WO2016099236A1 - Hétérogénéisation d'aluminohydrures de zirconocènes sur des supports organiques pour la polymérisation d'éthylène - Google Patents

Hétérogénéisation d'aluminohydrures de zirconocènes sur des supports organiques pour la polymérisation d'éthylène Download PDF

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WO2016099236A1
WO2016099236A1 PCT/MX2014/000210 MX2014000210W WO2016099236A1 WO 2016099236 A1 WO2016099236 A1 WO 2016099236A1 MX 2014000210 W MX2014000210 W MX 2014000210W WO 2016099236 A1 WO2016099236 A1 WO 2016099236A1
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particles
zirconocene
aluminohydride
polymerization
ethylene
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Odilia PÉREZ CAMACHO
René Darío PERALTA RODRÍGUEZ
Clara Isabel VILLASANA SALVADOR
Katharina Landfester
Daniel Crespy
Rafael MUÑOZ ESPÍ
Gladis Yaqueline CORTÉZ MAZATÁN
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Centro De Investigación En Química Aplicada
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • 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
    • C08F4/02—Carriers therefor
    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound

Definitions

  • the present invention relates to a process for preparing heterogenated zirconocene aluminohydrides on polymeric supports based on polystyrene crosslinked with divinylbenzene (PS-DVB) or DVB-PS terpolymers with acrylic acid (AA), obtained by the miniemulsion polymerization method.
  • PS-DVB polystyrene crosslinked with divinylbenzene
  • AA acrylic acid
  • the polystyrene was crosslinked with divinylbenzene, and commercial polymerizable surfactants (polyoxyethylene alkyl phenyl ether; polyoxyethylene alkyl phenyl ether sulfate) were used which provide ethylene oxide chains on the surface of PS-DVB and PS-DVB particles -AA.
  • the latexes obtained by polymerization in miniemulsion were lyophilized for the total elimination of the water used in its preparation, and the 90-250 nm polystyrene nanospheres were dispersed again in toluene.
  • Polystyrenes and styrene copolymers were modified with methylaluminoxane and then with metallocene aluminohydride, to obtain the pre-catalyst supported on a polymeric (organic) material.
  • Zirconocene aluminohydrides (highly sensitive to protic substances) showed high thermal and kinetic stability in functionalized polystyrene supports, as well as high catalytic activity in homopolymerizations and copolymerizations of ethylene and 1-hexene.
  • metallocene complexes such as zirconocene aluminohydrides have demonstrated high degree of desorption or leaching of the support material, producing poor morphology polymer (fine particles of low bulk density), which produce "fouling" (dirty, sticky material) in the reactor walls ["Suppression of Metallocene Catalyst Leaching by the Removal of Free Trimethylaluminum from Methylaluminoxane "Jani, PJ, Turunen, T., Pakkanen, T., (2006) J. Appl. Polym. Sci. 100, 4632-4635].
  • Latex particles prepared by emulsion or mini-emulsion polymerization showed aggregates of secondary particles, with fragmentation behaviors similar to those observed with inorganic silica supports.
  • the complete fragmentation of the particles of the Support is very important in a "slurry" polymerization process, since it is necessary to have access to the internal active sites in the supports, maintaining the system activity and good control of the growing polymer particle during the process.
  • the metallocenes supported on these polymeric particles showed very high activities in the polymerization of ethylene and propylene and good control of the morphology of the polymer.
  • Polymerization in Mini Emulsion is a kind of polymerization in heterophase, characterized by the presence of more than one phase.
  • a unique feature of this technique is that monomer drops are the main places where polymerization takes place [Crespy, D .; Landfester, K. Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers (2010). Beilstein J. Org. Chem. 6, 1 132-1 148. Schork, FJ, Luo, Y., Smulders, W., Russum, JP, Butté, A., Fontenot, K. Miniemulsion Polymerization (2005). Adv. Polym Sci.
  • Emulsions are degraded mainly by coalescence or diffusional degradation (maturation of Ostwaid). Coalescence can be restricted by the use of an appropriate surfactant, while diffusional degradation to the oil phase can be avoided by the addition of a hydrophobe (sometimes called ultrahydrophobic).
  • the average diameters of the droplets of the Mini-emulsions are typically in the range of 50 to 500 nm and are produced by applying high shear stresses in the system.
  • the high surface area of the resulting droplet increases the probability of nucleation of the droplets and leaves little surfactant free in the aqueous phase, available for homogeneous or micellar nucleation. In this way, the droplets become the main sites for polymerization in mini-emulsions.
  • stage III all the monomer in the drops is converted to particles of polymer.
  • the monomer is stored from the beginning of the process in the droplets, that is, in the polymer particles after the nucleation step. Due to the swelling capacity with the hydrophobe, the polymer particles often absorb their swelling capacity in the monomer.
  • the mini-emulsions are dispersions of kinetically stable oil droplets, with sizes from 50 to 500 nm and can be prepared by cutting efforts or by sonifying an oil (monomer) - water, surfactant and hydrophobic system [Schork, FJ, Luo, Y., Smulders, W., Russum, JP, Butté, A., Fontenot, K. Polymerization Miniemulsion (2005). Adv. Polym Sci. 175: 129-255; Antonietti M. and Landfester, K. Polyreactions in Miniemulsions (2002). Prog. Polym Sci., 27: 689-757; Asua, JM Polymerization Mini Emulsion (2002). Prog.
  • polystyrene-based supports of the present invention were developed by a mini-emulsion polymerization process using DVB and acrylic acid (AA) as comonomers and non-ionic commercial surfactants polymerizable (polyoxyethylene alkyl phenyl ether), polymerizable anionic surfactants (ether sulfate of polyoxyethylene alkyl phenyl) and a non-polymeric non-ionic surfactant (ethers of alkylpolyethylene glycol with a saturated fatty alcohol).
  • AA acrylic acid
  • All these surfactants confer ethylene oxide functionalities on the surface of the polystyrene particles.
  • the spherical particles of crosslinked polystyrene retain the functionality provided by the polymerizable surfactants, since these are bonded to the polymer by covalent bonds.
  • the present invention is related to the heterogeneization or support of complexes derived from metallocenes (zirconocene aluminohydrides) in organic polymers, based on polystyrenes.
  • the polystyrene crosslinked with DVB was synthesized by polymerization in miniemulsion, where the polymer is obtained with controlled spherical morphology and narrow particle size distribution, as is generally observed in miniemulsion processes (Fig. 1).
  • the preparation of the polymer particles was similar to the method reported by Klapper et al., Using a commercial polymerizable surfactant and a new metallocene derivative catalyst.
  • the metallocene derivative to be supported consists of a highly active heterobimetallic complex (Fig. 2), described in previous reports.
  • ["The Zirconocene Dihydride-Alane Adducts [(Cp ') 2ZrLu H) 2] 3Al and [(Cp') 2ZrH ⁇ -H) 2] 2AlH (Cp ' Me3SiC5H4)” Etkin, N., Stephan, DW, ( 1998), Organometallics, ⁇ 7 763-765].
  • Zirconocene aluminohydrides were synthesized from commercial metallocenes and
  • Figure 2 shows the "electron-deficient bonds" or bridged hydrogen bonds, formed between the atoms of Zr and Al, which are more sensitive bonds than the bonds contained in classical metallocenes, but, on the other hand, more reagents towards olefin polymerizations.
  • the MAO would interact with the polyether groups of the polymeric supports, avoiding the decomposition of the metallocene.
  • Zirconocene aluminohydride showed good adsorption on polystyrene-based supports, similar to the concentration determined on silica-like supports (Zr 1-2% by weight).
  • the catalytic activity of the polymerization of ethylene and the copolymerization of ethylene and 1-hexene were greater than 3000 kg Zr h PE / mol, which is considered high activity, and the morphology of the polymer was reproduced in most of the polymerizations, obtaining high density polyethylene spheres of apparent mass.
  • Figure 1 Shows the SEM micrograph (0.7 kv X 50,000) of the polystyrene particles crosslinked with DVB obtained by mini-emulsion as described in the PS-DVB5 d experiment of Table 4.
  • Figure 2 Details the synthesis and general chemical structure of zirconocene aluminohydride.
  • Figure 3 It shows a 10X optical micrograph of the polyethylene particles obtained with zirconocene aluminohydride supported on polystyrene nanoparticles obtained in experiment 7 described in Table 1.
  • Figure 4 Shows a photograph of the polyethylene particles obtained in experiment 5, described in Table 5.
  • Figure 5 Shows an SEM micrograph of the polyethylene particles obtained from experiment 3, described in Table 1.
  • the main objective of the present invention is to prepare a highly active zirconocene aluminohydride, supported on polymeric organic materials, based on cross-linked polystyrene, functionalized on its surface with polyether or polyether groups and carboxylic acids.
  • Polymeric organic supports were prepared by the mini-emulsion polymerization processes, described in Table 1, obtaining - uniformly sized 90-250 nm nanospheres, which were used as zirconocene aluminohydride supports, following the procedure reported for inorganic supports. TABLE 1
  • SDS Dodecylbencesulfonate
  • DVB Divinylbenzene
  • AA Acrylic acid
  • AIBN 2,2-Azo- ⁇ s-isobutyronitrile
  • V59 2,2-Azo-éis- 2-methylbutyronitriIo
  • Polystyrenes supported with the zirconocene / MAO aluminohydride system formed aggregates of particle sizes> ⁇ ⁇ , which can be disaggregated during the polymerization process, probably by a process similar to the fragmentation observed in the polymerizations using silica as a support.
  • the copolymers of polyethylene and poly (ethylene-l-hexene) obtained with zirconocene aluminohydride reproduce the spherical morphology of the organic supports and form high density bulk polymers.
  • the copolymers prepared as supports are actually terpolymers, according to the initial composition of the monomers in the polymerization.
  • the process for supporting zirconocene aluminohydrides in polymeric organic supports, for olefin polymerizations comprises the following steps:
  • A) Prepare a mini emulsion from water, styrene, at least one comonomer, at least one hydrophobic agent, at least one surfactant and one initiator.
  • a mini-emulsion is prepared from 75.40 - 76.98% water, styrene 1 8.85
  • At least one comonomer can be divinylbenzene (1.14
  • the hydrophobic agent can be chosen from long chain alkenes and alkenes, such as hexadecane and some hydrophobic polymers (0.76 - 0.81%)
  • the surfactant is polymerizable or non-polymerizable ( 0.50 - 2.68%), where the polymerizable surfactant is chosen from the nonylphenoletoxylated series and the non-polymerizable surfactant is chosen from the polyether family; from 'of these elements two phases, an aqueous phase and an organic phase, wherein the aqueous phase comprises water and at least one surfactant, and the organic phase the rest of the elements mentioned above are generated.
  • a preemulsion is formed from the two phases and they are subjected to the ultrasound action for a time of 1 to 5 minutes and a power of 200 to 500 W at a preferred temperature of 0 ° C to form the mini emulsion.
  • step B) Polymerize the mini emulsion obtained in step A) to obtain latex with particle diameters between 90 and 250 nm.
  • the mini-emulsion obtained in step a) is subjected to a temperature of 70 to 75 ° C, preferably 72 ° C for 10 to 16 hours, preferably 12 hours with stirring of 300 to 1000 rpm, preferably 500 rpm to obtain a latex with 15 to 30% solids.
  • step C) Dial the latex obtained in step B) to remove excess surfactant.
  • the polystyrene particles obtained from the lyophilized latex in stage C) are modified by redispersing between 2 to 50% by weight of the particles in anhydrous toluene, subjecting the solution to an ultrasound bath of 500 Watts, for 5 to 60 minutes, preferably 30 minutes.
  • the redispersed particles are cooled to 0 ° C and contacted with the MAO solution in a proportion of 10 to 30% mol of the suspended particles.
  • the mixture is stirred between 6 to 16 hours, preferably 12 hours.
  • the particles are then filtered, washed three times with toluene with particle proportions: toluene 2:50 to 4:50, at 500 rpm, for 15 to 30 min, and dried under vacuum for 2 hours.
  • the zirconocene aluminohydride dissolved in toluene is heterogenized, where the cyclopentadienyl binders of the zirconocene aluminohydride are substituted with R groups, where R can be alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentamethyl or fer / -butyl, preferably n-butyl- aluminohydride cyclopentadienyl zirconocene.
  • R groups can be alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentamethyl or fer / -butyl, preferably n-butyl- aluminohydride cyclopentadienyl zirconocene.
  • the toluene solution of zirconocene aluminohydride (0.1 g in 20 ml) is contacted with 2 g of the organic support modified with MAO in step D) suspended in 20 ml of toluene, mixing the solutions at 0 ° C between 30 at 60 min, preferably 30 min and then at room temperature between 6 to 12 hours, preferably 8 hours.
  • the organic support modified with MAO and zirconocene aluminohydride filtered and washed three times with 50 ml of toluene, and dried under vacuum for 2 hours.
  • Ethylene copolymerizations are carried out under similar conditions, using alpha olefins such as propylene, 1-butene, 1-hexene, 1- octene or 1-decene, pre faithfully 1-hexene, in concentrations from 0.05 mol / L to 3 mol / L.
  • alpha olefins such as propylene, 1-butene, 1-hexene, 1- octene or 1-decene, pre faithfully 1-hexene, in concentrations from 0.05 mol / L to 3 mol / L.
  • the experiments carried out by the mini-emulsion polymerization technique were designed to obtain crosslinked polystyrene nanoparticles between 90-250 nm.
  • the process consisted of preparing an aqueous solution of the surfactant or mixture of surfactants (solution A).
  • solution A aqueous solution of the surfactant or mixture of surfactants
  • organic phase was prepared by mixing a solution of hexadecane (HD), the monomer or monomers and the soluble initiator in the organic phase (solution B). Then, both solutions A and B were mixed under magnetic stirring in a closed container for one hour to form a pre-emulsion.
  • HD hexadecane
  • solution B soluble initiator
  • the next step consisted of the process of mini-emulsification of the mixture, transferring cold to a closed flask, degassing to remove oxygen from the air in the bottle and finally heating in an oil bath at 72 ° C for 13 hours to carry out the reaction of polymerization.
  • the solids content in organic latexes was determined by gravimetry. A 1g aliquot of the polymeric latex is poured dropwise into an aluminum dish placed in a thermobalance and heated to constant weight. The determination of the solids content includes solids from the residual initiator, the surfactant, the hydrophobe, in addition to the copolymer or terpolymer obtained in the reaction.
  • the excess surfactant or the excess surfactants were extracted by dialysis with bags prepared from membranes (Spectra / Por 6, MWCO: Da 10,000). The bags were submerged in a large tank of distilled water at room temperature; Water with the surfactants removed was discarded and replaced with fresh water every 12 hours. The dialysis process was carried out until the surface tension of the water discarded (measured by the du Nouy ring method) reaches the surface tension value of pure water at 23 ° C.
  • Some dialyzed polymeric latexes were lyophilized to be used for the particles in the polymerization of ethylene. Lyophilization of polymeric latexes was performed on representative samples of latex, freezing at -40 ° C in a glass vial, and then taken to the lyophilizer for 24 hours.
  • the latex particles were re-dispersed in toluene, under an inert atmosphere (Ar), using an ultrasound bath for 30 minutes, and then a 10% by weight MAO toluene solution was quickly added at 0 ° C. The temperature was increased and the mixture was stirred for twelve hours, at room temperature. The solution was then filtered on a sintered glass filter, and the solid was washed with three aliquots of toluene (40 mL) and the MAO modified polystyrene was dried under vacuum (10 "3 rare Hg) for 6 h.
  • the diethyl ether solution was filtered to separate the secondary product from LiCl and AIH3 and the solvent was evacuated to obtain the zirconocene aluminohydride as a white powder.
  • the product is extracted with toluene and filtered again (if necessary) and this solution is contacted with the organic support (PS-DVB / MAO or PS-AA-DVB / MAO) suspended in toluene, at room temperature.
  • the solution changes from white to pink or red, indicating the interaction between the MAO supported on the surface of the polystyrene and the zirconocene aluminohydride complex.
  • the solid is filtered and washed four times with 50 mL of toluene.
  • the supported catalyst is then dried at room temperature, under vacuum (10 ⁇ 3 mm Hg) for 6 h.
  • the catalytic activity of supported zirconocene aluminohydrides was tested in a 600 mL glass reactor, equipped with implements to work under an inert or vacuum atmosphere and equipped to feed ethylene continuously with a pressure regulator and a flow and control meter of temperature and agitation; A data acquisition system was used to detect the kinetic behavior of the catalysts.
  • the reactor glass vessel was dried for several hours at 150 ° C and previously treated with a solution of trimethylaluminum (AlMe3) at 90 ° C for one hour, before starting the polymerization process.
  • AlMe3 trimethylaluminum
  • the reactor was charged with the corresponding polymerization solvent, the temperature was adjusted to 70 ° C, and 1 ml of triisobutylaluminum (TIBA) was added as a purifier and the solvent was previously saturated with ethylene at 0.29 MPa (42 psi). These conditions were maintained for 30 minutes, stirring at 500 rpm. Then, the ethylene pressure was released and the pre-activated supported catalyst was added under ethylene pressure (0.14 MPa or 20 psi).
  • TIBA triisobutylaluminum
  • Table 1 shows the formulations for preparing the polystyrene particles.
  • the mini-emulsion was transferred to a closed round bottom flask in which the air was displaced by purging with argon for 15 min; The mini-emulsion was kept under magnetic stirring. The mini-emulsion flask was transferred to a preheated oil bath at 72 ° C to initiate polymerization (13 hours at 500 rpm).
  • nonionic polymerizable surfactant with 20 units of ethylene oxide
  • 7.7-16.7 g / L of H 2 0 The amounts of nonionic polymerizable surfactant (with 20 units of ethylene oxide) equivalent to 7.7-16.7 g / L of H 2 0 were used to prepare mini-emulsions with 250 mg of hexadecane to polymerize styrene, using 2,2-Azo-ow -methylbutyronitrile as initiator, following the procedure described above.
  • the resulting latex showed solid contents of 7.4 ⁇ 0.8 and 1 1.2 ⁇ 0.4% and conversions of 35.9 ⁇ 4.3 and 52.9 ⁇ 1.9%, respectively;
  • the polymer particles showed average diameters of 170.4 ⁇ 29.0 nm and 133.1 ⁇ 1.9 nm, respectively.
  • EXAMPLE 2 The amounts of non-ionic polymerizable surfactant (with 30 units of ethylene oxide) of 10.4 - 16.7 g / L of H 2 0 were used to prepare mini-emulsions with 250 mg of hexadecane, to polymerize styrene using 2,2-Azo- 6w-methylbutyronitrile as the initiator, following the general procedure described above.
  • the resulting latex showed solids content of 12.5 ⁇ 2.7 and 19.0 ⁇ 0.2% and conversions of 60.0 ⁇ 12.9 and 89.8 ⁇ 0.9%, respectively;
  • the polymer particles had average diameters of 160.1 ⁇ 39.4 nm and 200.1 ⁇ 23.6 nm, respectively.
  • non-ionic polymerizable surfactant with 50 units of ethylene oxide
  • 1 1.1-16.7 g / L of H 2 0 were used to prepare mini-emulsions with 250 mg of hexadecane and polymerize styrene (6.0 g) and styrene (5.7 g) with divinylbenzene (0.3 g), using 2,2-Azo-éw-isobutyronitrile as initiator, following the general procedure described above.
  • the ratio of styrene to DVB was 95/5 by weight.
  • the resulting latex showed solid contents of 18: 3 ⁇ 0.3 and 20.0%, respectively and conversions of 88.5 ⁇ 1.2 and 94.7%, respectively;
  • the polymer particles had average diameters of 215.4 (7.0 nm and 159.0 nm, respectively.
  • the specified amount of non-ionic non-polymerizable surfactant (with 50 units of ethylene oxide) equivalent to 16.7 g / LH 2 0 was used to prepare mini-emulsions with 250 mg of hexadecane to polymerize styrene (6.0 g), using 2.2 -Azo-bis-methylbutyronitrile as initiator, following the general procedure described above.
  • the resulting latex produced solids contents of 20.2% and conversion of 94.9%;
  • the polymer particles had average diameters of 148.5 nm.
  • the specific amounts of anionic polymerizable surfactant (with 10 units of ethylene oxide) equivalent to 5.4-16.7 g / L of H 2 0 were used to prepare mini-emulsions with 250 mg of hexadecane, to polymerize styrene (6.0 g), using 2, 2-Azo-toto-isobutyronitrile as initiator, following the general procedure described above.
  • the resulting latex produced solids contents of 18.7 ⁇ 1.0 and 21.2 ⁇ 1.0 and conversions of 91.5 ⁇ 4.7 and 98.4 ⁇ 2.1%;
  • the polymer particles had average diameters of 1 14.3 ⁇ 3.4 and 90.5 ⁇ 2.8 nm.
  • EXAMPLE 6 The specific amounts of anionic polymerizable surfactant (with 30 units of ethylene oxide) equivalent to 1 1.4-16.7 g / L of H 2 0 were used to prepare mini-emulsions with 250 mg of hexadecane, to polymerize styrene (6.0 g), using 2,2-Azo-or / s-isobutyronitrile as initiator, following the general procedure described above.
  • the resulting latex produced solids contents of 18.7 ⁇ 2.6 and 18.7 ⁇ 3.2% and conversions of 89.9 ⁇ 12.3 and 89.9 ⁇ 15.3%;
  • the polymer particles had average diameters of 1 13.2 ⁇ 1.0 and 102.5 ⁇ 2.5 nm.
  • non-ionic polymerizable surfactant with 50 units of ethylene oxide
  • 1.1 g / LH 2 0 The specific amount of non-ionic polymerizable surfactant (with 50 units of ethylene oxide) equivalent to 1.1 g / LH 2 0 was used to prepare mini-emulsions with 250 mg of hexadecane, to polymerize styrene (5.7 and 5.4 g) and divinylbenzene (0.3 and 0.6 g; 5 and 10% DVB by weight, respectively) using 2,2-Azo-Z> w-isobutyronitrile as initiator, following the general procedure described above.
  • the resulting latex produced solids contents of 19.5 ⁇ 0.3 and 19.7 ⁇ 0-4% and conversions of 94.3 ⁇ 1.5 and 95.0 ⁇ 1.9%;
  • the polymer particles had average diameters of 215.9 ⁇ 9.4 and 213.7 ⁇ 3.8 nm.
  • non-ionic polymerizable surfactant with 50 units of ethylene oxide
  • AIBN as an initiator
  • the specific amounts of reagents and characteristics of the resulting latexes are shown in Table 2.
  • non-ionic polymerizable surfactant with 50 units of ethylene oxide
  • non-ionic non-polymerizable surfactant with 50 units of ethylene oxide
  • the specified amounts of non-ionic polymerizable surfactant (with 50 units of ethylene oxide) and non-ionic non-polymerizable surfactant (with 50 units of ethylene oxide) were used to prepare mini-emulsions with 250 mg of hexadecane, to polymerize styrene and divinylbenzene using 2 , 2-Azo- ⁇ > / s-isobutyronitrile as initiator (100 mg), following the general procedure described above.
  • the specific amounts of reagents and characteristics of the resulting latex are shown in Table 3.
  • Table 4 shows the conditions for obtaining the selected individual latexes, used to test their operation as polymeric supports of the zirconocene aluminohydride catalyst.
  • the latexes were prepared following the general procedure described above, under the conditions shown in Table 4.
  • the zirconocene aluminohydride used in the present invention corresponds to nBuCp 2 ZrH 3 AlH4, which was synthesized from metallocene dichloride corresponding (nBuCp 2 ZrCb) and LIA1H4, as described below and the solution was added to the polystyrene particles suspended in toluene.
  • nBuCp2ZrH 3 AlH4 was extracted with 1 1 mL of toluene, and the solution was filtered to the MAO modified polystyrene support, freshly sonified in another Schlenk. The zirconocene aluminohydride solution was added at 0 ° C, then the temperature was increased and the reaction was stirred overnight. The solid obtained was filtered and washed four times with 50 mL of toluene. The supported nBuCp2ZrH 3 AlH4 was dried under vacuum (10 "3 mm Hg) for 6 h. The content of Al and Zr was determined by ICP, the data of which is reported in Table 5.
  • PS-D5 (Polystyrene-Divinylbenzene 5%), PS-D10 (Polystyrene-Divinylbenzene 10%), PS-AD5 (Polystyrene-Acid
  • AA acrylic acid, '% Al on the support determined by ICP,'% Zirconium on the support determined by ICP
  • the reactor was charged with 150 mL of the corresponding solvent (Isooctane or toluene), setting the temperature of 70 ° C. Then 1 mL of ir / -isobutlaluminum (TIBA) was added as a purifier, where the solvent was previously saturated with ethylene at 0.29 MPa (42 psi). These conditions were maintained for 30 minutes. Then, the ethylene pressure was released and the pre-activated supported catalyst was added under ethylene pressure (0.13 MPa or 20 psi).
  • solvent Isooctane or toluene
  • TIBA ir / -isobutlaluminum
  • This suspension of the pre-activated catalyst it was injected into the reactor using a safe syringe.
  • the molar concentration of zirconium corresponds to 2.4 X 10 ⁇ 6 M.
  • the reaction mixture was stirred at 500 rpm for 1 h, and ethylene consumption was recorded in a data acquisition equipment (DAS), to compare kinetic behaviors. of polymerization.
  • DAS data acquisition equipment
  • NBuCp 2 ZrH 3 AlH 4 was supported under conditions similar to the procedure described in Example 12, using PS-DVB (90: 10) as a support, where the adsorption percentage of Al and Zr are similar to those obtained in the example 1 1.
  • the polymerization of ethylene was carried out as described in example 3.
  • Molecular weights (Mw and D) and melting temperature (T m ) are also presented in Table 5.
  • PS-D10 Polystyrene-Divinylbenzene 10%
  • Al / Zr 500
  • T 70" C
  • 0.29 MPa C 2 500 rpm
  • t I h.
  • NBuCp2ZrH 3 AlH4 was supported on styrene copolymers with 10% divinylbenzene (PS-DVB 10) on dialyzed or non-dialyzed supports, as shown in Table 6.
  • the catalytic activity was increased to 100% or more, in these materials, as expected, in a more polar environment in the reactions.
  • the highest catalytic activities were obtained using polymeric supports containing acrylic acid (2%).
  • the evaluation of The polymerization conditions related to the solvent showed that the use of toluene in the polymerization of ethylene is more favorable for the increase in the catalytic activity of nBuCp 2 ZrH3AIH4 supported in polystyrene particles.
  • the concentration of the catalytic system, in the polymerization medium is another aspect to study in coordination polymerizations, where for better stabilized supported systems, greater catalytic activity is obtained at low molar concentrations of the catalyst. According to the above, the concentration of nBuCp 2 ZrH 3 AlH4 was decreased in the polymerization system, adding smaller amounts of the supported catalyst.
  • Table 7 shows the results of the catalytic activity obtained for zirconocene aluminohydride supported in polymers with 5% DVB (Exp. 3 and 4 of Table 7) using lower catalyst concentrations (one quarter and one half, respectively ) compared to the standard conditions used earlier in this study (tables 5 and 6).
  • PS-D10 Polystyrene Divinylbenzene 10%
  • PS-DS Polystyrene Divinylbenzene 5%
  • PS-AD10 Polystyrene Acrylic Acid 2% -
  • the reactor was charged with 150 mL of the corresponding solvent (isooctane or toluene) and the corresponding amount of co-monomer (5 mL) was added setting the temperature of 70 ° C. 1 mL of m '-isobutilaluminium (TIBA) was then added as a purifier, the solvent previously saturated with ethylene to 0.29 MPa (42 psi). These conditions were maintained for 30 minutes. The ethylene pressure was then released and the pre-activated supported catalyst was added under ethylene pressure (20 psi).
  • TIBA m '-isobutilaluminium
  • This suspension (pre-activated catalyst) was injected into the reactor using a safe syringe.
  • the copolymerization reaction was stirred for 1 h, at 500 rpm, where ethylene consumption was recorded in a device (DAS) data acquisition system, to compare the kinetic behaviors of the polymerizations.
  • DAS device
  • the temperature decreased to 40 ° C, and the polymerization reaction was deactivated by adding 20 mL of acidified methanol, to dissolve the excess of MAO. washed with a lot of methanol and dried in a vacuum oven (10 "3 mm Hg) at 60 ° C for 2 hours.
  • Poly (ethylene-l-hexene) was characterized by gel permeation chromatography (GPC), and by differential calorimetry (DSC); the values of molecular weights (Mw and D) and melting temperatures (T m ) are presented in table 8.
  • PS-AD10 Polystyrene-Divinylbenzene 10%, 2% AA
  • [Zr] 2.4 X 10 f ' M
  • the present invention provides a process for the preparation of highly active metallocene aluminohydrides, using polymeric supports obtained from the miniemulsion processes and based on the products of functionalized and crosslinked polymers.
  • the supported zirconocene aluminohydride can also be used in copolymerizations of ethylene and alpha-olefins, such as 1-hexene.

Abstract

La présente invention concerne un procédé destiné à supporter des aluminohydrures de zirconocènes hautement actifs (Cp2ZrH3AlH2) sur des supports polymères obtenus à partir de procédés de polymérisation en mini-émulsion, à base de particules de polystyrène entrecroisées et fonctionnalisées. Les supports à base de polystyrène sont préparés par mini-émulsion en utilisant du divinylbenzène (DVB) et de l'acide acrylique comme co-monomères et des tensioactifs polymérisables commerciaux (Noigen RN-50), lesquels confèrent des fonctionnalités d'oxyde d'éthylène à la surface des particules de polystyrène. Les particules de polystyrène entrecroisées présentent des diamètres moyens des particules compris entre 90 et 238 nm, le complexe aluminohydrure de zirconocène étant supporté selon les procédés similaires décrits pour les supports inorganiques (silice). L'aluminohydrure de zirconocène supporté est également utile dans des copolymérisations d'éthylène et d'alpha-oléfines, notamment du 1-hexène. La morphologie des polyéthylènes et des copolymères d'éthylène obtenus a été clairement améliorée par comparaison avec la morphologie obtenue dans les polymérisations d'éthylène faisant intervenir le même système catalytique supporté sur silice poreuse modifiée.
PCT/MX2014/000210 2014-12-17 2014-12-17 Hétérogénéisation d'aluminohydrures de zirconocènes sur des supports organiques pour la polymérisation d'éthylène WO2016099236A1 (fr)

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MX2014015566A MX2014015566A (es) 2014-12-17 2014-12-17 Heterogenización de aluminohidruros de zirconocenos en soportes orgánicos para la polimerización de etileno.
MXMX/A/2014/015566 2014-12-17

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6310164B1 (en) * 1997-07-18 2001-10-30 Mitsu Chemicals Inc Unsaturated copolymers, processes for preparing the same, and compositions containing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6310164B1 (en) * 1997-07-18 2001-10-30 Mitsu Chemicals Inc Unsaturated copolymers, processes for preparing the same, and compositions containing the same

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
L. SHI ET AL.: "Effect of swelling response of the support particles on ethylene polymerization", POLYMER, vol. 48, 2007, pages 2481 - 2488, XP022043323, DOI: doi:10.1016/j.polymer.2007.02.043 *
N. KISHI ET AL.: "Synthesis of polymer supported borate cocatalysts and their applicaction to metallocene polymerizations", POLYMER, vol. 41, 2000, pages 4001 - 4012 *
R. CHARLES ET AL.: "Novel supported catalysts for ethylene polymerization based on aluminohydride- zirconocene complexes", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 307, 2009, pages 98 - 104, XP026211489, DOI: doi:10.1016/j.molcata.2009.03.018 *
W. WANG ET AL.: "Study on copolymerization of ethylene/1-hexene catalyzed by a novel polystyrene- supported metallocene catalyst", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 102, 2006, pages 1574 - 1577 *

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