Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/08—Butenes
• • 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
  • C08F110/08—Butenes
• • 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

Definitions

• the present invention relates to a process for polymerizing 1-butene by using metallocene compounds and to the isotactic polybutene obtained thereby.
• 1-Butene polymers are well known in the art. In view of their good properties in terms of pressure resistance, creep resistance, and impact strength they have a lot of uses such as the manufacture of pipes to be used in the metal pipe replacement, easy-open packaging and films.
• the 1-butene (co)polymers are generally prepared by polymerizing 1-butene in the presence of
• diethyl aluminum iodide (DEAI) is also used in mixtures with DEAC.
• DEAC diethyl aluminum iodide
• the 1-Butene polymers prepared with these catalysts have a high content of catalyst residues (generally more than 300 ppm of Ti) which lowers the properties of the polymers making it necessary a deashing step.
• 1-butene (co)polymers can also be obtained by polymerizing 'the monomers in the presence of a stereospecific catalyst comprising (A) a solid component comprising a Ti compound and an electron-donor compound supported on MgCl 2 ; (B) an alkylaluminum compound and, optionally, (C) an external electron-donor compound.
• a process of this type is disclosed in
• the present invention relates to a process for polymerizing
• M is an atom of a transition metal selected from those belonging to group 3, 4, or to the lanthanide or actinide groups in the Periodic Table of the Elements (new IUPAC version); preferably M is zirconium titanium or hafnium;
• X is a hydrogen atom, a halogen atom, a R, OR, OR'O, OSO 2 CF 3 , OCOR, SR, NR 2 or PR 2 group wherein R is a linear or branched, saturated or unsaturated C]-C 2 o-alkyl, C 3 -C 2 o-cycloalkyl, C 6 -C 2 o-aryl, C 7 -C 2 o-alkylaryl or C -C 2 o-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R' is a C ⁇ -C 2 o-alkylidene, C 6 -C 2 o-arylidene, C -C 2 o-alkylarylidene, or C 7 -C 2 o-arylalkylidene radical; preferably X is a hydrogen atom, a halogen atom, a OR
• R 1 is a hydrogen atom or a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl
• R 2 with R 3 , and R 4 with R 5 form a 5 or 6 membered unsaturated rings, preferably said rings are aromatic, optionally said rings contain heteroatoms belonging to groups 13 -16 of the Periodic Table of the Elements, and optionally said rings bear alkyl substituents, preferably said alkyl substituents are Cj-Cio-alkyl radicals;
• R is a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl, C -C 2 o-cycloalkyl, C ⁇ - o-aryl, C 7 -C o-alkylaryl, or C 7 -C o-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the
• Elements; p equal to or different from each other, are hydrogen atoms or a linear or branched, saturated or unsaturated
• T 2 is a hydrogen atom or a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl
• T 1 and T 2 can also join to form a saturated or unsaturated, condensed 5 or 6 membered ring optionally containing heteroatoms belonging to groups 13-16 of the
• said ring cam be substituted, preferably the substituents are C]-C 2 o alkyl groups optionally containing heteroatoms belonging to groups 13-16 of the Periodic Table of the Elements; to form for example a condensed benzene ring; a condensed thiophene ring; a condensed pyrrole ring; L is a divalent bridging group selected from the group consisting of CR 7 2 , SiR 7 2 , (CR 7 2 ) 2 and (SiR 7 2 ) 2 radicals, wherein R 7 , equal to or different from each other, are hydrogen atoms or a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl, C 3 -C2o-cycloalkyl, C 6 -C 2 o-aryl, C 7 -C 2 o-alkylaryl, or C -C2o-arylalkyl radical, optionally containing heteroatoms belonging to
• Non hmiting examples of rings formed by R 2 and R 3 or R 4 and R 5 are condensed benzene rings; condensed thiophene rings; and condensed pyrrole rings;
• Preferred metallocene compounds of formula (I) belongs to the following three classes (1),
• Metallocene compounds belonging to class (1) have the following formula (IT)
• R 13 is a hydrogen atom or a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl, C 3 -C 2 o-cycloalkyl, C 6 -C 2 o-aryl, C 7 -C 2 o-alkylaryl, or C 7 -C 2 o-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; preferably R 13 is a linear or branched C 1 -C 20 alkyl radical; more preferably R 13 is a methyl or an ethyl radical;
• R 9 , R 10 , R 11 and R 12 are hydrogen atoms or linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl, C 3 -C 2 o-cycloalkyl, C 6 -C 20 -aryl, C 7 -C 2 o-alkylaryl, or C 7 -C 2 o-arylalkyl radicals, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; R 9 , R 10 , R 11 and R 12 can also form one or more 5 or 6 membered saturated or unsaturated rings optionally containing heteroatoms belonging to groups 13-16 of the Periodic Table of the Elements, said rings can bear alkyl substituents; preferably R 9 is selected from the group consisting of C 1 -C 2 o alkyl and C 6 -C2o aryl radicals, even more preferably R 9 is a methyl, tertbutyl, isopropyl, phenyl, al
• T 3 and T 4 are moieties of formula (Ila) or (lib):
• a 1 is a sulphur atom (S), a oxygen atom (O), or a NR, PR, or CR 15 group; wherein R is a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl, C 3 -C 2 o-cycloalkyl, C 6 -C2o-aryl, C 7 -C 2 o-alkylaryl, or C 7 -C 2 o-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; and R 15 is a hydrogen atom or a linear or branched, saturated or unsaturated d-C ⁇ -alkyl, C 3 -C 20 -cycloalkyl, C 6 -C2o-aryl, C 7 -C 2 o-alkylaryl, or C 7 -C 2 o-arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements
• R 14 is a hydrogen atom or a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl
• R 14 is a C ⁇ -C 2 o alkyl radical; more preferably R 14 is a methyl radical; preferably T 3 and T 4 are moieties of formula (Ila); preferred compounds of formula (II) has formula (fie)
• Metallocene compounds belonging to class (2) have the following formula (III)
• T 3 , T 4 , R 13 M, X, p and L have the same meaning as described above;
• T 5 is a moiety of formula (Ilia) or (Illb) wherein: in the moiety of formula (Ilia) A 2 bonds to the cyclopentadienyl group in position 5; in the moiety of formula (Illb) A 3 bonds to the cyclopentadienyl group in position 4;
• a 2 is a sulfur atom (S), an oxygen atom (O), or a CR 15 group; wherein R 15 is defined as above; preferably A 2 is a sulphur atom;
• R 16 is a hydrogen atom or a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl
• R 15 is a Q-C 20 alkyl radical; more preferably R 16 is a methyl radical;
• R 17 is a linear or branched, saturated or unsaturated C 1 -C 2 o-alkyl, C 3 -C 2 o-cycloalkyl,
• R and R can also join to form a 5 or 6 membered aliphatic or aromatic ring; said ring can bear alkyl substituents, preferably said alkyl substituents are d-Cio-al yl radicals; preferably R 17 is a C Cao alkyl or C 6 -C 2 o alkylaryl radical; more preferably R 17 is phenyl radical substituted with one or more 0 ⁇ 0 20 alkyl radical; preferably the substitution is in position 2 or 2 and 4 with respect to the phenyl ring;
• a 3 is a NR group or a CR 15 group wherein R is a linear or branched, saturated or unsaturated
• R 15 is defined as above; preferably A 3 is a NR group; more preferably A 3 is a
• T is a moiety of formula (I-Ia) and T and T 4 are moieties of formula (Ila) to form a compound of formula (IIIc)
• R 18 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are hydrogen atoms or a linear or branched, saturated or unsaturated C ⁇ -C 2 o-alkyl, C 3 -C 20 -cycloalkyl, C 6 -C 2 o-aryl, C 7 -C 2 o-alkylaryl, or C 7 -C 2 o- arylalkyl radical, optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two or more adjacent R 23 , R 24 , R 25 , R 26 , R 27 , and R 28 can form one or more aliphatic or aromatic C 4 -C 8 rings that can bear alkyl substituents, preferably said alkyl substituents are Ci-do-alkyl radicals; R 19 , R 20 and R 21 are hydrogen atoms or a linear or branched, saturated or unsaturated d-do-alkyl
• R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are hydrogen atoms;
• R 18 is a hydrogen atom or a d-C 2 o alkyl radical;
• R 19 , R 20 , R 21 are a C ⁇ -C 20 alkyl radical; more preferably they are methyl groups.
• Metallocene compounds of formula (I) are well known in the art. In particular compounds of class (1) and (2) have been described in WO 01/47939; compounds belonging to class (3) have been described in EP 537 130.
• Alumoxanes used as component B) can be obtained by reacting water with an organo- aluminium compound of formula HJA1U 3 .J or H j AbU ⁇ - j , where U substituents, same or different, are hydrogen atoms, halogen atoms, d-do-alkyl, d-do-cyclalkyl, d-do-aryl, C 7 -C 2 o- alkylaryl or or C7-C20-arylalkyl radical, optionally containing silicon or germanium atoms with the proviso that at least one U is different from halogen, andj ranges from 0 to 1, being also a non-integer number.
• the molar ratio of Al/water is preferably comprised between
• the molar ratio between aluminium and the metal of the metallocene generally is comprised between about 10:1 and about 20000:1, and more preferably between about 100:1 and about
• 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:
• n 1 is 0 or an integer from 1 to 40 and the substituents U are defined as above, or alumoxanes of the formula: u
• n 2 can be used in the case of cyclic compounds, wherein n 2 is an integer from 2 to 40 and the U 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 WO 99/21899 and WO01/21674 are: tris(2,3,3-trimethyl-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-mefhyl-3-ethyl-pentyl)aluminium, 1ris(2-methyl-3-ethyl-hexyl)alumimum, 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)a
• TMA trimethylaluminium
• TIBAL triisobutylaluminium
• TIOA tris(2,4,4-trimethyl-pentyl)aluminium
• TDMBA tris(2,3-dimethylbutyl)aluminium
• TTMBA tris(2,3 5 3-trimethylbutyl)aluminium
• Non-limiting examples of compounds able to form an alkylmetallocene cation 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 4 (") , 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.
• Non limiting examples of compounds of formula D E " are:
• Triethylarnmoniumtetra(phenyl)borate Tributylarnmoniumtetra(phenyl)borate
• Organic aluminum compounds used as compound C) are those of formula HjAlU 3 -j or described above.
• the catalysts of the present invention can also be supported on an inert- carrier. This is achieved by depositing the metallocene compound A) or the product of the reaction thereof with the component B), or the component B) and then the metallocene compound A) on an inert support such as, for example, silica, alumina, Al-Si, Al-Mg mixed oxides, magnesium halides, styrene/divinylbenzene copolymers, polyethylene or polypropylene.
• an inert support such as, for example, silica, alumina, Al-Si, Al-Mg mixed oxides, magnesium halides, styrene/divinylbenzene copolymers, polyethylene or polypropylene.
• the supportation process is carried out in an inert solvent such as hydrocarbon for example toluene, hexane, pentane or propane and at a temperature ranging from 0°C to 100°C, , preferably the process is carried out at a temperature ranging from 25°C to 90°C or the process is carried out at room temperature.
• an inert solvent such as hydrocarbon for example toluene, hexane, pentane or propane
• a suitable class of supports which can be used is that constituted by porous organic supports functionalized with groups having active hydrogen atoms. Particularly suitable are those in which the organic support is a partially crosslinked styrene polymer. Supports of this type are described in European application EP-633272.
• inert supports particularly suitable for use according to the invention is that of polyolefin porous prepolymers, particularly polyethylene.
• a further suitable class of inert supports for use according to the invention is that of porous magnesium halides such as those described in International application WO 95/32995.
• the solid compound thus obtained, in combination with the further addition of the alkylaluminium compound either as such or prereacted with water if necessary, can be usefully employed in the gas-phase polymerization.
• Another object of the present invention is a 1-butene homopolymer obtainable with the process of the present invention in particular when compounds of class 1 or 2 are used, having the following characteristics:
• the 1-butene homopolymer of the present invention does not have 4,1 insertions (regioerrors) detectable with a 400 MHz spectrometer operating at 100.61 MHz.
• thel-butene homopolymer of the present invention has is ⁇ tactic pentads (mnrmm) > 90% more preferably > 93%.
• the 1-butene homopolymer of the present invention does not have extractable content in boiling diethylether.
• mmmm is the value of the isotactic pentads and rr is the value of the Sindiotactic triads calculated with 400 MHz spectrometer operating at 100.61 MHz.
• the 1-butene homopolymers of the present invention are endowed with a flexural modulus value (ASTM D-790) comprised between 150 and 300 Mpa.
• ASTM D-790 flexural modulus value
• This value of the modulus in conjunction with the relatively high melting point render the 1-butene homopolymers of the present invention useful for advantageously replacing the 1-butene copolymers that at equivalent melting point show a lower flexural modulus.
• the polymerization process of the present invention can be carried out in liquid phase, optionally in the presence of an inert hydrocarbon solvent, or in gas phase.
• Said hydrocarbon solvent can be either aromatic (such as toluene) or aliphatic (such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane).
• aromatic such as toluene
• aliphatic such as propane, hexane, heptane, isobutane, cyclohexane and 2,2,4-trimethylpentane.
• the polymerization temperature preferably ranges from 0°C to 250°C; preferably comprised between 20°C and 150°C and, more particularly between 40°C and 90°C;
• the polymers of the present invention are endowed with a narrow molecular weight distribution.
• the molecular weight distribution is represented by the ratio M w /M n which, for the polymers of the present invention, when the metallocene used is a pure isomer, is generally lower than 4, preferably lower than 3.5 and, more preferably, lower than 3.
• the molecular weight distribution can be varied by using mixtures of different metallocene compounds or by carrying out the polymerization in several stages which differ as to the polymerization temperature and/or the concentrations of the molecular weight regulators and/or the monomers concentration. Moreover by carrying out the polymerization process by using a combination of two different metallocene compounds of formula (I) a polymer endowed with a broad melting is produced.
• the polymerization yield depends on the purity of the transition metal organometallic catalyst compound (A) in the catalyst, therefore, said compound can be used as such or can be subjected to purification treatments before use.
• the intrinsic viscosity (IN.) was measured in tetrahydronaphtalene (TH ⁇ ) at 135°C.
• the melting points of the polymers (T m ) were measured by Differential Scanning Calorimetry
• the peak temperature was taken as crystallization temperature (T c ).
• T c crystallization temperature
• the sample was heated for the second time at 200°C with a scanning speed corresponding to 20°C/min. In this second heating run, the peak temperature was taken as the melting temperature (T m ) and the area as global melting enthalpy ( ⁇ Hf).
• the molecular weight distribution was determined on a WATERS 150 C using the following chromato graphic conditions:
• rac dimethylsilylbis(2-methyl-4-phenyl-indenyl) zirconium dichloride (A-5) was prepared according to USP 5,786,432.
• rac dimethylsilylbis(2-methyl-4-5-benzoindenyl) zirconium dichloride (A-6) was prepared according to USP 5,932,669.
• the cocatalyst methylalumoxane (MAO) was a commercial product which was used as received (Witco AG, 10 %wt/vol toluene solution, 1.7 M in Al).
• the cocatalyst methylalumoxane (MAO) was a commercial product which was used as received (Witco AG, 10 %wt/vol toluene solution, 1.7 M in Al).
• the catalyst mixture was prepared by dissolving the desired amount of the metallocene with the proper amount of the
• BHT 2,6- di-t-butyl- 4-methyl phenol

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