| Titanocenen-based catalyst system -> Monitor Keywords |
|
|
  Titanocenen-based catalyst systemUSPTO Application #: 20070179049Title: Titanocenen-based catalyst system Abstract: wherein T is chlorine, bromine, or iodine; R″ is a linear or branched C1-C10 alkyl radical; y ranges from 1.00 to 0.05; and j ranges from 0.01 to 3.00; with at least one metallocene compound having titanium as central metal and at least one ligand having a cyclopentadienyl skeleton. MgT2.yAlQj(OR″)3-j (I) A catalyst system obtainable by the process comprising the steps of contacting an adduct of formula (I) (end of abstract) Agent: Basell Usa Inc. - Elkton, MD, US USPTO Applicaton #: 20070179049 - Class: 502155000 (USPTO) Related Patent Categories: Catalyst, Solid Sorbent, Or Support Therefor: Product Or Process Of Making, Catalyst Or Precursor Therefor, Organic Compound Containing, Organic Compound Including Carbon-metal Bond, Including Phosphorus Or Sulfur Or Compound Containing Nitrogen Or Phosphorus Or Sulfur The Patent Description & Claims data below is from USPTO Patent Application 20070179049. Brief Patent Description - Full Patent Description - Patent Application Claims
[0001] The present invention relates to a solid catalyst system comprising a metallocene containing titanium as central metal (titanocene) and a partially dealcoholated adduct of magnesium dihalide and alcohol. [0002] The use of metallocene compounds and, in particular, titanocene compounds as catalyst components for the polymerization of olefins is well known in the art. They are usually used in conjunction with alumoxanes as cocatalysts. The catalyst systems comprising titanocene compounds and alumoxanes can be used supported on an inert support in order to control the morphology of the obtained polymer and to avoid fouling in the reactor, especially in a gas-phase or slurry polymerization processes. [0003] The drawback of the catalyst systems so obtained is that since alumoxanes need to be used in large excess with respect to titanocene compounds the resulting catalyst is very expensive. Therefore it is desirable to reduce or eliminate the use of alumoxanes. [0004] Magnesium chloride is a well-known support for Ziegler-Natta based catalyst systems containing titanium halide. The use of this compound as a carrier for single-site catalysts could be very advantageous, in view of its chemical and structural simplicity, and to the possibility to finely control the porosity of this support and, therefore, to easily tune the porosity of the final catalyst system. [0005] Several catalyst systems trying to solve the problem of the use of alumoxanes in a magnesium halide supported catalyst system have been proposed in the art. [0006] For example in Macromol. Chem. Phys. 195, 1369-1379 (1984) MgCl.sub.2 in combination with a zirconocene catalyst and trialkylaluminum is used. More recently, In Macromolecules 1993, 26, 4712 mixtures of MgR.sub.2 and AlR.sub.2Cl (generating MgCl.sub.2 and AlR.sub.3) as cocatalyst components for olefin polymerization using various metallocenes have been used. In various papers, namely, Korean J. Chem. Eng. 16(5) 562-570, Journal of Applied Polymer science Vol 70, 1707-1715, Korean J. Chem. Eng. 19(4) 557-563 and J. Molec. Catal A 191, 2003, 155-165 Lee and co-workers, proposed a metallocene-based catalyst system in which alcohol and anhydrous MgCl.sub.2 are reacted to form an adduct MgCl.sub.2-alcohol. The adduct, further reacted with trialkylaluminum, is used for supporting zirconocene compounds. The obtained catalyst system can be used without a further addition of alumoxanes. [0007] In all these documents only metallocene compounds in which the central metal is zirconium have been used, moreover the adduct MgCl.sub.2 alcohol used is not dealcoholated and it is not characterized by particular values of porosity and surface area. As shown in the comparative tests of the present application the use of a dealcoholated adduct of magnesium halide and alcohol improves the activity of the titanium-based catalyst system. [0008] U.S. Pat. No. 5,698,487 relates to a magnesium halide having a surface area (BET) greater than 50 m.sup.2/g, porosity (BET) greater than 0.15 cm.sup.3/g and porosity (Hg) greater than 0.3 cm.sup.3/g. The adduct MgCl.sub.2-alcohol having these features has been used in combination with trialkylaluminum or alumoxane for supporting metallocene compounds. In all the working examples the metallocene compound is combined with trialkylaluminum or alumoxane before contact with the above support. As shown in the comparative test of the present application when the titanocene is not prereacted with trialkylaluminum the polymerization activity of the resulting catalyst system is improved. [0009] The object of the present invention is a catalyst system obtainable by the process comprising the following steps: [0010] a) contacting [0011] (i) a partially dealcoholated adduct of formula MgT.sub.2.wR'OH wherein T is chlorine, bromine, or iodine, preferably chlorine; R' is a linear or branched C.sub.1-C.sub.10 alkyl radical, preferably R' is a linear C.sub.1-C.sub.10 alkyl radical; more preferably R' is a methyl or an ethyl radical; w ranges from 3 to 0.1, preferably from 3 to 0.5; more preferably from 3 to 1 being also a non integer number; with [0012] (ii) an organo-aluminium compound of formula H.sub.eAlU.sub.3-e or H.sub.eAl.sub.2U.sub.6-e, wherein each U substituent, same or different, is a hydrogen atom, a halogen atom, or a hydrocarbon radical containing from 1 to 20 carbon atoms optionally containing silicon or germanium atoms; with the proviso that at least one U is different from halogen, and e ranges from 0 to 1, being also a non-integer number; preferably said hydrocarbon radicals are linear or branched, cyclic or acyclic, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-alkylaryl or C.sub.7-C.sub.20-arylalkyl radicals optionally containing silicon or germanium atoms; preferably U is a linear or branched C.sub.1-C.sub.20-alkyl radical; more preferably U is an ethyl, a n-propyl, a iso propyl, a n-butyl, a iso-butyl, a tert-butyl, a hexyl or an octyl radical; [0013] to obtain an adduct of formula (I) MgT.sub.2.yAlQ.sub.j(OR'').sub.3-j (I) [0014] wherein [0015] y ranges from 1.00 to 0.05; [0016] Q has the same meaning of U hydrogen and halogen atoms being excluded; [0017] R'' has been described above [0018] and j ranges from 0.01 to 3.00, being also a non-integer number. [0019] b) contacting the product obtained from step a) with at least one metallocene compound having titanium as central metal and at least one ligand having a cyclopentadienyl skeleton; with the proviso that the metallocene compound of step b) is not previously treated with an organo-aluminium compound of formula H.sub.eAlU.sub.3-e or H.sub.eAl.sub.2U.sub.6-e, or with an alumoxane. [0020] In step a) the product obtained by combining the partially dealcoholated adduct of formula MgT.sub.2.wR'OH and organo-aluminium compound of formula H.sub.eAlU.sub.3-e or H.sub.eAl.sub.2U.sub.6-e, (ii) is an adduct of formula (I) MgT.sub.2.yAlQ.sub.j(OR'').sub.3-j (I) preferably in the compound of formula (I) y ranges from 0.50 to 0.10; more preferably it ranges from 0.40 to 0.10; [0021] j preferably ranges from 2.50 to 2.00; more preferably it ranges from 2.50 to 2.20. [0022] Preferably said adduct of formula (I) has a surface area (BET) higher than 30 m.sup.2/g; more preferably higher than 38 m.sup.2/g; even more preferably higher than 200 m.sup.2/g; but it can reach values higher than 300 m.sup.2/g. [0023] A preferred class of metallocene compounds to be used in step b) belongs to the following formulas (II), (III), (IV) or (V) wherein [0024] Ti is titanium; [0025] the substituents X, equal to or different from each other, are monoanionic sigma ligands selected from the group consisting of hydrogen, halogen, R.sup.6, OR.sup.6, OCOR.sup.6, SR.sup.6, NR.sup.6.sub.2 and PR.sup.6.sub.2, wherein R.sup.6 is a hydrocarbon radical containing from 1 to 20 carbon atoms optionally containing one or more Si or Ge atoms; preferably R.sup.6 is a linear or branched, cyclic or acyclic, C.sub.1l-C.sub.20-alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-alkylaryl or C.sub.7-C.sub.20-arylalkyl optionally containing one or more Si or Ge atoms; [0026] the substituents X are preferably the same and are preferably halogen, R.sup.6, OR.sup.6 and NR.sub.6.sup.2; [0027] wherein R.sup.6 is preferably a C.sub.1-C.sub.7 alkyl, C.sub.6-C.sub.14 aryl or C.sub.7-C.sub.14 arylalkyl group, optionally containing one or more Si or Ge atoms; more preferably, the substituents X are selected from the group consisting of --Cl, --Br, --Me, --Et, -n-Bu, -sec-Bu, --Ph, --Bz, --CH.sub.2SiMe.sub.3, --OEt, --OPr, --OBu, --OBz and --NMe.sub.2; more preferably X is Cl or Me. [0028] p is an integer ranging from 1 to 2; [0029] L is a divalent bridging group selected from C.sub.1-C.sub.20 alkylidene, C.sub.3-C.sub.20 cycloalkylidene, C.sub.6-C.sub.20 arylidene, C.sub.7-C.sub.20 alkylarylidene, or C.sub.7-C.sub.20 arylalkylidene radicals optionally containing heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements, and silylidene radical containing up to 5 silicon atoms such as SiMe.sub.2, SiPh.sub.2; preferably L is a divalent group (ZR.sup.7.sub.m).sub.n; Z being C, Si, Ge, N or P, and the R.sup.7 groups, equal to or different from each other, being hydrogen or hydrocarbon groups containing from 1 to 20 carbon atoms, or two R.sup.7 can form a aliphatic or aromatic C.sub.4-C.sub.7 ring; preferably R.sup.7 is hydrogen or a linear or branched, cyclic or acyclic, C.sub.1-C.sub.20-alkyl, C.sub.2-C.sub.20 alkenyl, C.sub.2-C.sub.20 alkynyl, C.sub.6-C.sub.20-aryl, C.sub.7-C.sub.20-alkylaryl or C.sub.7-C.sub.20-arylalkyl radical; [0030] more preferably L is selected from Si(CH.sub.3).sub.2, SiPh.sub.2, SiPhMe, SiMe(SiMe.sub.3), CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3 or C(CH.sub.3).sub.2; [0031] m is 1 or 2, and more specifically it is 1 when Z is N or P, and it is 2 when Z is C, Si or Ge; [0032] n is an integer ranging from 1 to 4; preferably it is 1 or 2; [0033] each R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5, equal to or different from each other, is a hydrogen atom, a C.sub.1-C.sub.40 hydrocarbon group optionally containing one or more heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two adjacent R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 form one or more 3-7 membered ring optional containing heteroatoms belonging to groups 13-17 of the periodic table; such as to form with the cyclopentadienyl moiety the following radicals: indenyl; mono-, di-, tri- and tetra-methyl indenyl; 2-methyl indenyl, 3-.sup.tbutyl-indenyl, 2-isopropyli-4-phenyl indenyl, 2-methyl-4-phenyl indenyl, 2-methyl-4,5 benzo indenyl; 3-trimethylsilyl-indenyl; 4,5,6,7-tetrahydroindenyl; fluorenyl; 5,10-dihydroindeno[1,2-b]indol-10-yl; N-methyl- or N-phenyl-5,10-dihydroindeno [1,2-b]indol-10-yl; 5,6-dihydroindeno[2,1-b]indol-6-yl; N-methyl-or N-phenyl-5,6-dihydroindeno[2,1-b]indol-6-yl; azapentalene4-yl; thiapentalene-4-yl; azapentalene-6-yl; thiapentalene-6-yl; mono-, di- and tri-methylazapentalene4-yl, 2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene; [0034] preferably each R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 is a hydrogen atom or a linear or branched, cyclic or acyclic, C.sub.1-C.sub.40-alkyl, C.sub.2-C.sub.40 alkenyl, C.sub.2-C.sub.40 alkynyl, C.sub.6-C.sub.40-aryl, C.sub.7-C.sub.40-alkylaryl or C.sub.7-C.sub.40-arylalkyl radical, optionally containing one or more heteroatoms belonging to groups 13-17 of the Periodic Table of the Elements; or two adjacent R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 form one or more 3-7 membered ring optional containing heteroatoms belonging to groups 13-17 of the periodic table; Continue reading... Full patent description for Titanocenen-based catalyst system Brief Patent Description - Full Patent Description - Patent Application Claims Click on the above for other options relating to this Titanocenen-based catalyst system patent application. ###  How KEYWORD MONITOR works... a FREE service from FreshPatents1. Sign up (takes 30 seconds). 2. Fill in the keywords to be monitored. 3. Each week you receive an email with patent applications related to your keywords. Start now! - Receive info on patent apps like Titanocenen-based catalyst system or other areas of interest. ### Previous Patent Application: Ziegler-natta catalyst for olefin polymerization including aryloxy group and method for polymerization of olefin using same Next Patent Application: Methods of making carbide and oxycarbide containing catalysts Industry Class: Catalyst, solid sorbent, or support therefor: product or process of making ### FreshPatents.com Support Thank you for viewing the Titanocenen-based catalyst system patent info. IP-related news and info Results in 1.98113 seconds Other interesting Feshpatents.com categories: Medical: Surgery , Surgery(2) , Surgery(3) , Drug , Drug(2) , Prosthesis , Dentistry |
||
