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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
  • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • 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
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene
• • 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
  • C08F4/65927—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/14—Applications used for foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

• the present invention relates to a process for the preparation of an elastomeric polymer composition
• a process for the preparation of an elastomeric polymer composition comprising the steps of polymerizing ethylene, an alpha-olefin and a non- conjugated diene in the presence of a catalyst system based on a transition metal component supported on a porous polyolefm.
• the most common polyolefm elastomers produced are copolymers of ethylene and propylene (EPM) and terpolymers of ethylene, propylene and a diene (EPDM).
• EPM ethylene and propylene
• EPDM terpolymers of ethylene, propylene and a diene
• Ordinary EPDM elastomers can be cured using such curatives as organic peroxides, phenolic resins or sulphur.
• the catalysts conventionally employed in the production of high molecular weight EPDM elastomers are soluble vanadium catalysts such as VC1 , VOCl 3 , VO(Ac) 3 , V(Acac) 3 or VO(OR) 3 where R is an alkyl group together with an organoaluminum compound.
• the activity of the vanadium catalysts are relatively low, e.g., producing 5-20 kg polymer/g vanadium.
• Metallocene compounds have been used for the production of EPDM, for example Kaminsky et al., J. Poly. Sc, Vol. 23, 2151-2164 (1985) discloses the use of a metallocene- methylaluminoxane (MAO) catalyst system to produce low molecular weight EPDM elastomers. Such catalysts require long reaction times and provide low yields and are therefore impractical for commercial EPDM manufacture.
• MAO metallocene- methylaluminoxane
• Other polymerization processes for producing EPDM featuring the use of a metallocene catalyst activated by an aluminoxane such as MAO are described in U.S. 4,871,705, 5,001,205, 5,229,478 and 5,442,020, EP 347,129 and WO 95/16716.
• EP 593 083 describes a gas phase polymerization process for producing EPDM employing a bridged metallocene catalyst introduced in the reactor in the form of droplets.
• EPDM terpolymers are often used as components for blends with other polymer having different characteristics, such as different crystallinity. In particular they are blended with isotactic polypropylene for obtaining the so-called TPV polymer.
• Blends by direct polymerization are well known in the art.
• EPDM can be blended by using soluble vanadium based catalysts by using reactors in series and making a polymer with different properties in each reactor.
• WO 99/45046 relates to a process for producing reactor blends in which, in the presence of a metallocene catalyst in one reactor EPDM terpolymers are produced and in a second reactor propylene is polymerized in the presence of the polymer produced in the first reactor.
• An object of the present invention is a process for the preparation of an elastomeric polymer composition containing EPDM polymers, in high yields and with a random incorporation of the non-conjugated diene. This can be achieved according to the invention by impregnating the diene monomer onto a porous alpha-olefin polymer.
• impregnated means that the diene is retained in the porous alpha-olefin polymer.
• the impregnation step a) is performed by: al) first impregnating the porous alpha-olefin polymer with the non-conjugated diene; and then a2) impregnating the product obtained in step al) with the catalyst based on a transition metal compound.
• the polymerization process can be carried out in the hquid phase in the presence or absence of an inert hydrocarbon solvent, or in the gas phase.
• the hydrocarbon solvent can be either aromatic, such as toluene, or aliphatic, such as propane, hexane, heptane, isobutane or cyclohexane.
• the polymerization step b) is carried out in the gas phase, it is suitably done in a fluidized bed reactor.
• the polymerization temperature is generally comprised between -100°C and +200°C, and, suitably, between 10°C and +90°C.
• the polymerization pressure is generally comprised between 0,5 and 100 bar.
• Said alpha-olefin polymer has a pore volume greater than 0.45 cc/g (determined by mercury absorption); preferably, greater than 0.5 cc/g; more preferably greater than 0.55 cc/g.
• said porous alpha-olefin polymer is an homopolymer or a copolymer of propylene or ethylene.
• porous propylene polymers Two particularly suitable classes of porous propylene polymers are those obtained according to WO 0146272 and WO 02/22732 particularly good results are obtained when the catalyst described in WO 0146272 is used with the process described in WO 02/22732.
• Polymers obtained according to WO 0146272 have a high content of the so-called stereoblocks, i.e. of polymer fractions which, although predominantly isotactic, contain a not negligible amount of non-isotactic sequences of propylene units, h the conventional fractionation techniques such as the TREF (Temperature Rising Elution Temperature) those fractions are eluted at temperatures lower than those necessary for the more isotactic fractions.
• the polymers obtained according to the process described in WO 02/22732 show improved porosities.
• a suitable propylene homopolymer used as support in step a) has the following characteristics:
• the fraction eluted at a temperature range from 25°C to 97° is higher then 20% preferably higher than 30%; more preferably higher than 40% of the total polymer eluted; a melting enthalpy lower than 90 J/g; preferably lower than 80 J/g;more preferably lower than 70 J/g; a pore volume (determined by mercury absorption) greater than 0.45 cc/g; preferably - greater than 0.5 cc/g; more preferably greater than 0.55 cc/g.
• a melting enthalpy lower than 90 J/g preferably lower than 80 J/g;more preferably lower than 70 J/g
• a pore volume (determined by mercury absorption) greater than 0.45 cc/g; preferably - greater than 0.5 cc/g; more preferably greater than 0.55 cc/g.
• the use of this class of polymers give rise a better impregnation of the diene and of the transition metal catalyst component that leads to an increasing of the activity of the catalyst system in the presence of the diene and to a reducing of the fouling. Moreover, with this polymer the compatibility between the polymeric matrix and the terpolymer is enhanced.
• the elastomeric terpolymer prepared in step b) contains from 20% to 90% by weight of ethylene derived units, more preferably from 30% to 85% by weight, even more preferably from 35% to 70%> by weight.
• alpha-olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-dodecene.
• Preferred alpha-olefin is propylene.
• the non-conjugated diene component of the terpolymer which is impregnated on the porous alpha olefin polymer at least in part before the polymerization step, can be a straight chain, branched chain or cyclic hydrocarbon diene having from 6 to 20 carbon atoms.
• suitable non-conjugated dienes are:
• branched chain acyclic dienes such as 5 -methyl- 1,4-hexadiene, 3, 7-dimethyl- 1,6- octadiene, 3,7-dimethyl-l,7-octadiene and mixed isomers of dihydro myricene and dihydroocinene; single ring alicyclic dienes, such as 1,3-cyclopentadiene, 1,4-cyclohexadiene, 1,5- cyclooctadiene and 1,5-cyclododecadiene;
• - multi-ring alicyclic fused and bridged ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo-(2,2,l)-hepta-2, 5-diene; and
• alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes such as 5-methylene-2- norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,5-(4- cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene.
• MNB 5-methylene-2- norbornene
• NNB 5-propenyl-2-norbornene
• 5-isopropylidene-2-norbornene 5-isopropylidene-2-norbornene
• 5-(4- cyclopentenyl)-2-norbornene 5-cyclohexylidene-2-norbornene
• 5-vinyl-2-norbornene and norbornadiene norbornadiene
• Preferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (E B), 5-vinylidene-2- norbornene (VNB), 5-methylene-2-norbornene (MNB) and dicyclopentadiene (DCPD).
• HD 1,4-hexadiene
• E B 5-ethylidene-2-norbornene
• VNB 5-vinylidene-2- norbornene
• MNB 5-methylene-2-norbornene
• DCPD dicyclopentadiene
• dienes are 5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).
• the non-conjugated dienes are generally incorporated into the terpolymer in an amount from 0.5%) to about 20%) by weight; preferably from 1%> to 15% by weight, and more preferably from 2% to 10% by weight. If desired, more than one diene may be incorporated simultaneously, for example HD and ENB, with total diene incorporation within the limits specified above.
• the diene can be impregnated into the porous polymer with various methods.
• the porous polymer can be put in contact with a solution of the diene in a solvent such as propane, under stirring.
• the solvent is then removed, for example, by flashing the solution.
• Non limitative examples of the transition metal catalyst component are compounds of titanium not containing metal- ⁇ bonds supported on a Mg halide, compounds of vanadium and metallocene compounds.
• the catalyst system used in the process of the present invention comprises:
• Al-alkyl an aluminium-alkyl compound (Al-alkyl); and optionally
• Non-limiting examples of aluminium-alkyl compounds are compound of formula HjAlR 3 . j or HjAl 2 R !7 6 -j, where R 17 substituents, same or different, are hydrogen atoms, halogen atoms, - C 20 -alkyl, C 3 -C 20 -cyclalkyl, C 6 -C 0 -aryl, C 7 -C 20 -alkylaryl or C 7 ⁇ C 20 -arylalkyl, optionally contaimng silicon or germanium atoms with the proviso that at least one R is different from halogen, and j ranges from 0 to 1, being also a non-integer number.
• the above mentioned Al-alkyl compounds can be used either alone or in mixtures thereof.
• trimethylaluminium (TMA), triisobutylaluminium (TIBAL) and tris(2,4,4-trimethyl- pentyl)aluminium (TIOA) are preferred.
• the internal electron-donor compounds can be selected from ethers, esters, amines, ketones and the like. Non-limiting examples are alkyl esters, cycloalkyls and aryls of polycarboxylic acids, such as phthalic and maleic esters and ethers, such as those which are described in EP-A 45977, the disclosure of which is incorporated herein by reference.
• the external donor can be the same or can be different from the internal donor.
• the stereospecificity of the catalyst is sufficiently high, such that the presence of an external-donor is not required. Examples of these kind of catalysts are disclosed, for instance, in USP 4,399,054 and USP 5,221,651, the disclosure of which is incorporated herein by reference.
• the catalyst system used in the process of the present invention comprises:
• Al-alkyl an aluminium-alkyl compound
• Aluminium alkyl compound are the aluminium compound disclosed above.
• Preferred vanadium compound is V(Acac) 3 used in conjunction with Aluminium alkyl compound containing an halogen atom, preferably chlorine.
• the catalyst system used in the process of the present invention comprises:
• Cp is a substituted or unsubstituted cyclopentadienyl group, optionally condensed to one or more substituted or unsubstituted, saturated, unsaturated or aromatic rings, containing from 4 to 6 carbon atoms, optionally containing one or more heteroatoms;
• A is O, S, NR 2 , PR 2 wherein R 2 is hydrogen, a linear or branched, saturated or unsaturated
• Ci- o alkyl, C 3 -C 20 cycloalkyl, C 6 -C 2 o aryl, C 7 -C 20 alkylaryl or C -C 20 arylalkyl, or A has the same meaning of Cp;
• M is a transition metal belonging to group 4, 5 or to the lanthanide or actinide groups of the Periodic Table of the Elements (IUPAC version); the substituents X, equal to or different from each other, are monoanionic sigma ligands selected from the group consisting of hydrogen, halogen, R 3 , OR 3 , OCOR 3 , SR 3 , NR 3 2 and PR , wherein R is a linear or branched, saturated or unsaturated C 1 -C2 0 alkyl, C 3 -
• n is an integer ranging from 0 to 4; r is 0, lor 2; preferably 0 or 1 ; n is 0 when r is 0 or 2; p is an integer equal to the oxidation state of the metal M minus r+1; it ranges from 1 to
• the divalent bridge (ZR 1 ,,,), is preferably selected from the group consisting of CR ⁇ , (CR 1 2 ) 2 , (CR 1 2 ) 3 , SiR ⁇ , GeR ⁇ , NR 1 and PR 1 , R 1 having the meamng reported above; more preferably, said divalent bridge is Si(CH ) 2 , SiPh 2 , CH 2 , (CH ) 2 , (CH 2 ) 3 or C(CH 3 ) 2 .
• the ligand Cp which is ⁇ -bonded to said metal M, is preferably selected from the group consisting of cyclopentadienyl, mono-, di-, tri- and tetra-methyl cyclopentadienyl; 4- t butyl- cyclopentadienyl; 4-adamantyl-cyclopentadienyl; indenyl; mono-, di-, tri- and tetra-methyl indenyl; 2-methyl indenyl, 3- l butyl-indenyl, 4-phenyl indenyl, 4,5 benzo indenyl; 3- trimethylsilyl-indenyl; 4,5,6,7-tetrahydroindenyl; fluorenyl; 5,10-dihydroindeno[l,2-b]indol- 10-yl; N-methyl- or N-phenyl-5,10-dihydroindeno [l,2-b]indol-10-yl; 5,6
• the group A is O, S, N(R 2 ), preferably R 2 is methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, phenyl, p-n-butyl-phenyl, benzyl, cyclohexyl and cyclododecyl; more preferably R 2 is t-butyl; preferably A is N(R 2 ) or has the same meaning of Cp.
• the metal M is preferably Ti, Zr or Hf, and more preferably Zr.
• the substituents X are preferably the same and more preferably, the substituents X are selected from the group consisting of -Cl, -Br, -Me, -Et, -n-Bu, -sec-Bu, -Ph, -Bz, -CH 2 SiMe 3 , -OEt, - OPr, -OBu, -OBz and -NMe 2 .
• the variable m is preferably 1 or 2.
• variable n ranges preferably from 1 to 2, when n > 1, the atoms Z can be the same or different from each other, such as in divalent bridges CH 2 -O, CH -S and CH 2 -Si(CH 3 ) 2 .
• the variable p is preferably 2.
• Non limiting examples of compounds belonging to formula (I) are the rac and meso form (when present) of the following compounds: bis(cyclopentadienyl)zirconiumdichloride; bis(indenyl)zirconiumdichloride; bis(tetrahydroindenyl)zirconiumdichloride; bis(fluorenyl)zirconiumdichloride; (cyclopentadienyi ⁇ indenyl)zirconiumdichloride; (cyclopentadienyl)(fluorenyl)zirconiumdichloride; (cyclopentadienyl)(tetrahydroindenyl)zirconiumdichloride; (fluorenyi ⁇ indenyl)zirconiumdichloride; dimethylsilanediylbis(indenyl)zirconiumdichloride, dimethylsilanediylbis(2-methyl-4-phenylindenyl)zir
• a suitable class of metallocene complexes (A) for use in the catalysts complexes of the invention comprises the well-known constrained geometry catalysts, as described in EP-A-0 416 815, EP-A-0 420 436, EP-A-0 671 404, EP-A-0 643 066 and WO-A- 91/04257.
• the group A has the same meaning of Cp, it is preferably substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl (2,5-dimethyl-cyclopenta[l,2- b:4,3-b']-dithiophene).
• cyclopentadienyl indenyl
• tetrahydroindenyl 2,5-dimethyl-cyclopenta[l,2- b:4,3-b']-dithiophene
• a particularly preferred class of metallocene compounds has the following formulas (Ila) or
• R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are selected from the group consisting of hydrogen, linear or branched saturated or unsaturated C 1 -C 20 -alkyl,
• R 4 is hydrogen, methyl, phenyl isopropyl
• R 5 is hydrogen, tertbutyl, isopropyl
• R is hydrogen, methyl, phenyl, or form with R a condensed benzene ring
• R is hydrogen or forms with R a condensed benzene ring
• A is O, S, NR 2 , PR 2 wherein R 2 has the meaning reported above;
• the groups R 10 equal to or different from each other are selected from the group consisting of hydrogen, linear or branched saturated or unsaturated C 1 -C 20 -alkyl, C 3 -C 20 -cycloalkyl, C 6 -C 20 -aryl, C -C 2 o-alkylaryl, C -C 2 o-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two adjacent groups can form a C 4 -C ring optionally containing O, S, N, P or Si atoms that can bear substituents;
• M is titanium; the group (R l m Z) n is selected from the group consisting of dimethylsilyl, diphenylsilyl, diethylsilyl, di-n-propylsilyl, di-isopropylsilyl, di-n-butyl-silyl, di-t-butyl-silyl, di-n-hexylsilyl, ethylmethylsilyl, n-hexylmethylsilyl, cyclopentamethylenesilyl, cyclotetramethylenesilyl, cyclotrimethylenesilyl, methylene, dimethylmethylene and diethylmethylene; even more preferably, it is dimethylsilyl, diphenylsilyl or dimethylmethylene; A is R 2 .
• Preferred subclasses of metallocene compounds belonging to formula (III) have formulas (IVa) and (IVb)
• Alumoxanes used as component (B) can be obtained by reacting water with an organo- aluminium compound of formula HjAlR 17 3 . j or HjAl 2 R 17 6- j , where R 17 substituents, same or different, are hydrogen atoms, halogen atoms, C 1 -C 20 -alkyl, C 3 -C 20 -cyclalkyl, C 6 -C 20 -aryl, C 7 - C 2 o-alkylaryl or C 7 -C 2 o-arylalkyl, optionally containing silicon or germanium atoms with the proviso that at least one R 17 is different from halogen, and j ranges from 0 to 1, being also a non-integer number, h this reaction the molar ratio of Al water is preferably comprised between 1:1 and 100:1.
• the molar ratio between aluminium and the metal of the metallocene is comprised between about 10:1 and about 20000:1, and more preferably between about 100:1 and about 5000:1.
• the alumoxanes used in the catalyst according to the invention are considered to be linear, branched or cyclic compounds containing at least one group of the type:
• alumoxanes of the formula can be used in the case of linear compounds, wherein n 1 is 0 or an integer from 1 to 40 and the substituents R 17 are defined as above, or alumoxanes of the formula:
• n is an integer from 2 to 40 and the R substituents are defined as above.
• alumoxanes suitable for use according to the present invention are methylalumoxane (MAO), tetra-(isobutyl)alumoxane (TIBAO), tetra-(2,4,4-trimethyl- pentyl)alumoxane (TIOAO), tetra-(2,3-dimethylbutyl)alumoxane (TDMBAO) and tetra-(2,3,3- trimethylbutyl)alumoxane (TTMBAO).
• MAO methylalumoxane
• TIBAO tetra-(isobutyl)alumoxane
• TIOAO tetra-(2,4,4-trimethyl- pentyl)alumoxane
• TDMBAO tetra-(2,3-dimethylbutyl)alumoxane
• TTMBAO tetra-(2,3,3- trimethylbutyl)alumox
• Non-limiting examples of aluminium compounds according to said PCT applications are: tris(2,3,3-tri ⁇ nethyl-butyl)aluminium, tris(2,3-dimethyl-hexyl)aluminium, tris(2,3-dimethyl-butyl)aluminium, tris(2,3-dimethyl-pentyl)aluminium, tris(2,3-dimethyl-heptyl)aluminium, tris(2-methyl-3-ethyl-pentyl)aluminium, tris(2-methyl-3-ethyl-hexyl)aluminium, tris(2-methyl- 3-ethyl-heptyl)aluminium, tris(2-methyl-3-propyl-hexyl)aluminium, tris(2-ethyl-3-methyl-butyl)aluminium, tris(2-ethyl-3-methyl-pentyl)aluminium, tris(2,3-
• TMA trimethylaluminixxm
• TIBAL triisobutylaluminium
• TIOA tris(2,4,4-trimethyl-pentyl)aluminium
• TDMBA tris(2,3-dimethylbutyl)alumini ⁇ m
• TTMBA tris(2,3,3-trimethylbutyl)aluminium
• Non-limiting examples of compounds able to form an alkylmetallocene cation that can be used as component (B) are compounds of formula D E " , wherein D is a Br ⁇ nsted acid, able to donate a proton and to react irreversibly with a substituent X of the metallocene of formula (I) and E " is a compatible anion, which is able to stabilize the active catalytic species originating from the reaction of the two compounds, and which is sufficiently labile to be able to be removed by an olefinic monomer.
• the anion E " comprises of one or more boron atoms.
• the anion E " is an anion of the formula BAr (_) , wherein the substituents Ar which can be identical or different are aryl radicals such as phenyl, pentafluorophenyl or bis(trifluoromethyl)phenyl. Tetrakis-pentafluorophenyl borate is particularly preferred examples of these compounds are described in WO 91/02012. Moreover, compounds of the formula BAr 3 can conveniently be used. Compounds of this type are described, for example, in WO 92/00333.
• compounds able to form an alkylmetallocene cation are compounds of formula BAr 3 P wherein P is a substituted or unsubstituted pyrrol radicals, and B is a boron atom. These compounds are described in WOO 1/62764. All these compounds containing boron atoms can be used in a molar ratio between boron and the metal of the metallocene comprised between about 1:1 and about 10:1; preferably 1 : 1 and 2.1; more preferably about 1:1.
• Non limiting examples of compounds of formula D + E " are: Triethylammoniumtetra(phenyl)borate, Tributylammoniumtet ⁇ a(phenyl)borate, Trimethylammoniumtetra(tolyl)borate, Tributylammoniumtetra(tolyl)borate, Tributylammoniumtetra(pentafluorophenyl)borate, Tributylammomumtetra(pentafluorophenyl)aluminate, Tripropylammoniumtetra(dimethylphenyl)borate, Tribu1ylammoniumtetra(trifluoromethylphenyl)borate, Tributylammoniumtetra(4-fluorophenyl)borate, N,N-Dimethylaniliniumtetra(phenyl)borate, N,N-Diethylaniliniumtetra(phenyl)borate,
• the catalyst system of the present invention can be supported on the porous alpha-olefin polymer with various methods known in the art. For example to a suspension of the porous polymer, optionally containing the diene, in a solvent, such as propane, a solution or a suspension of the catalyst system can be injected under stirring and then the solvent is removed, for example by flashing.
• a solvent such as propane
• a particularly suitable process for supporting the catalyst system is described in WO 01/44319 wherein the process comprises the steps of:
• step (c) discharging the material resulting from step (b) from the contacting vessel and suspending it in an inert gas flow, under such conditions that the solvent evaporates;
• step (d) reintroducing at least part of the material resulting from step (c) into the contacting vessel together with another volume of the catalyst solution not greater than the total pore volume of the reintroduced material.
• the material resulting from step (d) can be subjected to further cycles of steps (c) and (d).
• the supported catalyst can be suitably recovered after a drying step (c).
• the process of the present invention can also be used as the last step of a multistep process according to WO 96/11218 and WO 96/2583.
• the porous alpha-olefin polymer is prepared in the first reactor then, after the impregnation steps, ethylene, alpha-olefin and diene can be polymerized.
• Another object of the present invention is an heterophasic elastomeric polymer composition containing: from 10%) to 70% by weight, preferably between 15% and 50% by weight, more preferably between 25% and 50% by weight of a propylene homopolymer having the following characteristics:
• a pore volume greater than 0.45 cc/g (determined by mercury absorption); preferably greater than 0.5 cc/g; more preferably greater than 0.55 cc/g; and from 30%) to 90% by weight, preferably between 85% and 50%> by weight, more preferably between 75% and 50%> by weight of an ethylene, propylene and non conjugated diene terpolymer containing:
• ethylene derived units more preferably from 30% to 85% by weight of ethylene, even more preferably from 35%> to 80%> by weight; from 10%) to 80%) by weight of propylene derived units, more preferably from 20% to 65%o by weight; and
• a further object of the present invention is a solid catalyst system comprising: a porous alpha-olefin polymer impregnated with a non conjugated diene; a transition metal catalyst component; and a suitable cocatalyst.
• the porous alpha-olefin polymer is endowed with the following characteristics:
• the fraction eluted at a temperature range from 25°C to 97° is higher then 20% preferably higher than 30%>; more preferably higher than 40%; and
• thermoplastic elastomeric products having optimum elastomeric properties and a good balance of elasto-mechanical properties can be obtained after dynamic vulcanization.
• thermoplastic elastomeric composition comprising putting in contact the product obtained by the process described above with crosslinking agents and, if appropriate, coadjuvants thereof, at temperatures of between 140°C and 240 °C.
• the preferred technique is dynamic vulcanization.
• the compositions of the invention are subjected to kneading or to other shear forces in the presence of crosslinking agents and, if appropriate, coadjuvants thereof, at temperatures between 140°C and 240°C, preferably at temperatures higher than the melting point of the crystalline phase.
• the compositions of the invention can be impregnated with an oil extender for regulating their hardness, either before the addition of the crosslinking agent or at the start or end of vulcanization.
• the oil extender used can be of various types, for example aromatic, naphthenic or preferably paraffinic.
• the crosslinking agents which can be used are those commonly known in the art, such as organic peroxides, phenolic resins and sulphur.
• the selection of the crosslinking agent influences the properties of the final product. For example, by using phenolic resins a well known TPV can be obtained.
• liquid 1,2-polybutadiene or compounds of the triallyl cyanurate type can be used as coadjuvant compounds for the crosslinking.
• compositions of the invention can be charged with various additives, such as heat stabilizers, antioxidants, mineral fillers or any other type of agents customarily used in the art.
• additives such as heat stabilizers, antioxidants, mineral fillers or any other type of agents customarily used in the art.
• Intrinsic viscosity measured in tetrahydronaphtalene (TH ⁇ ) at 135 °C .
• Fraction soluble in xylene Fraction soluble in xylene:
• Porosity determined by immersing a known quantity of the sample in a known quantity of mercury inside a dilatometer and gradually hydraulically increasing the pressure of the mercury. The pressure of introduction of the mercury in the pores is in function of the diameter of the same. The measurement was carried out using a porosimeter "Porosimeter 2000 Series" (C. Erba). The total porosity was calculated from the volume decrease of the mercury and the values of the pressure applied.
• the porosity expressed as percentage of voids is determined by absorption of mercury under pressure.
• the volume of mercury absorbed corresponds to the volume of the pores.
• a calibrated dilatometer (diameter 3 mm) CD3 (Carlo Erba) connected to a reservoir of mercury and to a high- vacuum pump (1.10 "2 mbar) is used.
• a weighed amount of sample (about 0,5 g) is placed in the dilatometer.
• the apparatus is then placed under high vacuum ( ⁇ 0,1 mm Hg) and is maintained in these conditions for 10 minutes.
• the dilatometer is then connected to the mercury reservoir and the mercury is allowed to flow slowly into it until it reaches the level marked on the dilatometer at a height of 10 cm.
• the value of the apparent volume Ni of the sample prior to penetration of the pores can be calculated.
• the volume of the sample is given by: v ⁇ PrCPz-pyj/D
• P is the weight of the sample in grams
• V is the weight of the dilameter+mercury in grams
• P 2 is the weight of the dilatometer+mercury+sample in grams
• Flexural modulus ASTM D-5023. Compression. Set: ASTM D395 22hr/70°C. Hardness Shore A: ASTM D2240. Modulus 100, psi: ASTM D412. Tensile strength: ASTM D412.
• the solid titanium catalyst component was prepared according to example 2 of EP-A-395 083. Using 0,011 g of this solid, a propylene polymerization was carried out in a 4 1 autoclave equipped with magnetically driven stirrer and a thermostatic system, previously fluxed with nitrogen at 70°C for one hour and then with propylene. Into the reactor at room temperature, without stirring but under propylene stream, a catalyst system consisting of a suspension of the solid component in 15 ml of hexane, 1,14 g of triethylaluminium, and 114 mg of dicyclopentyldimethoxysilane (donor D) is introduced, this system is prepared just prior to its use in the polymerization test.
• donor D dicyclopentyldimethoxysilane
• the solid titanium catalyst component was prepared according to example 2 of EP-A-395 083.
• a polymerization reactor was heated to 70°C, purged with a slow argon flow for 1 hour, its pressure was then raised to 100 psi-g with argon at 70°C and then the reactor was vented. This procedure was repeated 4 more times. The reactor was then cooled to 30°C.
• the catalytic complex so obtained was introduced, under an argon purge, into the polymerization reactor at room temperature.
• the remaining hexane/TEAL/silane solution was then drained from the additional funnel to the flask, the flask was swirled and drained into the reactor and the injection valve was closed.
• the polymerization reactor was slowly charged with 2.2. L of liquid propylene and H 2 while strring. Then the reactor was heated to 70°C maintaining the temperature and pressure constant for about 2 hours. After about two hours agitation was stopped and the remaining propylene was slowly vented.
• the reactor wwas heated to 80°C, pured with argon for 10 minutes and then cooled to room temperature and opened.
• the polymer waas removed and dried in a vacuum oven at 80°C for 1 hour.
• Octilmethyldimetoxy silane (OctMeMS) was used as external donor instead of dicyclopentyl dimetoxy silane.
• a catalyst solution was prepared by dissolving rac-ethylenbis(tetrahydroindenyl)ZrCl2 (rac EBTHIZrCl 2 ), methyl alumoxane
• the polymerisation was stopped by quickly degassing the monomers.
• the polymer was plunged in 800 ml of methanol and filtered.
• the filtered polymer was plunged again in 800 ml of methanol containing Irganox 1020, added to be about 200 ppm on the polymer.
• Methanol was then evaporated with a nitrogen stream under reduced pressure at 60°C.
• the polymer obtained in examples 1-4 were vulcanized in a Brabender mixer by mixing the polymers until the plastic phase melt and the torque leveled off. At that time the cure system was added and mixing was continued for 4 minutes. The material was mixed at 180°C and 100 RPM and the temperature rised during cure to about 200°C.
• the composition of the cured polymer is reported in table 3. Properties of the vulcanized polymers are reported in table 4.

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• 2002
  • 2002-11-22 JP JP2003547470A patent/JP2005510590A/ja not_active Withdrawn
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