) | Procédé pour la polymérisation des alpha-oléfines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 10476152 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002585492 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002735509 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 2002735509 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2002735509 Country of ref document: EP |