TWI460193B - Vinyl terminated higher olefin polymers and methods to produce thereof - Google Patents

Description

Polymer of higher olefin terminated by vinyl and manufacturing method thereof [Priority of claim]

This application claims the benefit and priority of US Pat. No. 13/072,288, filed on March 25, 2011, and EP 1116703, filed on March 23, 2011. This application is also part of the continuation application of USSN 13/072,288 filed on March 25, 2011.

This invention relates to the polymerization of olefins, and more particularly to the manufacture of polymers of higher olefins terminated with vinyl groups.

Alpha-olefins, especially those containing from about 6 to about 20 carbon atoms, have been used as intermediates in the manufacture of detergents or other types of commercially available products. These alpha-olefins are also used as comonomers, especially in linear low density polyethylene. Alpha-olefins produced on the market are typically prepared by oligomerizing ethylene. Long chain alpha-olefins, such as vinyl terminated polyethylene, are also known and can be used as building blocks after functionalization or as macromonomers.

Alkyd-terminated low molecular weight solids and liquids of ethylene or propylene have also been produced, which are typically used as branches in polymerization. See, for example, Rulhoff, Sascha and Kaminsky ("Synthesis and Characterization of Defined Branched Poly (propylene)s with Different Microstructures by Copolymerization of Propylene and Linear Ethylene Oligomers (C _n = 26-28) with Metallocenes / MAO Catalysts," Macromolecules, 16, 2006, pp. 1450-1460) and Kaneyoshi, Hiromu et al. ("Synthesis of Block and Graft Copolymers with Linear Polyethylene Segments by Combination of Degenerative Transfer Coordination Polymerization and Atom Transfer Radical Polymerization," Macromolecules, 38, 2005, pp. 5425- 5435).

Further, U.S. Patent No. 4,814,540 discloses bis(pentamethylcyclopentadienyl)phosphonium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride and bis(tetramethyl-n-butylcyclohexane). Pentadienyl) ruthenium dichloride and methylaluminoxane in toluene or hexane with or without hydrogen to obtain a propylene having a low degree of polymerization of 2-10 with an allyl vinyl group Oligomer. The oligomers do not have a high Mn and do not have at least 93% allylic vinyl unsaturation. Likewise, these oligomers lack comonomers and are produced with low productivity, with a large excess of aluminoxane (Al/M of Mobi ≧600; M=Zr, Hf). Further, in all the examples, not less than 60% by weight of the solvent (based on solvent + propylene) was present.

Teuben et al. (J. Mol. Catal., 62, 1990, pp. 277-287) reveals [Cp ^* ₂ MMe(THT)] + [BPh ₄ ] (M = Zr and Hf; Cp ^* = pentamethyl ring) The use of pentadienyl; Me = methyl, Ph = phenyl; THT = tetrahydrothiophene to produce propylene oligomers. In the case of M=Zr, a broad product distribution of up to _C24 oligomers (number average molecular weight (Mn) of 336) is obtained at room temperature. In the case of M = Hf, only the dimer 4-methyl-1-pentene and the terpolymer 4,6-dimethyl-1-heptene were formed. The dominant terminal mechanism seems to shift the beta-methyl group from the growth chain back to the metal center, as evidenced by the 氘-labeled research institute.

X. Yang et al. (Angew. Chem. Intl Ed. Engl., 31, 1992, pp. 1375) discloses amorphous low molecular weight polypropylenes prepared at low temperatures in which the reaction exhibits low activity and the product has 90% of alkene. Propyl vinyl (as measured by ¹ H NMR, relative to all unsaturation). Subsequently, Resconi et al. (J. Am. Chem. Soc., 114, 1992, pp. 1025-1032) discloses the use of bis(pentamethylcyclopentadienyl)zirconium and bis(pentamethylcyclopentadienyl). The ruthenium is polymerized, and the obtained β-methyl terminal results in an oligomer having a ruthenium which is mainly terminated by an allyl group and an isobutyl group, and a low molecular weight polymer. As exemplified in U.S. Patent No. 4,814,540, the oligomer produced does not have at least 93% of allyl chain ends, from about 500 to about 20,000 grams per mole of Mn (as measured by ¹ H NMR), And the catalyst has low productivity (1-12, 620 grams / millimoles of metallocene / hour; > 3000 wppm of Al in the product).

Similarly, Small and Brookhart (Macromolecules, 32, 1999, pp. 2322) disclose the use of pyridylbisguanamine iron catalysts to produce low molecular weight amorphous propylene materials in low temperature polymerization by eliminating chain termination of beta-hydrides and A large number of vinyl ends, which apparently have an advantage or exclusive 2,1 chain growth.

Weng et al. (Macromol Rapid Comm. 2000, 21, 1103-1107) discloses the use of dimethyl decyl bis(2-methyl, 4-phenyl-indenyl) zirconium dichloride and methyl aluminum in toluene. The oxane produces a material having up to about 81% vinyl termination at about 120 °C. The material has a Mn of about 12,300 (as measured by ¹ H NMR) and a melting point of about 143 °C.

Macromolecules, 33, 2000, 8541-8548 discloses the preparation of branched-block ethylene-butene polymers by reincorporation of vinyl-terminated polyethylene, which is a branched-block polymer It is prepared by combining Cp ₂ ZrCL ₂ with (C ₅ Me ₄ SiMe ₂ NC ₁₂ H ₂₃ )TiCl ₂ activated with methylaluminoxane.

Moscardi et al. (Organometallics, 20, 2001, pp. 1918) discloses the use of rac-dimethylnonalkylmethylenebis(3-tert-butylfluorenyl)zirconium dichloride in batch polymerization of propylene. Methylaluminoxane is used to make materials in which the 〝 allyl end group always outperforms any other end group 〞 on any [propylene]. In these reactions, morphological control is limited and about 60% of the chain ends are allyl groups.

Coates et al. (Macromolecules, 38, 2005, pp. 6259) discloses the use of modified methyl aluminoxane (MMAO) activated bis(phenoxyimine) titanium dichloride ((PHI) ₂ TiCl ₂ ) (Mo/A ratio of Al/Ti = 200) A low molecular weight para-oriented polypropylene having an allyl end group of about 100% was prepared over 4 hours at a batch polymerization operation between 20 and +20 °C. [rrrr]=0.46-0.93). The propylene used in the polymerization was dissolved in toluene to give a 1.65 M solution in toluene. Catalyst productivity is very low (0.95 to 1.14 grams / millimeter Ti / hour).

JP 2005-336092 A2 discloses the production of a vinyl-terminated propylene polymer using a material such as microcrystalline kaolinite, triethylaluminum, triisopropylaluminum treated with H ₂ SO ₄ , wherein liquid propylene is fed to In the catalyst slurry in toluene. This method produces substantial macromonomers in the same row that do not have a large amount of amorphous material.

Rose et al. (Macromolecules, 41, 2008, pp. 559-567) discloses poly(ethylene-co-propylene) macromonomers that do not have a large amount of isobutyl chain ends. These macro-systems are bis(phenoxyimine) titanium dichloride ((PHI) ₂ TiCl ₂ ) activated by modified methyl aluminoxane (MMAO) (Al/Ti from 150 to 292) Ear ratio range) was prepared in a semi-batch polymerization (30 psi), propylene was added to toluene at 0 ° C for 30 minutes, followed by an ethylene gas flow at 32 psi overpressure and about 0 ° C at 2.3 to 4 The polymerization time of the hour was used to produce an EP copolymer having a Mn of about 4,800 to 23,300. In the four described copolymerization reactions, the end of the propylene-based chain decreases as the incorporation of ethylene increases, which is roughly according to the following formula: % of allyl chain ends (relative to total unsaturation) = -0.95 (Mo The combined ethylene in the ear is +100.

For example, 65% of allyl groups (compared to total unsaturation) are described as EP copolymers containing 29 mole percent ethylene. This is the highest total amount of allyl groups achieved. As for 64 mole % of the incorporated ethylene, only 42% of the unsaturated is allyl. The productivity of these polymerizations is in the range of from 0.78 x 10 ² g/mole Ti/hr to 4.62 x 10 ² g/m ² Ti/hr.

Prior to this study, Zhu et al. reported a geometry-limited metallocene catalyst [C ₅ Me ₄ (SiMe ₂ N-t-butyl) TiMe ₂ activated with B(C ₆ F ₅ ) ₃ and MMAO. Only low (~38%) ethylene-terminated ethylene-propylene copolymers (Macromolecules, 35, 2002, pp. 10062-10070 and Macromolecules Rap. Commun., 24, 2003, pp. 311-315) were obtained.

Janiak and Blank summarize various studies related to the oligomerization of olefins (Macromol. Symp., 236, 2006, pp. 14-22).

However, a higher olefin-based polymerization reaction is used to produce vinyl The polymers of the higher olefins of the terminal are still unknown. Accordingly, there is a need for a new catalyst for the manufacture of polymers of vinyl-terminated higher olefins, particularly high yields, broad molecular weights and high catalyst activity. Furthermore, there is a need for polymers having a large number of vinyl-terminated higher olefins present in the allyl terminal, at mass production temperatures and at mass production speeds (5,000 g/mole/hr or Higher productivity) achieves control over a wide range of molecular weights. Furthermore, there is a need for polymers having a vinyl terminated higher olefin that can be functionalized and used in addition applications, or as macromonomers for poly(macrocell) synthesis.

The present invention relates to a polymer having at least 200 gram/mol of Mn (measured by ¹ H NMR) of a vinyl-terminated higher olefin comprising one or more C ₄ to C ₄₀ higher olefin derived units The polymer in which the vinyl-terminated higher olefin is substantially free of propylene-derived units; and wherein the higher olefin polymer has at least 5% allylic chain ends (relative to total unsaturation). Polymers of higher olefins terminated with a vinyl group may optionally contain ethylene derived units. The polymer of the higher olefin terminated with a vinyl group preferably does not contain an isobutyl chain end. The isobutyl chain ends are determined according to the procedure set forth in WO 2009/155471.

The invention also relates to a process for the manufacture of polymers of vinyl-terminated higher olefins, wherein the process comprises contacting under polymerization conditions: one or more C ₄ to C ₄₀ higher olefins (where substantially no propylene is present) Wherein the contact system occurs in the presence of a catalyst system comprising an activator and at least one metallocene compound represented by one of the following formulae: (i) Or (ii) Or (iii) Or (iv) Wherein M is ruthenium or zirconium; each X system is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, guanamines, alkoxides, sulfides, phosphides, halogens, Alkene, amine, phosphine, ether, and combinations thereof (two X may form part of a fused ring or ring system); each Q system is independently a carbon or a hetero atom; each R ¹ is independently a C ₁ to C ₈ alkyl group, R ¹ may be the same or different from R ^2; each R ² is independently a C ₁ system to C ₈ alkyl; each R ³ is independently hydrogen or a system substituted by from 1 to 8 carbon atoms or unsubstituted hydrocarbon group of, However, it is a prerequisite that at least 3 R ³ groups are not hydrogen; each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; R ⁵ is hydrogen or C ₁ to C ₈ alkyl; R ⁶ is hydrogen or C ₁ to C ₈ alkyl; each R ⁷ is independently hydrogen or C ₁ to C ₈ alkyl, but the prerequisite is that at least 7 R ⁷ groups are not hydrogen; ₂ ^a T is a bridging group, wherein T is a Group 14 element (preferably C, Si or Ge, preferably Si); and each R ^a is independently hydrogen, halogen or a C ₁ to C ₂₀ hydrocarbon group; and two R ^a may form a cyclic structure including aromatic, partially saturated or And a cyclic or fused ring system; and an additional prerequisite is that any two adjacent R groups may form a fused ring or a multi-center fused ring system (wherein the rings may be aromatic, partially saturated or saturated) Ring); or (v) Wherein M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halides, a diene, an amine, a phosphine, an ether, and combinations thereof (two X may form part of a fused ring or ring system); each R ⁸ is independently a C ₁ to C ₁₀ alkyl group; each R ⁹ system independently is C ₁ to C ₁₀ alkyl; each R ¹⁰ is hydrogen; each R ¹¹ , R ¹² and R ¹³ are independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; T is a bridging group (such as R ₂ ^a T described above); and a further prerequisite that any adjacent R ¹¹ , R ¹² and R ¹³ groups may form a fused ring or a polycentric fused ring system, wherein the ring may be aromatic, Partially saturated or saturated ring; or (vi) Wherein M is ruthenium or zirconium; each X system is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, guanamines, alkoxides, sulfides, phosphides, halogens, a olefin, an amine, a phosphine, an ether or a combination thereof; each of R ¹⁵ and R ¹⁷ is independently a C ₁ to C ₈ alkyl group; and each of R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ And R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen or a substituted or unsubstituted hydrocarbon group having from 1 to 8 carbon atoms.

Detailed description

The inventors have surprisingly discovered novel vinyl terminated polymers. The present invention describes a polymer which does not substantially contain a propylene-derived unit of a vinyl-terminated higher olefin, a process for producing a polymer of such a vinyl-terminated higher olefin, and a vinyl-terminated higher olefin The composition of the polymer. Polymers of such vinyl-terminated higher olefins can be found as synthetic poly(macromonomers), macromonomers of block copolymers, and as additives (for example, as additives to lubricants). The vinyl groups of such vinyl terminated polymers are useful to provide a functionalized route. The functionalized polymers can also be used as additives, such as in lubricants.

As used herein, the molecular weight 〞 means the number average molecular weight (Mn) unless otherwise stated.

For the purposes of the present invention and the scope of its patent application, a new numbering scheme of the periodic table as in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985) is used. Therefore, the Group 4 metal lanthanum is an element of Group 4 of the periodic table.

〝 〞 〞 activity is the measured value of how many grams of polymer (P) is produced by the polymerization catalyst containing W gram catalyst (cat) over a period of T hours; and can be expressed by the following formula: P / (TxW) and It is expressed in units of gram P gram cat ^{- 1} hour ^-1 .

The hydrazine oxime (or decene hydrocarbon oxime) is a linear, branched or cyclic compound having at least one double bond of carbon and hydrogen. For the purposes of this specification and the accompanying patent claims, when the polymer or copolymer comprises an olefin (including but not limited to ethylene, propylene, and butene), then the polymer or copolymer The olefin present is a polymeric form of the olefin. For example, when the copolymer is said to have a cerium ethylene content of from 35% by weight to 55% by weight, it is understood that the monomer unit in the copolymer is derived from the polymerization of ethylene, and the derived unit It is present in an amount of from 35% by weight to 55% by weight based on the weight of the copolymer. The ruthenium polymer oxime has two or more identical or different monomer units. The term fluorene polymer hydrazine as used herein includes oligos (up to 100 monomer units) and larger polymers (greater than 100 monomer units). The 〝 homopolymer oxime is a polymer having the same monomer unit. The ruthenium copolymer 〞 is a polymer having two or more monomer units different from each other. The terpene terpolymer is a polymer having three monomer units different from each other. The oxime used to describe the monomer unit is different, indicating that the monomer units differ from each other by at least one atom or have a difference in isomerism. Accordingly, the definition of a copolymer as used herein includes trimers and analogs.

As used herein, higher olefin oxime means a C ₄ to C ₄₀ olefin; preferably a C ₄ to C ₃₀ α-olefin; more preferably a C ₄ to C ₂₀ α-olefin; or even more preferably C ₄ to C ₁₂ α-olefin. The copolymer of fluorene higher olefin is a polymer comprising two or more different monomer units, at least one of which is a higher olefin. In a preferred embodiment, all of the monomer units in the polymer are derived from higher olefins.

Mn as used herein is a number average molecular weight (measured by ¹ H NMR unless otherwise stated), Mw is the weight average molecular weight (measured by gel permeation chromatography GPC), and Mz is the z average molecular weight ( As measured by GPC), wt% is a percentage by weight, mol% is a percentage by mole, vol% is a volume percent, and mol is mol. The molecular weight distribution (MWD) is defined as Mw (measured by GPC) divided by Mn (measured by GPC): Mw/Mn. All molecular weights (eg, Mw, Mn, Mz) have units of grams per mole unless otherwise noted.

In JWO Lesik, "Inductively Coupled Plasma-Optical Emission Spectroscopy," in the Encyclopedia of Materials Characterization, CR Brundle, CA Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp. ICPES (inductively coupled plasma emission spectroscopy) as described in 633-644 is used to determine the amount of elements in a material.

Vinyl terminated polymer

The preferred vinyl-terminated higher olefin polymer (VT-HO) of the present invention has a Mn of at least 200 grams per mole (preferably from 200 to 100,000 grams per mole, preferably from 200 to 75,000 grams per liter/ Mohr, preferably from 200 to 60,000 g/mole, preferably from 300 to 60,000 g/mole, or preferably from 750 to 30,000 g/mole (measured by ¹ H NMR), the polymer comprises One or more (preferably two or more, three or more, four or more, and similar amounts) C ₄ to C ₄₀ (preferably C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C) ₄ to C ₁₂ , preferably butene, pentene, hexene, heptene, octene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentane Alkene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxapentene, 7-oxa decadiene, substituted derivatives thereof and their derivatives a higher olefin-derived unit wherein the vinyl-terminated higher olefin polymer does not substantially comprise propylene-derived units (preferably less than 0.1% by weight propylene, preferably 0% by weight); The polymer of the higher olefin has at least 5 % (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%) of allyl Base chain ends (relative to total unsaturation); and optionally have a ratio of allyl chain end to vinylidene chain ends of 1:1 or greater (preferably greater than 2:1, greater than 2.5:1, greater than 3) :1, greater than 5:1, or greater than 10:1), and even more random and preferably substantially free of isobutyl chain ends (preferably less than 0.1% by weight of isobutyl chain ends). In some embodiments, the vinyl-terminated higher olefin polymer may comprise ethylene derived units, preferably at least 5 mole percent ethylene (preferably at least 15 mole percent ethylene, preferably It is at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol%. Ethylene, or preferably at least 90 mole percent ethylene. In other embodiments, the vinyl terminated high olefin polymer of the present invention comprises less than 90 mole percent ethylene derived units (preferably less than 5 mole percent ethylene, preferably less) Ethylene at 15 mol%, preferably less than 25 mol% ethylene, preferably less than 35 mol% ethylene, preferably less than 45 mol% ethylene, preferably less than 60 Mole% of ethylene, preferably less than 75 mol% of ethylene). In some embodiments of the invention, the polymer of the higher olefin terminated with a vinyl group does not substantially comprise ethylene derived units (preferably less than 0.1% by weight of propylene, preferably 0% by weight).

The preferred vinyl-terminated higher olefin polymer (VT-HO) of the present invention has at least 200 grams per mole (preferably from 200 to 100,000 grams per mole, preferably from 200 to 75,000 grams per mole). Preferably, it is from 200 to 60,000 g/mole, preferably from 300 to 60,000 g/mole, or preferably from 750 to 30,000 g/mole, of Mn (measured by ¹ H NMR) and comprises at least 5 mo Ear % (preferably at least 10 mole %, at least 15 mole %, at least 20 mole %, at least 30 mole %, at least 40 mole %, at least 50 mole %, at least 60 mole %, at least 70%) One or more of mol%, at least 80 mol%, at least 90 mol%, or at least 95 mol%) (preferably two or more, three or more, four or more, and the like) C ₄ to C ₄₀ (preferably C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C ₄ to C ₁₂ , preferably butene, pentene, hexene, heptene, octene, decene, Terpene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7- Oxene decene, 7-oxa decadiene, substituted derivatives thereof and isomers thereof a unit wherein the polymer of a higher olefin terminated by a vinyl group substantially does not comprise a propylene-derived unit (preferably less than 0.1% by weight of propylene, preferably 0% by weight); and a polymer of a medium to higher olefin thereof Having at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%) Allyl chain ends (relative to total unsaturation); and optionally have a ratio of allyl chain end to vinylidene chain ends of 1:1 or greater (preferably greater than 2:1, greater than 2.5:1) , greater than 3:1, greater than 5:1, or greater than 10:1); and even more random and preferably substantially free of isobutyl chain ends (preferably less than 0.1% by weight of isobutyl chain ends). In some embodiments, the vinyl-terminated higher olefin polymer may comprise ethylene derived units, preferably at least 5 mole percent ethylene (preferably at least 15 mole percent ethylene, preferably It is at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol%. Ethylene, or preferably at least 90 mole percent ethylene. In other embodiments, the vinyl terminated high olefin polymer of the present invention comprises less than 90 mole percent ethylene derived units (preferably less than 5 mole percent ethylene, preferably less) Ethylene at 15 mol%, preferably less than 25 mol% ethylene, preferably less than 35 mol% ethylene, preferably less than 45 mol% ethylene, preferably less than 60 Mole% of ethylene, preferably less than 75 mol% of ethylene). In some embodiments of the invention, the polymer of the higher olefin terminated with a vinyl group does not substantially comprise ethylene derived units (preferably less than 0.1% by weight propylene, preferably 0% by weight).

The preferred vinyl-terminated higher olefin polymer (VT-HO) of the present invention has at least 200 grams per mole (preferably from 200 to 100,000 grams per mole, preferably from 200 to 75,000 grams per mole). Preferably, it is from 200 to 60,000 g/mole, preferably from 300 to 60,000 g/mole, or preferably from 750 to 30,000 g/mole, of Mn (measured by ¹ H NMR) and comprises at least 5 mo Ear% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70%) One or more of mole %, at least 80 mole %, at least 90 mole %, or at least 95 mole % or 100 mole %) (preferably two or more, three or more, four or more) And similar amounts) C ₄ to C ₄₀ (preferably C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C ₄ to C ₁₂ , preferably butene, pentene, hexene, heptene, octane Alkene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, ring ten Diene, 7-oxa decene, 7-oxa decadiene, substituted derivatives thereof and isomers thereof) a higher olefin-derived unit wherein the polymer of a vinyl-terminated higher olefin does not substantially comprise propylene-derived units (preferably less than 0.1% by weight propylene, preferably 0% by weight); The polymer has at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95) %) allyl chain end (relative to total unsaturation); and optionally has a ratio of allyl chain end to vinylidene chain end of 1:1 or greater (preferably greater than 2:1, greater than 2.5) :1, greater than 3:1, greater than 5:1, or greater than 10:1); and even more random and preferably substantially free of isobutyl chain ends (preferably less than 0.1% by weight of isobutyl chain ends). In some embodiments of the invention, the vinyl-terminated higher olefin polymer may comprise ethylene derived units, preferably at least 5 mole percent ethylene (preferably at least 15 mole percent ethylene) Preferably, it is at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75. Mole% of ethylene, or preferably at least 90 mol% of ethylene). In other embodiments of the invention, the vinyl terminated high olefin polymer of the present invention comprises less than 90 mole percent ethylene derived units (preferably less than 5 mole percent ethylene, preferably Preferably less than 15 mole % ethylene, preferably less than 25 mole % ethylene, preferably less than 35 mole % ethylene, preferably less than 45 mole % ethylene, preferably less At 60 mole % ethylene, preferably less than 75 mole % ethylene). In some embodiments of the invention, the polymer of the higher olefin terminated with a vinyl group does not substantially comprise ethylene derived units (preferably less than 0.1% by weight of propylene, preferably 0% by weight). In a particularly preferred embodiment of the invention, the C ₄ to C ₄₀ higher olefin derived unit is selected from the group consisting essentially of or selected from the group consisting of C ₅ to C ₃₀ olefins, preferably C ₆ to C ₃₀ olefin, preferably C ₆ to C ₂₀ olefin, preferably C ₈ to C ₁₆ olefin, preferably C ₈ to C ₁₂ olefin, preferably butene, pentene, hexene, heptene, octane Alkene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, ring ten One, two, three, four, five, six or more of a diene, a 7-oxa decene, a 7-oxa decadiene, a substituted derivative thereof, and a isomer thereof. In a particularly preferred embodiment of the invention, VT-HO is a homopolymer (such as homopentene, homopolyhexene, homo-octene, homopolydecene, homopolydodecene) or substantially C _a copolymer of ₅ to C ₄₀ olefins, such as a copolymer of hexene and octene, or a copolymer of octene and decene, or a copolymer of octene, decene and dodecene. In a preferred embodiment of the invention, the VT-HO comprises at least 5 mol% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 30 mol%, at least 40 mo Ear %, at least 50 mole %, at least 60 mole %, at least 70 mole %, at least 80 mole %, at least 90 mole %, or at least 95 mole %) of C ₅ to C ₄₀ olefins (such as pent The balance is ene, hexene, octene or decene, and the balance is complemented by different C ₅ to C ₄₀ olefins.

The VT-HO polymer can be a homopolymer, a copolymer, a trimer or the like.

VT-HO polymers typically have a saturated chain terminus (or terminus) and/or an unsaturated chain terminus or terminal. The unsaturated chain end of the VT-HO polymer of the present invention comprises a decallyl chain terminal oxime. The allyl chain end is represented by CH ₂ CH-CH ₂ - as shown in the following formula: Wherein M represents a polymer chain. The decyl propyl vinyl fluorene, the decyl propyl end 〞, the 〝 vinyl chain end 〞, the 〝 vinyl terminal 〞, the 〝 allyl vinyl fluorene and the fluorene are terminated by a vinyl group. The instructions can be used interchangeably.

In some embodiments, the VT-HO polymer has at least 5% allylic chain ends (preferably at least 10% allylic chain ends, at least 15% allylic chain ends, at least 20% olefinic) Propyl chain terminus, at least 30% of allyl chain terminus, at least 40% of allyl chain terminus, at least 50% of allyl chain terminus, at least 60% of allyl chain terminus, at least 70% of alkene The propyl chain terminus, at least 80% of the allyl chain terminus, at least 90% of the allyl chain terminus, or at least 95% of the allyl chain terminus) (relative to total unsaturation). The number of allyl chain ends, vinylidene chain ends, vinyl chain ends and other unsaturated chain ends is determined by ¹ H NMR on a 250 NMR spectrometer at 120 ° C using deuterated tetrachloroethylene. The alkane was used as a solvent; and in the selected examples, it was confirmed by ¹³ C NMR. Resconi has reported proton and carbon partitioning of vinyl-terminated oligomers (pure full deuterated tetrachloroethane for protons) in J. American Chemical Soc., 114, 1992, pp. 1025-1032, useful herein. The spectra were used in a carbon spectrum with a 50:50 positive and full deuterated tetrachloroethane mixture; all spectra were recorded on a Bruker spectrometer at 500 °C for protons and 125 MHz for carbon operation at 100 °C). The allyl chain terminus is described as the percentage of moles of total moles of unsaturated groups (i.e., the sum of allyl chain ends, vinylidene chain ends, extended vinyl chain ends, and the like).

The ratio of decyl group end to vinylidene chain end 〞 is defined as the ratio of the percentage of the ends of the allyl chain to the percentage of the ends of the vinylidene chain. In some embodiments, the ratio of allyl chain end to vinylidene chain ends is 1:1 or greater (preferably greater than 2:1, greater than 2.5:1, greater than 3:1, greater than 4:1, greater than 5:1, greater than 7:1, greater than 9:1, or greater than 10:1). In some embodiments, the ratio of allyl chain end to vinylidene chain ends is in the range of from about 10:1 to about 1:1 (preferably from about 5:1 to about 2:1, preferably from 10:1 to about 2.5:1, or preferably from 10:1 to about 3.5:1).

The ratio of the decyl group end to the vinyl end group is defined as the ratio of the percentage of the end of the allyl chain to the percentage of the end of the vinyl chain. In some embodiments, the ratio of terminal ends of the allyl chain to the extended vinyl chain is greater than 1:1 (preferably greater than 2:1, or greater than 5:1).

VT-HO polymers typically also have saturated chain ends. In the ethylene-free polymerization, the end of the saturated chain is the end of the higher olefin chain, as shown in the following formula: Wherein M represents a polymer chain and n is an integer selected from 4 to 40. In the copolymerization of ethylene/higher olefins, the polymer chain can initiate the growth of ethylene monomer to produce a saturated chain end which is the ethyl chain end. The VT-HO polymer does not substantially comprise propylene (preferably less than 0.1% by weight, preferably 0% by weight), and thus does not substantially have an isobutyl chain end (preferably less than 0.1% by weight, Good is 0% by weight). The isobutyl chain ends were determined according to the procedure set forth in WO 2009/155471.

The VT-HO polymer may additionally comprise ethylene derived units. In some embodiments, the VT-HO polymers comprise at least 5 mole percent ethylene (preferably at least 15 mole percent ethylene, preferably at least 25 mole percent ethylene, preferably at least 35 moles) Ethylene, preferably at least 45 mole percent ethylene, preferably at least 60 mole percent ethylene, preferably at least 75 mole percent ethylene, or preferably at least 90 mole percent ethylene. . In other embodiments, the VT-HO polymer comprises from about 1.0 to about 99 mole percent ethylene (from about 10 to about 90 mole percent, from about 15 to about 95 mole percent, from about 20 to about 85 mole %, from about 25 to about 75 mole percent, or from about 30 to about 70 mole percent).

In a particular embodiment, the VT-HO copolymer has a Mn of greater than 300 grams per mole (preferably from about 300 to about 60,000 grams per mole, from 400 to 50,000 grams per mole, preferably from 500 to 35,000). Gm/mole, preferably 300 to 15,000 g/mole, preferably 400 to 12,000 g/mole, or preferably 750 to 10,000 g/mole, Mw of 1000 or more (compared Preferably, it is from about 1,000 to about 60,400,000 g/mole, preferably from about 2,000 to 50,300,000 g/mole, preferably from about 3,000 to 35,200,000 g/mole, and from about 1,700 to about 150,000. Gm/mole, or preferably from about 800 to 100,000 g/m Mz. Further, the desired molecular weight range can be any combination of any of the above molecular weight upper limits and any lower molecular weight limits. Mn ( ¹ H NMR) was determined according to the NMR method described in the Examples section below. Mn can also be measured using the GPC-DRI method as described below. For the purpose of patent application, Mn was measured by ¹ H NMR.

Mn, Mw, and Mz can be measured using a gel permeation chromatography (GPC) method using a high temperature size exclusion chromatography (SEC, supplied by Waters Corporation or Polymer) equipped with a differential refractive index detector (DRI). Laboratories). Experimental details are described in: T. Sun, P. Brant, RRChance, and WW Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and incorporated herein by reference. Three Polymer Laboratories PLgel 10mm Mixed-B columns were used. The nominal flow rate is 0.5 cubic centimeters per minute and the nominal injection volume is 300 microliters. Various transfer lines, columns, and differential refractors (DRI detectors) were included in an oven maintained at 135 °C. The solvent for the SEC experiment was prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7 micron glass pre-filter followed by a 0.1 micron Teflon filter. The TCB is then degassed with an on-line degasser before entering the SEC. The polymer solution was prepared by placing the anhydrous polymer in a glass vessel, adding the desired amount of TCB, and then heating the mixture at 160 ° C with continuous stirring for about 2 hours. All amounts are measured by weight. The TCB density (in mass/volume unit) used to indicate the polymer concentration was 1.463 g/ml at room temperature and 1.324 g/ml at 135 °C. Injection concentrations ranged from 1.0 to 2.0 mg/ml for lower molecular weight samples at lower concentrations. Rinse the DRI detector and syringe before running each sample. The flow rate in the device was then increased to 0.5 ml/min and the DRI was allowed to stabilize for 8 to 9 hours prior to injection of the first sample. The concentration of each point in the chromatogram is calculated by subtracting the DRI signal (I _DRI ) of the reference line using the following formula: c = K _DRI I _DRI / (dn / dc) where K _DRI is determined by correcting the DRI The constant, and (dn/dc) is the refractive index increment of the system. The refractive index of TCB at 135 ° C is n = 1.500 and λ = 690 nm. For the purposes of the present invention and the scope of the patent application, the propylene polymer has (dn/dc) = 0.104 and the others are 0.1. The units of the parameters used throughout the description of the SEC method are: concentration in grams per cubic centimeter, molecular weight in grams per mole, and intrinsic viscosity in grams per gram.

In a preferred embodiment, the VT-HO polymer comprises less than 3% by weight, based on the weight of the copolymer, of a functional group selected from the group consisting of hydroxides, aryls and substituted aryls, halogens. Alkoxy, carboxylic acid ester, ester, acrylate, oxygen, nitrogen and carboxyl groups, preferably less than 2% by weight, more preferably less than 1% by weight, still more preferably less than 0.5% by weight, more preferably Less than 0.1% by weight, more preferably 0% by weight.

In another embodiment, the VT-HO polymer comprises at least 36 carbon atoms, based on the weight of the copolymer composition, of at least 60 carbon atoms, preferably at least 75% by weight, preferably at least 90% by weight. (Measured by ¹ H NMR, assuming one unsaturated per chain) of olefins (preferably at least 51 carbon atoms, preferably at least 102 carbon atoms).

In another embodiment, the VT-HO polymer comprises less than 20% by weight, based on the weight of the copolymer composition, of dimers and trimers (preferably less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight, as measured by gas chromatography (GC). The product was analyzed at 38 cm/sec in a GC (Agilent 6890N with autoinjector) using helium as a carrier gas. A 60-meter-long column (J & W Scientific DB-1, 60 meters x 0.25 mm inner diameter x 1.0 micron film thickness) assembled with a flame free detector (FID), 250 ° C syringe temperature And the detector temperature of 250 °C. The sample was injected into a column in an oven at 70 ° C, followed by heating to 275 ° C over 22 minutes (rise rate 10 ° C / min to 100 ° C, 30 ° C / min to 275 ° C, maintained). The amount of dimer or trimer obtained is derived using an internal standard (usually a monomer). The yield of dimer and trimer products is from The data recorded on the spectrometer is calculated. The amount of dimer or trimer product is calculated from the area under the relevant peak on the GC curve (relative to the internal standard).

In another embodiment, the VT-HO polymer contains less than 25 ppm cerium or zirconium, preferably less than 10 ppm cerium or zirconium, based on the polymer produced and the mass of catalyst used. Preferably less than 5 ppm bismuth or zirconium. ICPES as described in JWO Lesik "Inductively Coupled Plasma-Optical Emission Spectroscopy," in the Encyclopedia of Materials Characterization, Brundle et al., Editors, Butterworth-Heinemann, Boston, Mass., 1992, pp. 633-644. Inductively coupled plasma emission spectroscopy) measures the atomic weight in a material.

In still other embodiments, the VT-HO polymer is a liquid at 25 °C. In another embodiment, the VT-HO polymer described herein has a viscosity of greater than 1000 cP, greater than 12,000 cP, or greater than 100,000 cP at 60 °C. In other embodiments, the vinyl terminated polymer has a viscosity of less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP. Viscosity was measured using a Brookfield Digital Viscometer.

In another particular embodiment, VT-HO of the polymers described herein preferably has a melting temperature in the range of 60 to 150 deg.] C (T _m, DSC first melt), or 50 to 100 ℃. In another embodiment, the copolymers described herein do not have a melting temperature detectable by DSC after storage for at least 48 hours at ambient temperature (23 ° C). The VT-HO polymer preferably has a glass transition temperature (Tg) of less than 0 ° C or less (as measured by the differential scanning calorimetry method described below), preferably -10 ° C or lower, more preferably - 20 ° C or lower, more preferably -30 ° C or lower, more preferably -50 ° C or lower. Melting temperature (T _m) and a glass transition temperature (Tg) system using differential scanning calorimetry (DSC) and commercially available devices (such as a TA Instruments 2920 DSC) measurement. Typically, 6 to 10 mg of the sample that has been stored at room temperature for at least 48 hours is sealed in an aluminum pan and loaded in an instrument at room temperature. The sample was equilibrated at 25 ° C and then cooled to -80 ° C at a cooling rate of 10 ° C / min. The sample was held at -80 ° C for 5 minutes and then heated to 25 ° C at a heating rate of 10 ° C / minute. The glass transition temperature is measured from the heating cycle. Alternatively, the sample was equilibrated at 25 ° C and then heated to 150 ° C at a heating rate of 10 ° C / min. Analyze the end-to-end conversion and endothermic melt conversion of the peak temperature, if present. The melting temperature described is the peak melting temperature of the first heating unless otherwise specified. The melting point (or melting temperature) of a multimodal sample is defined as the peak melting temperature from the DSC melting curve (i.e., associated with the largest endothermic thermal response in the temperature range).

In another embodiment, the VT-HO polymer described herein has a viscosity of greater than 1000 cP, greater than 12,000 cP, or greater than 100,000 cP at 60 °C. In other embodiments, the VT-HO polymer has a viscosity of less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP. Viscosity is defined as flow resistance and the melt viscosity of the neat copolymer is measured using a Brookfield Digital Viscometer at elevated temperatures.

In some embodiments, the VT-HO polymer is a hexene/octene copolymer, a hexene/decene copolymer, a hexene/dodecene copolymer, an octene/decene copolymer, an octene/twelve Ene copolymer, terpene/dodecene copolymer, hexene/decene/dodecene trimer, hexene/octene/decene trimer, octene/decene/tweldium Alkene terpolymers and analogs.

In another embodiment, any of the vinyl-terminated polyolefins described or useful herein has a 3-alkylvinyl end group represented by the formula (wherein the alkyl group is a C ₁ to C ₃₈ alkane) Base), also known as 〝3-alkyl chain end 〞 or 〝3-alkyl vinyl terminal 〞: Wherein 〝 ̇ ̇ ̇〞 represents a polyolefin chain and R ^b is a C ₁ to C ₃₈ alkyl group, preferably a C ₁ to C ₂₀ alkyl group such as methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl and the like. The amount of 3-alkyl chain terminus was determined using ¹³ C NMR as set forth below.

In a preferred embodiment, any of the vinyl terminated polyolefins described or useful herein has at least 5% 3-alkyl chain end (preferably at least 10% 3-alkyl chain) Terminal, at least 20% 3-alkyl chain terminus, at least 30% 3-alkyl chain terminus, at least 40% 3-alkyl chain terminus, at least 50% 3-alkyl chain terminus, at least 60% 3-alkyl chain terminus, at least 70% 3-alkyl chain terminus, at least 80% 3-alkyl chain terminus, at least 90% 3-alkyl chain terminus; at least 95% 3-alkyl chain terminus (relative to total unsaturation).

In a preferred embodiment, any of the vinyl terminated polyolefins described or useful herein has at least 5% 3-alkyl+allyl chain ends (for example, all 3-alkyl chain ends plus all allylic chain ends), preferably at least 10% 3-alkyl+allyl chain ends, at least 20% 3-alkyl+ene a propyl chain terminus, at least 30% 3-alkyl+allyl chain terminus, at least 40% 3-alkyl+allyl chain terminus, at least 50% 3-alkyl+allyl chain terminus, At least 60% 3-alkyl+allyl chain terminus, at least 70% 3-alkyl+allyl chain terminus, at least 80% 3-alkyl+allyl chain terminus, at least 90% 3- Alkyl+allyl chain terminus, at least 95% 3-alkyl+allyl chain terminus (relative to total unsaturation).

Use of polymers of higher olefins terminated by vinyl

The vinyl terminated polymer prepared herein can be functionalized by reacting a hetero atom-containing group with the polymer's allyl hydrazine with or without a catalyst. Examples include catalytic hydroquinonelation with or without an activator such as a free radical generator such as a peroxide, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydrogen Amination or maleic acidification.

In some embodiments, vinyl-terminated polymers produced herein are functionalized as described in U.S. Patent No. 6,022,929; A. Toyota, T. Tsutsui, and N. Kashiwa, Polymer Bulletin 48, pp. 213. - 219, 2002; J. Am. Chem. Soc., 1990, 112, pp. 7433-7434; and USSN 12/487,739, filed on Jun. 19, 2009.

Functionalized polymers are useful in petroleum addition and many other applications. Preferred uses include additives for lubricants and/or fuels. Preferred hetero atom-containing groups include amines, aldehydes, alcohols, acids, succinic acid, butenene Diacids and maleic anhydride.

In particular embodiments herein, a vinyl terminated polymer or a functionalized analog thereof disclosed herein is used as an additive. In some embodiments, a vinyl terminated polymer or a functionalized analog thereof disclosed herein is used as an additive to a lubricant. A particular embodiment is directed to a lubricant comprising a vinyl terminated polymer or a functionalized analog thereof as disclosed herein.

In other embodiments, the vinyl terminated polymer disclosed herein can be used as a monomer to prepare a polymer product. Processes useful in the preparation of such polymeric products include coordination polymerization and acid catalyzed polymerization. In some embodiments, the polymer product can be a homopolymer. For example, if a vinyl terminated polymer (A) is used as the monomer, it is possible to form a homopolymer product having the formula (A) _n wherein n is the degree of polymerization.

In other specific examples, the polymer product formed from a mixture of monomers (vinyl-terminated polymers) may be a mixed polymer comprising two or more repeating units that are different from each other. For example, if a vinyl terminated polymer (A) is copolymerized with a different vinyl terminated polymer (B), a mixed polymer having the formula (A) _n (B) _m may be formed. a product, wherein n is the number of mole equivalents of the vinyl terminated polymer (A) present in the mixed polymer product and m is a vinyl terminated polymer present in the mixed polymer product The number of mole equivalents of (B).

In still other embodiments, the polymer product can be formed from a mixture of a vinyl terminated polymer and another olefinic hydrocarbon. For example, if a vinyl terminated polymer (A) is copolymerized with an olefinic hydrocarbon (B), it is possible to form a mixed polymer product having the formula (A) _n (B) _m wherein n is present in The number of mole equivalents of the vinyl terminated polymer in the mixed polymer product and m are the number of molar equivalents of the olefinic hydrocarbon present in the mixed polymer product.

In a particular embodiment herein, the invention relates to a composition comprising a VT-HO polymer having a Mn of at least 200 grams per mole (preferably from 200 to 100,000 grams per mole). Preferably, it is from 200 to 75,000 g/mole, preferably from 200 to 60,000 g/mole, preferably from 300 to 60,000 g/mole, or preferably from 750 to 30,000 g/mole (by ¹ H NMR) Measured), the VT-HO polymer comprises one or more (preferably two or more, three or more, four or more, and the like) C ₄ to C ₄₀ (preferably C ₄ to C) ₃₀ , C ₄ to C ₂₀ , or C ₄ to C ₁₂ , preferably butene, pentene, hexene, heptene, octene, decene, decene, undecene, dodecene, norbornene , norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxa decene, 7-oxa decadiene a substituted olefin derivative-derived unit thereof, wherein the polymer of a vinyl-terminated higher olefin substantially does not comprise a propylene-derived unit (preferably less than 0.1% by weight of propylene) Or preferably 0% by weight of propylene) And polymers of the intermediate olefins thereof have at least 5% (at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90) %, or at least 95%) of the allyl chain ends; and optionally have a ratio of allyl chain end to vinylidene chain ends of 1:1 or greater (preferably greater than 2:1, greater than 2.5:1) , greater than 3:1, greater than 5:1, or greater than 10:1), and even more random and preferably substantially free of isobutyl chain ends (preferably less than 0.1% by weight of isobutyl chain ends). In some embodiments, the vinyl-terminated higher olefin polymer may comprise ethylene derived units, preferably at least 5 mole percent ethylene (preferably at least 15 mole percent ethylene, at least 25) Mole% ethylene, at least 35 mole% ethylene, at least 45 mole% ethylene, at least 60 mole% ethylene, at least 75 mole% ethylene, or at least 90 mole% ethylene).

In some embodiments, the composition is a lubricant blend. In other specific examples, the invention relates to the use of the above composition as a lubricant blend.

Method for producing a copolymer of a higher olefin having a vinyl terminal

The present invention relates to a process for the manufacture of polymers of higher olefins, wherein the process comprises contacting one or more (preferably two or more, three or more, four or more, and similar amounts) C ₄ to C ₄₀ (preferably C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C ₄ to C ₁₂ , preferably butene, pentene, hexene, heptene, octene, decene, decene, eleven Alkene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxapentene a 7-oxahydroxadiene, a substituted derivative thereof and an isomer thereof, wherein substantially no propylene monomer is present (preferably less than 0.1% by weight of propylene, or preferably 0% by weight of propylene); and optionally at least 5 mol% of ethylene (preferably at least 15 mol% of ethylene, preferably at least 25 mol% of ethylene, preferably at least 35 mol% of ethylene) Preferably, at least 45 mole percent ethylene, preferably at least 60 mole percent ethylene, preferably at least 75 mole percent ethylene, or preferably at least 90 mole percent ethylene, wherein the contact system Occurs in the presence of a catalyst system, the touch The vehicle system comprises an activator and at least one metallocene compound represented by one of the following formulas: (i) Or (ii) Or (iii) Or (iv) Wherein M is ruthenium or zirconium; each X system is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, guanamines, alkoxides, sulfides, phosphides, halogens, Alkene, amine, phosphine, ether, and combinations thereof (two X may form part of a fused ring or ring system); each Q system is independently a carbon or a hetero atom; each R ¹ is independently a C ₁ to C ₈ alkyl group, R ¹ may be the same or different from R ^2; each R ² is independently a C ₁ system to C ₈ alkyl; each R ³ is independently hydrogen or a system substituted by from 1 to 8 carbon atoms or unsubstituted hydrocarbon group of, However, it is a prerequisite that at least 3 R ³ groups are not hydrogen; each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; R ⁵ is hydrogen or C ₁ to C ₈ alkyl; R ⁶ is hydrogen or C ₁ to C ₈ alkyl; each R ⁷ is independently hydrogen or C ₁ to C ₈ alkyl, but the prerequisite is that at least 7 R ⁷ groups are not hydrogen; ₂ ^a T is a bridging group, wherein T is a Group 14 element (preferably C, Si or Ge, preferably Si); and each R ^a is independently hydrogen, halogen or a C ₁ to C ₂₀ hydrocarbon group; and two R ^a may form a cyclic structure including aromatic, partially saturated or And a cyclic or fused ring system; and an additional prerequisite is that any two adjacent R groups may form a fused ring or a multi-center fused ring system (wherein the rings may be aromatic, partially saturated or saturated) Ring); or (v) Wherein M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halides, a diene, an amine, a phosphine, an ether, and combinations thereof (two X may form part of a fused ring or ring system); each R ⁸ is independently a C ₁ to C ₁₀ alkyl group; each R ⁹ system independently is C ₁ to C ₁₀ alkyl; each R ¹⁰ is hydrogen; each R ¹¹ , R ¹² and R ¹³ are independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; T is a bridging group (such as R ₂ ^a T above); an additional prerequisite is that any adjacent R ¹¹ , R ¹² and R ¹³ groups may form a fused ring or a polycentric fused ring system (wherein the rings may be aromatic) , partially saturated or saturated ring); or (vi) Wherein M is ruthenium or zirconium; each X system is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, guanamines, alkoxides, sulfides, phosphides, halogens, a olefin, an amine, a phosphine, an ether or a combination thereof; each of R ¹⁵ and R ¹⁷ is independently a C ₁ to C ₈ alkyl group; and each of R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ And R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen or a substituted or unsubstituted hydrocarbon group having from 1 to 8 carbon atoms.

In order to produce a vinyl terminated VT-HO polymer as described herein, higher olefin monomers, such as hexene or octene, are typically polymerized by contacting: one or more (preferably two) Or a plurality, three or more, four or more, and the like) C ₄ to C ₄₀ (preferably C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C ₄ to C ₁₂ , preferably D Alkene, pentene, hexene, heptene, octene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene , cyclooctene, cyclooctadiene, cyclododecene, 7-oxa decene, 7-oxa decadiene, substituted derivatives thereof and isomers thereof; wherein the contact system occurs in The presence of a catalyst system comprising one or more metallocene compounds and one or more activators, as described below. Other additives may also be used if desired, such as one or more scavengers, accelerators, modifiers, reducing agents, oxidizing agents, hydrogen, aluminum alkyl or decane. In a preferred embodiment, little or no scavenger is used in the process for making the VT-HO copolymer. The scavenger is preferably present at 0 mole percent, or the scavenger is less than 100:1, preferably less than 50:1, preferably less than 15:1, preferably less than 10:1. The scavenger metal is present on the transition metal molar ratio.

The monomers of the higher olefins may be linear, branched or cyclic. The cyclic olefin of the higher olefin may be deformed or undeformed, monocyclic or polycyclic, and may optionally include a hetero atom and/or one or more functional groups. Exemplary higher olefin monomers include butene, pentene, hexene, heptene, octene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentane Alkene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxapentene, 7-oxa decadiene, substituted derivatives thereof and their derivatives Structure (preferably hexene, heptene, octene, decene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1- Ethyloxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene and their respective homologs and derivatives, preferably Decalene, norbornene and dicyclopentadiene, as shown below).

In some embodiments in which butene is a co-monomer, the butene source may be a mixed butene stream comprising various isomers of butene. It is expected that the 1-butene monomer is preferentially consumed by the polymerization method. Use of such mixed butene stream to provide economic benefits, such as mixed waste streams often flow refining process (e.g., C ₄ raffinate stream), and thus substantially cheaper than the pure 1-butene.

The method of the invention can be carried out in any manner known in the art. Any suspension polymerization method, bulk homogeneous polymerization method, solution polymerization method, slurry polymerization method or gas phase polymerization method known in the art can be used. These methods can be carried out in batch, semi-batch or continuous mode. These methods and modes are well known in the art. It is preferred to use a homogeneous polymerization method and a slurry polymerization method (a homogeneous polymerization method is defined as a method in which at least 90% by weight of the product is soluble in the reaction medium). The overall homogeneous polymerization process is particularly preferred (the overall polymerization process is defined as a monomer concentration of 70% by volume or more in all of the feeds to the reactor). Alternatively, no solvent or diluent is present or added to the reaction medium (except for a small amount of carrier or other additive used as a catalyst system, or an amount typically found for the monomer; for example, propane in propylene).

Suitable diluents/solvents for the polymerization include non-coordinating inert liquids. Examples include linear and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and acyclic hydrocarbons , such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, such as a discoverer in (Isopar ^TM) on the market; perhalogenated hydrocarbons such as perfluorinated C _4-10 alkyl , chlorobenzene; and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, 1,3,5-trimethylbenzene and xylene. Suitable solvents also include liquid olefins which may be used as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl 1-pentene, 1-octene, 1-decene, and mixtures thereof. In a preferred embodiment, an aliphatic hydrocarbon solvent is used as a solvent, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; Cyclic and aliphatic cyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, and preferably the aromatic is present in the solvent in an amount of less than 1% by weight based on the weight of the solvent, preferably 0.5% by weight, preferably 0% by weight.

In a preferred embodiment, the polymerization feed concentration is 60% by volume or less based on the total volume of the feed stream, preferably 40% by volume or less, or preferably 20% by volume. Or less. The polymerization is preferably carried out in a bulk polymerization process.

〝 Catalyst productivity 量 is the measured value of how many grams of polymer (P) is produced by the polymerization catalyst containing W gram catalyst (cat) over a period of T hours; and can be expressed by the following formula: P / (TxW) and It is expressed in units of gram P gram cat ^{- 1} hour ^-1 . The conversion is the amount of monomer converted to the polymer product and is reported in mole percent and is calculated based on the polymer yield and the amount of monomer fed to the reactor. Catalyst activity is a measure of the activity of the catalyst and is described in terms of the mass of the polymer product (P) produced per mole of cat (cat) used (kg P/mole cat).

In an alternative embodiment, the catalyst activity is at least 50 grams per millimole per hour, preferably 500 grams per millimole per hour or greater, preferably 5000 grams per millimole per hour or more. Large, preferably 50,000 grams per millimeter per hour or more. In an alternative embodiment, the conversion of olefin monomers The rate is at least 10%, preferably 20% or more, preferably 30% or more, preferably 50% or more, based on the polymer yield and the weight of the monomer entering the reaction zone. It is 80% or more.

In some embodiments, the productivity is 4500 g/mm/hr or more, preferably 5000 g/mole/hr or more, preferably 10,000 g/mole/hr or more. It is preferably 50,000 g/mole/hr or more. In other embodiments, the productivity is at least 80,000 grams per millimole per hour, preferably at least 150,000 grams per millimole per hour, preferably at least 200,000 grams per millimole per hour, preferably at least 250,000. The gram per milligram per hour is preferably at least 300,000 grams per milligram per hour.

Preferred polymerizations can be carried out at any temperature and/or pressure suitable to obtain the desired VT-HO polymer. The polymerization can be carried out at any suitable temperature, such as at a temperature ranging from about 0 to 250 ° C, preferably from 15 to 200 ° C, preferably from 23 to 120 ° C; and at any suitable pressure, The preferred pressure may range from about 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, or preferably from 0.5 to 4 MPa.

In a typical polymerization reaction, the reaction is carried out for a period of up to 300 minutes, preferably from about 5 to 250 minutes, or preferably from about 10 to 120 minutes.

In a preferred embodiment, the hydrogen is present in the polymerization reactor at a partial pressure of from 0.001 to 50 psig (0.007 to 345 kPa), preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1. Up to 10 psig (0.7 to 70 kPa). It has been found that hydrogen can be used in the system of the invention to provide increased activity Without significantly impairing the ability of the catalyst to make allyl chain ends. The preferred catalyst activity (calculated in grams per milligram of catalyst per hour) is at least 20% higher, preferably at least 50% higher, and preferably at least 100% higher than the same reaction in the absence of hydrogen.

In a preferred embodiment, the polymerization reaction: 1) is carried out at a temperature of from 0 to 300 ° C (preferably from 25 to 150 ° C, preferably from 40 to 120 ° C, preferably from 45 to 80 ° C); It is carried out at a pressure of from atmospheric pressure to 10 MPa (preferably 0.35 to 10 MPa, preferably from 0.45 to 6 MPa, preferably from 0.5 to 4 MPa); 3) is carried out in an aliphatic hydrocarbon solvent (such as Butane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methyl Cyclohexane, methylcycloheptane, and mixtures thereof; wherein preferably the aromatic is present in the solvent in an amount of less than 1% by weight based on the weight of the solvent, preferably less than 0.5% by weight, preferably 0% by weight. %); 4) wherein the catalyst system used in the polymerization comprises less than 0.5 mol%, preferably 0 mol% of aluminoxane, or aluminoxane is less than 500:1 aluminum pair The transition metal molar ratio is preferably less than 300:1, preferably less than 100:1, preferably less than 1:1; 5) the polymerization reaction takes place in one reaction zone; 6) the catalyst The productivity of the compound is at least 80,000 grams /millim / hour (preferably at least 150,000 grams / millimoles / hour, preferably at least 200,000 grams / millimoles / hour, preferably at least 250,000 grams / millimoles / hour, preferably at least 300,000 g/mole/hr); 7) optionally without the presence of a scavenger (such as a trialkylaluminum compound) (eg, present at 0 mol%, or scavenger with less than 100:1 scavenger) Metal-to-transition metal The ear ratio is preferably less than 50:1, preferably less than 15:1, preferably less than 10:1); and 8) hydrogen is optionally at 0.001 to 50 psig (0.007 to 345 kPa) ( A partial pressure of preferably from 0.01 to 25 psig (0.07 to 172 kPa), more preferably from 0.1 to 10 psig (0.7 to 70 kPa), is present in the polymerization reactor. In a preferred embodiment, the catalyst system used in the polymerization reaction contains no more than one or more catalyst compounds. The ruthenium reaction zone (also known as the ruthenium polymerization zone 为) is a vessel in which polymerization occurs, such as a batch reactor. When multiple reactors configured in series or in parallel are used, each reactor is considered a separate polymerization zone. Regarding the multi-stage polymerization in both the batch reactor and the continuous reactor, each polymerization stage is treated as a separate polymerization zone. In a preferred embodiment, the polymerization reaction takes place in a reaction zone. Room temperature is 23 ° C unless otherwise noted.

Catalyst system

In a specific example herein, the present invention is directed to a method of making a polymer of a higher olefin, wherein the method comprises contacting a monomer of a higher olefin in the presence of a catalyst system, the catalyst system comprising an activator and at least one of the following The metallocene compound shown.

In the description herein, a metallocene catalyst can be illustrated as a catalyst precursor, a precatalyst compound, or a transition metal compound, and the terms are used interchangeably. The polymeric catalyst system is a catalyst system that polymerizes monomers into polymers. The ruthenium catalyst system is a combination of at least one catalyst compound, at least one activator, a random co-activator, and a random carrier material. 〝 anion ligand 〞 is a negatively charged ligand that is administered one or more electron pairs to gold Is a genus. The 〝 neutral donor ligand 〞 is a neutrally charged ligand that imparts one or more electron pairs to the metal ion.

For the purposes of the present invention and the scope of its patent application, when the catalyst system is described as comprising a component in a neutral stable form, the general skill of the art will appreciate that the ionic component is reacted with the monomer to produce The form of the polymer.

A metallocene catalyst is defined as having at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more often having two π-bonded cyclopentadienyl groups Partial or substituted part of the organometallic compound. This includes other π-bonded moieties such as fluorenyl or fluorenyl or derivatives thereof.

The metallocenes, activators, random co-activators and random carrier components of the catalyst system are discussed below.

(a) a metallocene component

The term "substituted" means that the hydrogen group has been replaced with a hydrocarbon group, a hetero atom or a hetero atom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group, ethanol is an ethyl group substituted with an -OH group, and a hydrocarbyl group substituted with a hydrazine is a group composed of carbon and hydrogen. Wherein at least one hydrogen is replaced with a hetero atom.

For purposes of the present invention and the scope of the patent application, the "alkoxide" include those wherein alkyl is a C ₁ to C ₁₀ hydrocarbyl persons. The alkyl group may be straight chain, branched or cyclic. The alkyl group can be saturated or unsaturated. In some embodiments, the alkyl group can comprise at least one aromatic group.

The metallocene component of the catalyst system is represented by at least one of Formulas I, II, III, IV, V or VI.

(i) Formulas I, II, III and IV

In some embodiments, the metallocene compound is represented by at least one of Formulas I, II, III, and IV.

Or (ii) Or (iii) Or (iv) Wherein M is ruthenium or zirconium; each X system is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, guanamines, alkoxides, sulfides, phosphides, halogens, An alkene, an amine, a phosphine, an ether or a combination thereof; preferably a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a benzyl group, a chloride, a bromide or an iodide (or two X forms a condensed form) a part of the ring or ring system; each Q system is independently carbon or a hetero atom, preferably C, N, P, S (preferably at least one Q is a hetero atom, or at least 2 Q are the same or different impurities) Atom, or at least 3 Q are the same or different heteroatoms, or at least 4 Q are the same or different heteroatoms; each R ¹ is independently hydrogen or C ₁ to C ₈ alkyl, preferably C ₁ to C ₈ linear alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, ^{R. 1} may be the same or different from R ^2; each R ² independently based Hydrogen or a C ₁ to C ₈ alkyl group, preferably a C ₁ to C ₈ linear alkyl group, preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group, The condition is at least one of R ¹ or R ² Is not hydrogen, preferably both of R ² and R ¹ is neither hydrogen, preferably R ¹ and / or R ² are not branched; each R ³ is independently hydrogen or a system having from 1 to 8 carbon The substituted or unsubstituted hydrocarbon group of the atom (preferably 1 to 6 carbon atoms) is preferably a substituted or unsubstituted C ₁ to C ₈ linear alkyl group, preferably a methyl group or an ethyl group. , propyl, butyl, pentyl, hexyl, heptyl, octyl, but with the proviso that at least 3 R ³ groups are not hydrogen (or 4 R ³ groups are not hydrogen, or 5 R ³ groups) The group is not hydrogen; each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group, preferably having from 1 to 20 carbon atoms (preferably 1 to The substituted or unsubstituted hydrocarbon group of 8 carbon atoms is preferably a substituted or unsubstituted C ₁ to C ₈ linear alkyl group, preferably a methyl group, an ethyl group, a propyl group or a butyl group. Pentyl, hexyl, heptyl, octyl, substituted phenyl (such as propylphenyl), phenyl, decyl, substituted decyl (such as CH ₂ SiR', where R' is C ₁ to C ₁₂ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl); R ⁵ is hydrogen or C _{1 C. 8-alkyl,} preferably a C ₁ to _{C. 8} straight chain alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl group; R ⁶ is hydrogen or C ₁ to C ₈ alkyl, preferably C ₁ to C ₈ linear alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl; each R ⁷ system Independently hydrogen or C ₁ to C ₈ alkyl, preferably C ₁ to C ₈ linear alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl , but the prerequisite is that at least 7 R ⁷ groups are not hydrogen, or at least 8 R ⁷ groups are not hydrogen, or all of the R ⁷ groups are not hydrogen (preferably on each Cp ring of formula IV) The R ⁷ group at the 3 and 4 positions is not hydrogen); R ₂ ^a T is a bridging group, and T preferably comprises C, Si or Ge, preferably Si; each R ^a is independently hydrogen, Halogen or a C ₁ to C ₂₀ hydrocarbyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, substituted phenyl, and two R ^a can form a cyclic structure, including aromatic, partially saturated or saturated cyclic or fused ring systems; and additional prerequisites are any two Adjacent R groups can form fused or polycentric fused ring systems (wherein the rings can be aromatic, partially saturated or saturated).

In an alternative embodiment, at least one R ⁴ group is not hydrogen, or at least 2 R ⁴ groups are not hydrogen, or at least 3 R ⁴ groups are not hydrogen, or at least 4 R ⁴ groups The group is not hydrogen, or all of the R ⁴ groups are not hydrogen.

In some embodiments, the bridging group T includes a bridging group containing at least one Group 13 to Group 16 atom, often referred to as a divalent moiety, such as, but not limited to, carbon, oxygen, nitrogen, helium, At least one of aluminum, boron, antimony and tin atoms or a combination thereof. Preferably, the bridging group T contains a carbon, ruthenium or osmium atom, and most preferably T contains at least one ruthenium atom or at least one carbon atom. The bridging group T may also contain a substituent R* as defined below, including halogen and iron.

Non-limiting examples of substituents R* include one or more groups selected from the group consisting of hydrogen or a straight or branched alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a decyl group, an aryl group, Alkoxy, aryloxy, alkylthio, dialkylamino, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, alkyl- or dialkyl-aminecarbamyl, decyloxy, A mercaptoamine group, an arylamine group or a combination thereof. In a preferred embodiment, the substituent R* has up to 50 non-hydrogen atoms, preferably from 1 to 30 carbons, which may also be substituted by halogen or a hetero atom or the like. Non-limiting examples of alkyl substituents R* include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl and the like, including all Constructs such as tert-butyl, isopropyl and the like. Other hydrocarbon groups include fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl; and organometallic groups substituted with hydrocarbyl groups, including trimethyldecyl, trimethyl a decyl group, a methyldiethyl decyl group, and the like; and an organometallic group substituted with a halocarbon group, including gin(trifluoromethyl)decyl, methyl-bis(difluoromethyl)decane a bromomethyl dimethyl decyl group and the like; and a disubstituted boron group, including, for example, dimethyl boron; and a disubstituted phosphino group, including dimethylamine , dimethylphosphine, diphenylamine, methylphenylphosphine; chalcogen group, including methoxy, ethoxy, propoxy, phenoxy, methyl sulfide and ethyl sulfide . Non-hydrogen substituents R* include atomic carbon, germanium, boron, aluminum, nitrogen, phosphorus, oxygen, tin, sulfur, antimony and the like, including olefins such as, but not limited to, olefinically unsaturated substituents, including vinyl Terminal ligands such as but-3-enyl, prop-2-enyl, hex-5-alkenyl and the like. Also in some embodiments, at least two R* groups (preferably two adjacent R groups) are joined to form from 3 to 30 selected from the group consisting of carbon, nitrogen, oxygen, phosphorus, ruthenium, A ring structure of an atom of ruthenium, aluminum, boron or a combination thereof. In other specific examples, R* may also be a di-group bonded to L at one end and forming a carbon sigma bond to metal M. Particularly preferred R* substituents include a C ₁ to C ₃₀ hydrocarbyl group, a hetero atom or a hetero atom-containing group (preferably methyl, ethyl, propyl (including isopropyl, second propyl), butyl) (including tert-butyl and second butyl), neopentyl, cyclopentyl, hexyl, octyl, decyl, decyl, phenyl, substituted phenyl, benzyl (including substituted benzene) Methyl), cyclohexyl, cyclododecyl, norbornyl and all of their isomers.

Examples of the bridging group R ₂ ^a T or the bridging group T in the formula V in the formula III useful herein may be represented by the following: R' ₂ C, R' ₂ Si, R' ₂ Ge, R' ₂ CCR' ₂ , R' ₂ CCR' ₂ CR' ₂ , R' ₂ CCR' ₂ CR' ₂ CR' ₂ , R'C=CR', R'C=CR'CR' ₂ , R' ₂ CCR'=CR'CR' ₂ , R'C=CR'CR'=CR', R'C=CR'CR' ₂ CR' ₂ , R' ₂ CSiR' ₂ , R' ₂ SiSiR' ₂ , R ₂ CSiR' ₂ CR' ₂ , R' ₂ SiCR' ₂ SiR' ₂ , R'C=CR'SiR' ₂ , R' ₂ CGeR' ₂ , R' ₂ GeGeR' ₂ , R' ₂ CGeR' ₂ CR' ₂ , R ' ₂ GeCR' ₂ GeR' ₂ , R' ₂ SiGeR' ₂ , R'C=CR'GeR' ₂ , R'B, R' ₂ C-BR', R' ₂ C-BR'-CR' ₂ , R' ₂ CO-CR' ₂ , R' ₂ CR' ₂ CO-CR' ₂ CR' ₂ , R' ₂ CO-CR' ₂ CR' ₂ , R' ₂ CO-CR' = CR', R' ₂ CS-CR' ₂ , R' ₂ CR' ₂ CS-CR' ₂ CR' ₂ , R' ₂ CS-CR' ₂ CR' ₂ , R' ₂ CS-CR' = CR', R' ₂ C-Se -CR' ₂ , R' ₂ CR' ₂ C-Se-CR' ₂ CR' ₂ , R' ₂ C-Se-CR ₂ CR' ₂ , R' ₂ C-Se-CR'=CR', R' ₂ CN=CR', R' ₂ C-NR'-CR' ₂ , R' ₂ C-NR'-CR' ₂ CR' ₂ , R' ₂ C-NR'-CR'=CR', R' ₂ CR' ₂ C-NR'-CR' ₂ CR' ₂ , R' ₂ CP=CR' and R' ₂ C-PR'-CR' ₂ , wherein R' is hydrogen or a C ₁ -C ₂₀ -containing hydrocarbon group, Replaced by a hydrocarbyl, halocarbon, substituted halocarbon, decanecarbyl or decanecarbyl substituent, and optionally two or more adjacent R' linkages to form substituted or unsubstituted, saturated a partially unsaturated or aromatic, cyclic or polycyclic substituent. The bridging group preferably comprises carbon or deuterium (such as a dialkylalkylene group), and the bridging group is preferably selected from the group consisting of CH ₂ , CH ₂ CH ₂ , C(CH ₃ ) ₂ , SiMe ₂ , SiPh ₂ , SiMePh, decylcyclobutyl (Si(CH ₂ ) ₃ , (Ph) ₂ C, (p-(Et) ₃ SiPh) ₂ C and decylcyclopentyl (Si(CH ₂ ) ₄ )).

Catalyst compounds that are particularly useful in the present invention include one of the following or Many: (1,3-dimethylmethyl) (pentamethylcyclopentadienyl) indenyldimethyl, (1,3,4,7-tetramethylindenyl) (pentamethylcyclopentyl) Dienyl)phosphonium dimethyl, (1,3-dimethylmethyl) (tetramethylcyclopentadienyl) fluorene dimethyl, (1,3-diethyl fluorenyl) (pentamethyl Cyclopentadienyl) fluorene dimethyl, (1,3-dipropyl decyl) (pentamethylcyclopentadienyl) fluorenyl dimethyl, (1-methyl, 3-propyl fluorenyl) (pentamethylcyclopentadienyl)phosphonium dimethyl, (1,3-dimethylmethyl)(tetramethylpropylcyclopentadienyl)phosphonium dimethyl, (1,2,3- Trimethyldecyl)(pentamethylcyclopentadienyl)phosphonium dimethyl, (1,3-dimethylbenzofluorenyl)(pentamethylcyclopentadienyl)phosphonium dimethyl, 2,7-bis-tert-butylfluorenyl)(pentamethylcyclopentadienyl)phosphonium dimethyl, (9-methylfluorenyl)(pentamethylcyclopentadienyl)phosphonium dimethyl , (2,7,9-trimethyldecyl)(pentamethylcyclopentadienyl)phosphonium dimethyl, indanyl bis(tetramethylcyclopentadienyl)phosphonium dimethyl, two Hydroquinolyl bis(tetramethylcyclopentadienyl) fluorene dimethyl, dimethyl decyl (tetramethylcyclopentadienyl) (3-propyltrimethylcyclopentadienyl) fluorene Methyl; and two Propyl bis silicon alkyl (tetramethyl cyclopentadienyl) hafnium dimethyl.

In an alternative embodiment, the quinone dimethyl hydrazine after the transition metal in the above list of catalyst compounds is replaced with a dihalide (such as a dichloride or difluoride) or a bisoxide, especially for aluminum. Oxylkane activator is used.

(ii) Formula V

In some embodiments, the metallocene can be represented by the following formula V.

Wherein M is cerium or zirconium, preferably cerium; each X is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphorus , halides, dienes, amines, phosphines, ethers, and combinations thereof (two X may form part of a fused ring or ring system); each X is independently selected from halide and preferably a C ₁ to C ₆ hydrocarbon group, Each X is preferably methyl, ethyl, propyl, butyl, phenyl, benzyl, chloride, bromide or iodide; each R ⁸ is independently substituted or unsubstituted C ₁ to C ₁₀ alkyl, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl or an isomer thereof, preferably methyl or n-propyl Or n-butyl, or preferably methyl; each R ⁹ is independently substituted or unsubstituted C ₁ to C ₁₀ alkyl, preferably methyl, ethyl, propyl, butyl, pentyl , hexyl, heptyl, octyl, decyl, decyl or an isomer thereof, preferably methyl, n-propyl or butyl, or preferably n-propyl; each R ¹⁰ is hydrogen; each R ¹¹ , R ¹² and R ¹³ is based independently hydrogen or a substituted or The substituted hydrocarbon group, a heteroatom or heteroatom containing group atoms, preferably each R ^11, R ¹² are hydrogen and R ^13; T is the formula R ₂ ^a J represented bridging group, wherein J is C, Si or Ge, preferably Si; each R ^a is independently hydrogen, halogen or a C ₁ to C ₂₀ hydrocarbon group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Phenyl, benzyl, substituted phenyl, and two R ^a may form a cyclic structure, including aromatic, partially saturated or saturated cyclic or fused ring systems; additional prerequisites are any two adjacent The R group can form a fused ring or a polycentric fused ring system (wherein the rings can be aromatic, partially saturated or saturated). T may also be a bridging group as defined above; and an additional prerequisite is that any adjacent R ¹¹ , R ¹² and R ¹³ groups may form a fused ring or a polycentric fused ring system (wherein It can be aromatic, partially saturated or saturated).

Particularly useful metallocene compounds in the present invention include one or more of the following: rac-dimethyl decyl bis(2-methyl, 3-propylindenyl) fluorenyl dimethyl, rac-dimethyl Base bis(2-methyl, 3-propylindenyl) zirconium dimethyl, rac-dimethyl decyl bis(2-ethyl, 3-propylindenyl) fluorenyl, rac- Dimethyl decyl bis(2-ethyl, 3-propylindenyl) zirconium dimethyl, rac-dimethyl decyl bis(2-methyl, 3-ethylindenyl) fluorenyl, Rac-dimethyl decyl bis(2-methyl, 3-ethyl fluorenyl) zirconium dimethyl, rac-dimethyl decyl bis(2-methyl, 3-isopropyl fluorenyl) fluorene Methyl, rac-dimethyl decyl bis(2-methyl, 3-isopropyl fluorenyl) zirconium dimethyl, rac-dimethyl decyl bis (2-methyl, 3-butyl fluorenyl)铪 dimethyl, rac-dimethyl decyl bis(2-methyl, 3-butyl fluorenyl) zirconium dimethyl, rac-dimethyl decyl bis (2-methyl, 3-propenyl)茚 铪 铪 dimethyl, rac-dimethyl decyl bis (2-methyl, 3-propyl fluorenyl) zirconium dimethyl, rac-dimethyl decyl bis (2-ethyl , 3-propyl indenyl) 铪 dimethyl, rac-dimethyl decyl bis(2-ethyl, 3-propyl fluorenyl) zirconium dimethyl, rac-dimethyl decyl bis ( 2-methyl, 3-ethylindenyl) fluorene dimethyl, rac-dimethyl decyl bis(2-methyl, 3-ethylindenyl) zirconium dimethyl, rac-dimethyl hydrazine Alkyl bis(2-methyl, 3-isopropylindenyl) fluorene dimethyl, rac-dimethyl decyl bis(2-methyl, 3-isopropylindenyl) zirconium dimethyl, Rac-dimethyl decyl bis(2-methyl, 3-butyl fluorenyl) fluorene dimethyl, rac-dimethyl decyl bis (2-methyl, 3-propyl hydrazine) Zirconium dimethyl, rac-dimethyl decyl bis(2-propyl, 3-methylindolyl) fluorene dimethyl, rac-dimethyl decyl bis(2-propyl, 3-ethyl Mercapto) dimethyl, rac-dimethyl decyl bis(2-propyl, 3-butylfluorenyl) fluorene dimethyl, rac-dimethyl decyl bis (2-methyl, 3- Butyl fluorenyl) 铪 dimethyl, rac-dimethyl decyl bis(2,3-dimethylindenyl) fluorene dimethyl, rac-dimethyl decyl bis (2,3-dimethyl茚 铪) 铪 dimethyl, and rac-dimethyl decyl bis(2,3-diethyl fluorenyl) fluorene.

In an alternative embodiment, the quinone dimethyl hydrazine after the transition metal in the above list of catalyst compounds is dihalide (such as dichloride or difluoride) Substrate or bis-oxide replacement, especially for use with alumoxane activators.

In a specific embodiment, the metallocene compound is rac-dimethyl decyl bis(2-methyl, 3-propyl fluorenyl) fluorenyl (VI), rac-dimethyl represented by the following formula: Base bis(2-methyl, 3-propylindenyl) zirconium dimethyl (V-II):

(iii) Formula VI

In some embodiments, the metallocene can be represented by the following formula VI.

Wherein M is ruthenium or zirconium; each X system is independently selected from the group consisting of hydrocarbyl groups having from 1 to 20 carbon atoms, hydrides, guanamines, alkoxides, sulfides, phosphides, halogens, a olefin, an amine, a phosphine, an ether or a combination thereof; each of R ¹⁵ and R ¹⁷ is independently a C ₁ to C ₈ alkyl group; preferably a C ₁ to C ₈ linear alkyl group, preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group, and R ¹⁵ may be the same as or different from R ¹⁷ , and both of them are preferably a methyl group; and each of R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen or have from 1 to 8 carbon atoms (preferably 1 to 6 carbon atoms). The substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted C ₁ to C ₈ linear alkyl group, preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group. , octyl, but the prerequisite is that at least three of R ²⁴ -R ²⁸ are not hydrogen (or four of R ²⁴ -R ²⁸ are not hydrogen, or five of R ²⁴ -R ²⁸ are not hydrogen). All five of R ²⁴ -R ²⁸ are preferably methyl, and/or four of the R ²⁴ -R ²⁸ groups are not hydrogen and at least one of R ²⁴ -R ²⁸ is substituted or not Substituted C ₂ to C ₈ hydrocarbyl groups (at least two, three, four or five of the R ²⁴ -R ²⁸ groups are preferably substituted or unsubstituted C ₂ to C ₈ hydrocarbyl groups).

In one embodiment, R ¹⁵ and R ¹⁷ are methyl, R ¹⁶ is hydrogen, R ¹⁸ -R ²³ are all hydrogen, R ²⁴ -R ²⁸ are all methyl, and each X is methyl. Particularly useful catalyst compounds in the present invention include: (CpMe ₅ )(1,3-Me ₂ benzo[e]indenyl)HfMe ₂ , (CpMe ₅ )(1-methyl-3-n-propylbenzene And [e]decyl)HfMe ₂ , (CpMe ₅ )(1-n-propyl, 3-methylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₅ )(1-methyl-3-n-butyl Benzo[e]fluorenyl)HfMe ₂ ,(CpMe ₅ )(1-n-butyl, 3-methylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₅ )(1-ethyl,3- Methylbenzo[e]fluorenyl)HfMe ₂ ,(CpMe ₅ )(1-methyl,3-ethylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-propyl) (1,3 -Me ₂ benzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-propyl)(1-methyl-3-n-propylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -Polypropylene (1-n-propyl, 3-methylbenzo[e]decyl)HfMe ₂ , (CpMe ₄ -n-propyl)(1-methyl-3-n-butylbenzo[e]decyl HfMe ₂ , (CpMe ₄ - n-propyl) (1-n-butyl, 3-methylbenzo[e]indenyl)HfMe ₂ , (CpMe ₄ -n-propyl) (1-ethyl, 3- Methylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-propyl)(1-methyl,3-ethylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-butyl) (1,3-Me ₂ benzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-butyl)(1-methyl-3-n-propylbenzo[e]decyl)H fMe ₂ ,(CpMe ₄ -n-butyl)(1-n-propyl, 3-methylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-butyl)(1-methyl-3-正Butylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-butyl)(1-n-butyl, 3-methylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-butyl (1-ethyl, 3-methylbenzo[e]indenyl)HfMe ₂ ,(CpMe ₄ -n-butyl)(1-methyl,3-ethylbenzo[e]indenyl)HfMe ₂ , and its zirconium analogues.

In an alternative embodiment, the quinone dimethyl hydrazine (Me ₂ ) after the transition metal in the above list of catalyst compounds is replaced with a dihalide such as a dichloride or difluoride or a bisoxide. It is especially used with aluminoxane activators.

(b) Activator component of the catalyst system

The terms 〝Auxiliary 〞 and 〝 activator 〞 can be used interchangeably herein and are defined as any compound that can activate any of the above-described catalyst compounds by converting a neutral catalyst compound to a catalytically active catalyst compound cation. . Non-limiting activators include, for example, aluminoxanes, aluminum alkyls, ionizable activators which may be neutral or ionic, and conventional secondary catalyst types. Preferred activators typically include an aluminoxane compound, a modified aluminoxane compound, and an ionized anion precursor compound that extracts a sigma-bonded reactive metal ligand to produce a metal-missing cation. And provide a charge-balanced uncoordinated or weakly coordinating anion.

In one embodiment, an alumoxane activator is used as an activator in the catalyst composition. The aluminoxane is typically an oligomeric polymeric compound containing a -Al(R ¹ )-O- subunit wherein R ¹ is an alkyl group. Examples of aluminoxanes include methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, and isobutyl aluminoxane. Alkyl aluminoxanes and modified alkyl aluminoxanes are suitable as catalyst activators, especially when the extractable ligand is an alkyl group, a halide, an alkoxide or a decylamine. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It may be preferred to use a visually clear methylaluminoxane. The cloudy or gelled aluminoxane can be filtered to produce a clear solution, or the clear aluminoxane can be decanted from the cloudy solution. Another aluminoxane is a modified methylaluminoxane (MMAO) auxiliary catalyst type 3A (commercially available from Akzo Chemicals, Inc. under the modified methyl aluminoxane 3A type). Reported by U.S. Patent No. 5,041,584).

When the activator is aluminoxane (modified or unmodified), some specific examples select a maximum amount of Al/M activator (each metal catalyst) that is 5000 times more molar than the catalyst precursor. position). The minimum activator is 1:1 molar ratio to the catalyst precursor. A preferred range of options includes at most 500:1, or at most 200:1, or at most 100:1, or from 1:1 to 50:1. In a preferred embodiment, little or no aluminoxane is used in the process for making VT-HO polymers. The aluminoxane is preferably present at 0 mole percent, or the aluminoxane is present at a transition metal molar ratio of less than 500:1 aluminum, preferably less than 300:1, preferably less than 100: 1, preferably less than 1:1. In an alternative embodiment, if aluminoxane is used to make the VTM, the aluminoxane is treated to remove the free alkyl aluminum compound, particularly trimethyl aluminum. Moreover, in a preferred embodiment, the activators used herein to make the VT-HO polymer are discrete.

Aluminium alkyl or organoaluminum compounds useful as co-activators (or co-scavengers) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and the like. .

In a preferred embodiment, little or no scavenger is used in the process for making VT-HO polymers. The scavenger is preferably present at 0 mole percent, or the scavenger is present at less than 100:1 scavenger metal to transition metal molar ratio, preferably less than 50:1, preferably less than 15: 1, preferably less than 10:1.

Ionizing activator

Use of ionized or stoichiometric activators within the scope of the invention Or ionic), such as tris(n-butyl)ammonium phthalate (perfluorophenyl)borate, metal hexamethylene perfluoroborate or para-fluoronaphthyl boron precursor, polyhalogenated borane Anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459) or combinations thereof. It is also within the scope of the invention to use a neutral or ionic activator alone or in combination with an aluminoxane or a modified alumoxane activator. The most preferred activator is ionic rather than neutral borane.

Examples of neutral stoichiometric activators include trisubstituted boron, ruthenium, aluminum, gallium, and indium, or mixtures thereof. The three substituents may each independently be selected from the group consisting of alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy, and halide. The three groups are preferably independently selected from halogen, mono- or polycyclic (including halo-substituted) aryl, alkyl and alkenyl compounds, and mixtures thereof, preferably olefins having from 1 to 20 carbon atoms. a group having an alkyl group of 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 3 to 20 carbon atoms (including a substituted aryl group). The three groups are more preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group or a mixture thereof. The three groups are even more preferably halogenated (preferably fluorinated) aryl groups. The neutral stoichiometric activator is preferably fluorophenyl boron or perfluoronaphthyl boron.

The ionic stoichiometric activator compound may contain active protons or other cations that bind (but not coordinate) or only loosely coordinate with the remaining ions of the ionizing compound. Such compounds and analogs are described in European Patent Publication No. EP 0 570 982 A, EP 0 520 732 A, EP 0 495 375 A, EP 0 500 944 B1, EP 0 277 003 A, EP 0 277 004 A; Nos. 5, 153, 157, 5, 198, 401, 5, 066, 741, 5, 206, 197, 5, 241, 025, 5, 384, 299, U.S. Patent Application Serial No. 08/285,380, the entire disclosure of which is incorporated herein by reference.

The ionic catalyst can be prepared by reacting a transition metal compound with some neutral Lewis acid such as B(C ₆ F ₆ ) ₃ , which is a hydrolyzable ligand with a transition metal compound (X) The reaction forms an anion such as ([B(C ₆ F ₅ ) ₃ (X)) ^- ) which stabilizes the cation transition metal species produced by the reaction. The catalyst can be and preferably is prepared with an activator component which is an ionic compound or composition.

In the preparation of the ionic catalyst system used in the method of the present invention, the compound used as the activator component contains a cation (preferably a proton-producing Bronsted acid) and has a relatively large (large) anionic compatible non-coordinating anion (which is capable of stabilizing the active catalyst species (Group 4 cation) formed when the two compounds are combined), and the anion has sufficient olefins, diolefins and The instability of the replacement of an acetylene unsaturated matrix or other neutral Lewis base such as ethers, amines and the like. Two classes of compatible non-coordinating anions are disclosed in EP 0 277,003 A and EP 0 277,004 A, both published in 1988: 1) Anionic coordination complexes comprising a plurality of metals with intermediate charge or The metalloid core is covalently coordinated and shields the lipophilic group of the core, and 2) an anion comprising a plurality of boron atoms, such as carborane, metal carborane, and borane.

In a preferred embodiment, the stoichiometric activator comprises a cationic and an anionic component and can be represented by the formula: (LH) _d ⁺ (A ^d- ) (14) wherein L is a neutral Lewis base; H is hydrogen (LH) ⁺ is Brinell; A ^d- is a non-coordinating anion having a charge d-; and d is 1, 2 or 3.

The cationic component (LH) _d ⁺ may comprise a Brinell, such as a protonated Lewis capable of protonating a portion of a transition metal catalyst precursor containing a large ligand metallocene, such as an alkyl or aryl group. Base to form a cationic transition metal species.

The activated cation (LH) _d ⁺ may be a Brine acid capable of applying a proton to a transition metal catalyst precursor to form a transition metal cation, including ammonium, oxonium, hydrazine, hydrazine, and mixtures thereof, preferably methyl. Amine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine , pyridine, p-bromo N,N-dimethylaniline, ammonium p-nitro-N,N-dimethylaniline; oxime from triethylphosphine, triphenylphosphine and diphenylphosphine; Oxime of ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thionine derived from thioethers such as diethyl sulfide and tetrahydrothiophene; and mixtures thereof.

The anionic component A ^{d -} includes those having the formula [M ^{k +} Q _n ] ^d - wherein k is 1, 2 or 3; n is an integer from 2, 3, 4, 5 or 6; nk = d; M is An element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, a bridged or unbridged dialkyl guanylamino group, a halide, an alkoxide, an aryl oxide, a hydrocarbon group, a substituted hydrocarbon group, a halocarbon group, a substituted halocarbon group, and a halo group-substituted hydrocarbon group, the Q having up to 20 carbon atoms, the prerequisite being that Q is not more than one time is a halide. Each Q is preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and each Q is more preferably a fluorinated aryl group, and each Q is preferably a pentafluoroaryl group. Examples of suitable A ^{d -} also include diboron compounds, as disclosed in U.S. Patent No. 5,447,895, the disclosure of which is incorporated herein by reference.

An illustrative (non-limiting) example of a boron compound useful as an auxiliary catalyst in the preparation of the catalyst system of the process of the present invention is a trisubstituted ammonium salt such as trimethylammonium tetraphenylborate. , triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tris(t-butyl)ammonium tetraphenylborate, tetraphenylboronic acid N, N-dimethylanilinium, tetraphenylboronic acid N,N-diethylanilinium, tetraphenylboronic acid N,N-dimethyl-(2,4,6-trimethylanilinium), tetraphenyl Cycloheptatrienylboronic acid, triphenylcarbonium tetraphenylborate, triphenylsulfonium tetraphenylborate, triethylsulfonium tetraphenylborate, benzene (diazonium salt) tetraphenylborate, hydrazine Trimethylammonium pentafluorophenyl)borate, triethylammonium ruthenium (pentafluorophenyl)borate, tripropylammonium ruthenium (pentafluorophenyl)borate, tris(butyl)phosphonium (pentafluorophenyl)borate Ammonium, lanthanum (pentafluorophenyl)borate tri(t-butyl)ammonium, ruthenium (pentafluorophenyl)borate N,N-dimethylanilinium, quinone (pentafluorophenyl)boronic acid N,N- Diethyl benzyl ammonium, hydrazine (pentafluorophenyl) boric acid N,N-dimethyl-(2,4,6-trimethylanilinium), fluorene (pentafluorophenyl)borate Alkene, ruthenium (pentafluorophenyl)borate, triphenylcarbenium, ruthenium (pentafluorophenyl)borate, triphenylsulfonium, iridium (pentafluorophenyl)borate, triethylsulfonium, iridium (pentafluorophenyl) Benzyl borate (diazonium salt), trimethylammonium bismuth-(2,3,4,6-tetrafluorophenyl)borate, tris(p-(2,3,4,6-tetrafluorophenyl)borate Triammonium, bis-(2,3,4,6-tetrafluorophenyl)borate, tris(butyl)ammonium bis(n-butyl)-(2,3,4,6-tetrafluorophenyl)borate,肆-(2,3,4,6-tetrafluorophenyl)boronic acid dimethyl(t-butyl)ammonium, bismuth-(2,3,4,6-tetrafluorophenyl)boronic acid N,N-di Methyl phenyl ammonium, bismuth (2,3,4,6-tetrafluorophenyl) boron Acid N,N-diethylanilinium, 肆-(2,3,4,6-tetrafluorophenyl)boronic acid N,N-dimethyl-(2,4,6-trimethylanilinium),肆-(2,3,4,6-tetrafluorophenyl)boronic acid cycloheptatrienium, fluorenyl-(2,3,4,6-tetrafluorophenyl)boronic acid triphenylcarbenium, hydrazine-(2 , 3,4,6-tetrafluorophenyl)boronic acid triphenylsulfonium, fluorene-(2,3,4,6-tetrafluorophenyl)boronic acid triethyl hydrazine, hydrazine-(2,3,4, 6-tetrafluorophenyl)boronic acid benzene (diazonium salt), bismuth (perfluoronaphthyl)boronic acid trimethylammonium, fluorene (perfluoronaphthyl)boronic acid triethylammonium, cerium (perfluoronaphthyl)boronic acid Propyl ammonium, tris(n-butyl)ammonium phthalate (perfluoronaphthyl)borate, tris(t-butyl)ammonium hydride (perfluoronaphthyl)borate, N,N-di Methylanilinium, 全(perfluoronaphthyl)boronic acid N,N-diethylanilinium, 肆(perfluoronaphthyl)boronic acid N,N-dimethyl-(2,4,6-trimethylbenzene Ammonium), fluorene (perfluoronaphthyl)boronic acid, cycloheptatrienyl fluorene, fluorene (perfluoronaphthyl)boronic acid, triphenylcarbenium, fluorene (perfluoronaphthyl)boronic acid, triphenylsulfonium, fluorene (perfluoronaphthyl) ) Triethyl sulfonium borate, benzene (perfluoronaphthyl) boric acid benzene (diazonium salt), hydrazine (perfluorobiphenyl) boronic acid trimethylammonium, cerium (perfluorobiphenyl) boric acid triethylammonium肆 (perfluorobiphenyl) Tripropylammonium borate, tris(n-butyl)ammonium hydride (perfluorobiphenyl)borate, tris(t-butyl)ammonium ruthenium (perfluorobiphenyl)borate, fluorene (perfluorobiphenyl) N,N-dimethylanilinium borate, N,N-diethylanilinium hydride (perfluorobiphenyl)boronic acid, N,N-dimethyl-(2, 4,6-trimethylanilinium), fluorene (perfluorobiphenyl)boronic acid cycloheptatrienium, fluorene (perfluorobiphenyl)boronic acid triphenylcarbenium, fluorene (perfluorobiphenyl)boronic acid Triphenyl hydrazine, hydrazine (perfluorobiphenyl) borate triethyl hydrazine, hydrazine (perfluorobiphenyl) boric acid benzene (diazonium salt), hydrazine (3,5-bis(trifluoromethyl)benzene Trimethylammonium borate, triethylammonium ruthenium (3,5-bis(trifluoromethyl)phenyl)borate, tripropyl sulfonium (3,5-bis(trifluoromethyl)phenyl)borate Ammonium, cerium (3,5-bis(trifluoromethyl)phenyl)boronic acid tri(n-butyl)ammonium, Tris(t-butyl)ammonium (3,5-bis(trifluoromethyl)phenyl)borate, N,N-dimethyl (3,5-bis(trifluoromethyl)phenyl)borate Ammonium, cerium (3,5-bis(trifluoromethyl)phenyl)boronic acid N,N-diethylanilinium, cerium (3,5-bis(trifluoromethyl)phenyl)boronic acid N,N - dimethyl-(2,4,6-trimethylanilinium), ruthenium (3,5-bis(trifluoromethyl)phenyl)borate, cycloheptatrienium, hydrazine (3,5-double ( Triphenylcarbenium trifluoromethyl)phenyl)borate, triphenylsulfonium ruthenium (3,5-bis(trifluoromethyl)phenyl)borate, ruthenium (3,5-bis(trifluoromethyl)) Phenyl)triethylphosphonium borate, benzene (diazonium salt of 3,5-bis(trifluoromethyl)phenyl)borate; and dialkylammonium salt such as ruthenium (pentafluorophenyl) Di-(isopropyl)ammonium borate and dicyclohexylammonium pentium (pentafluorophenyl)borate; and additional trisubstituted sulfonium salts such as tris(o-tolyl)phosphonium quinone (pentafluorophenyl)borate And tris(2,6-dimethylphenyl)anthracene (pentafluorophenyl)borate.

The ionic stoichiometric activator (LH) _d ⁺ (A ^d- ) is preferably 肆 (perfluoronaphthyl) boric acid N,N-dimethylanilinium, fluorene (perfluorobiphenyl)boronic acid N,N- Dimethylanilinium, cerium (3,5-bis(trifluoromethyl)phenyl)boronic acid N,N-dimethylanilinium, fluorene (perfluoronaphthyl)boronic acid triphenylcarbenium, anthracene Fluorbiphenyl)triphenylcarbonium borate, triphenylcarbenium ruthenium (3,5-bis(trifluoromethyl)phenyl)borate or triphenylcarbenium iridium (perfluorophenyl)borate.

In one embodiment, an activation method using an ionized ionic compound which does not contain an active proton but is capable of producing a large ligand metallocene catalyst cation and a non-coordinating anion thereof is also encompassed, and the method is described in EP 0 426 637 A, EP 0 573 403 A, and U.S. Patent No. 5,387,568, the entire disclosure of each of which is incorporated herein by reference.

The term "non-coordinating anion" (NCA) means an anion that neither coordinates with the cation nor has a weak coordination with the cation, thereby remaining sufficient Instability replaced by neutral Lewis base. 〝 Compatibility 〞 Non-coordinating anions are those that do not degrade to neutral when the initially formed complex decomposes. Furthermore, the anion does not transfer an anionic substituent or fragment to a cation to cause it to form a neutral tetracoordinated metallocene compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with the present invention are those which are compatible such that the metallocene cations balance their ionic charge of +1, but remain sufficiently to permit ethylene or acetylation during polymerization. Instability of unsaturated monomer replacement. In addition to the activator compounds or secondary catalysts, scavengers such as triisobutylaluminum or trioctylaluminum are also used.

The method of the present invention may also use a secondary catalyst compound or activator which is initially a neutral Lewis acid, but forms a cationic metal complex and a non-coordinating anion or a zwitterionic complex upon reaction with the compound of the present invention. Compound. For example, gins(pentafluorophenyl)boron or aluminum is effective in extracting a hydrocarbyl or hydride ligand to give a cationic metal complex of the invention and a stable non-coordinating anion, see EP 0 427 697 A and EP 0 520 732 A, which is used to exemplify a similar Group 4 metallocene compound. See also the methods and compounds of EP 0 495 375 A. For the use of a zwitterion complex formation of a similar Group 4 compound, see U.S. Patent Nos. 5,624,878, 5,486,632 and 5,527,929.

Another salt suitable for forming and activating the auxiliary catalyst comprises a salt of a cationic oxidizing agent and a compatible non-coordinating anion, and the following formula represents: (OX ^e+ ) _d (A ^d- ) _e (16) wherein OX ^e+ is a cationic oxidant having a charge e+; e is 1, 2 or 3; A ^d- is a non-coordinating anion having a charge d-; and d is 1, 2 or 3.

Examples of the cationic oxidizing agent include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag ⁺ or Pb ⁺² . Preferred specific examples of A ^d- are those previously defined for the active agent containing Brinell (especially quinone (pentafluorophenyl) borate).

A typical NCA (or any non-aluminoxane activator) activator to catalyst ratio of 1:1 molar ratio. A preferred range of choices is from 0.1:1 to 100:1, or from 0.5:1 to 200:1, or from 1:1 to 500:1, or from 1:1 to 1000:1. A particularly useful range is from 0.5:1 to 10:1, preferably from 1:1 to 5:1.

Large activator

As used herein, a large activator 〞 refers to an anionic activator represented by the following formula: Wherein each R ₁ is independently a halide, preferably a fluoride; each R ₂ is independently a halide, a C ₆ to C ₂₀ substituted aromatic hydrocarbon group or _a decyloxy group of the formula -O-Si-R _a Wherein R _a is a C ₁ to C ₂₀ hydrocarbyl group or a hydrocarbyl alkyl group (R _{2 is} preferably a fluoride or a perfluorinated phenyl group); each R ₃ is a halide, a C ₆ to C ₂₀ substituted aromatic hydrocarbon group or _a decyloxy group of the formula -O-Si-R _a wherein R _a is a C ₁ to C ₂₀ hydrocarbyl group or a hydrocarbyl alkyl group (R _{3 is} preferably a fluoride or a C ₆ perfluorinated aromatic hydrocarbon group); wherein R ₂ and R ₃ may form one or more saturated or unsaturated substituted or unsubstituted rings (R ₂ and R ₃ preferably form a perfluorinated phenyl ring); L is a neutral Lewis base; (LH) ⁺ is Brinell; d is 1, 2 or 3; wherein the anion has a molecular weight greater than 1020 g/mole; and wherein at least three of the substituents on the B atom each have a molecular volume greater than 250 cubic angstroms, or More than 300 cubic angstroms, or greater than 500 cubic angstroms.

The molecular volume 〝 is used herein as an approximation of the spatial volume of the activator molecule in solution. Comparing substituents having different molecular volumes allows a substituent having a smaller molecular volume to be considered as a smaller volume enthalpy than a substituent having a larger molecular volume. Conversely, a substituent having a larger molecular volume is considered to have a larger volume enthalpy than a substituent having a smaller molecular volume.

The molecular volume can be reported in "A Simple" Back of the Envelope" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids, "Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964. The way to calculate. Molecular volume in cubic Angstrom Units (MV) system using the formula: MV = 8.3V _s calculated, where V _s is the volume scale. V _s is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the relative volume of the following table. The V _s of the fused ring is reduced by 7.5% per fused ring.

Exemplary large substituents suitable for the activators herein and their respective scale volumes and molecular volumes are shown in the table below. The dashed bond indicates the combination with boron, as in the above formula.

Exemplary large activators useful in the catalyst systems herein include: trimethylammonium (perfluoronaphthyl)borate, triethylammonium (perfluoronaphthyl)borate, bismuth (perfluoronaphthyl)boronic acid Tripropylammonium, tris(n-butyl)ammonium hydride (perfluoronaphthyl)borate, tris(tert-butyl)ammonium phthalate (perfluoronaphthyl)borate, N,N-fluorene (perfluoronaphthyl)boronic acid N,N-diethylanilinium, 全(perfluoronaphthyl)boronic acid N,N-dimethyl-(2,4,6-trimethyl) Ammonium Benzate), fluorene (perfluoronaphthyl)boronic acid cycloheptatrienyl fluorene, fluorene (perfluoronaphthyl)boronic acid triphenylcarbenium, fluorene (perfluoronaphthyl)boronic acid triphenyl sulfonium, hydrazine (perfluoronaphthalene) Triethyl sulfonium borate, benzene (perfluoronaphthyl) boric acid benzene (diazonium salt), bismuth (perfluorobiphenyl) boronic acid trimethylammonium, fluorene (perfluorobiphenyl) borate triethyl Ammonium, cerium (perfluorobiphenyl) tripropylammonium borate, tris(n-butyl)ammonium phthalate (perfluorobiphenyl)borate, tris(tert-butyl)ammonium strontium (perfluorobiphenyl)borate , (perfluorobiphenyl)boronic acid N,N-dimethylanilinium, fluorene (perfluorobiphenyl)boronic acid N,N-diethylanilinium, fluorene (perfluorobiphenyl)boronic acid N, N-dimethyl-(2,4,6-trimethylbenzene ), fluorene (perfluorobiphenyl)boronic acid cycloheptatriene fluorene, fluorene (perfluorobiphenyl)boronic acid triphenylcarbenium, fluorene (perfluorobiphenyl)boronic acid triphenyl sulfonium, hydrazine (perfluoro Biphenyl)triethylphosphonium borate, benzene (perfluorobiphenyl)boronic acid benzene (diazonium salt), [4-tert-butyl-PhNMe ₂ H][(C ₆ F ₃ (C ₆ F _{5 2} ) ₄ B] (wherein Ph is a phenyl group and Me is a methyl group), and the type disclosed in U.S. Patent No. 7,297,653.

Activator combination

Within the scope of the invention, the catalyst compound can be combined with one or more of the activators or activation methods described above. For example, combinations of activators are described in U.S. Patent Nos. 5,153,157, 5,453,410; European Patent Publication No. EP 0 573 120 B1; PCT Publication No. WO 94/07928 and WO 95/14044. These documents all discuss the use of a combination of aluminoxane and ionizing activator.

(iii) random co-activators and scavengers

In addition to the activator compounds, scavengers or co-activators can also be used. Aluminoalkyl or organoaluminum compounds useful as co-activators (or scavengers) include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

(iv) random carrier materials

In the specific examples herein, the catalyst system can comprise an inert carrier material. The support material is preferably a porous support material such as talc and an inorganic oxide. Other carrier materials include zeolites, clays, organic clays, or any other organic or inorganic carrier materials and the like, or mixtures thereof.

The support material is preferably an inorganic oxide in a finely divided form. Inorganic oxide materials suitable for use in the metallocene catalyst systems herein include Group 2, 4, 13 and 14 metal oxides such as cerium oxide, aluminum oxide and mixtures thereof. Other inorganic oxides which may be used alone or in combination with cerium oxide or aluminum oxide are magnesia, titania, zirconia and the like. However, other suitable carrier materials can be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Particularly useful supports include magnesium oxide, titanium oxide, zirconium oxide, microcrystalline kaolinite, sulphate minerals, zeolites, talc, clay, and the like. Combinations of such support materials can also be used, such as cerium oxide-chromium, cerium oxide-alumina, cerium oxide-titanium oxide, and the like. Preferred support materials include Al ₂ O ₃ , ZrO ₂ , SiO ₂ and combinations thereof, more preferably SiO ₂ , Al ₂ O ₃ or SiO ₂ /Al ₂ O ₃ .

Preferably, the support material (preferably inorganic oxide) has a surface area ranging from about 10 to about 700 square meters per gram, a pore volume ranging from about 0.1 to about 4.0 milliliters per gram, and An average particle size in the range of from about 5 to about 500 microns. More preferably, the surface area of the support material is in the range of from about 50 to about 500 square meters per gram, the pore volume is in the range of from about 0.5 to about 3.5 milliliters per gram, and the average particle size is from about 10 Up to about 200 microns. Preferably, the surface area of the support material is in the range of from about 100 to about 400 square meters per gram, the pore volume is in the range of from about 0.8 to about 3.0 milliliters per gram, and the average particle size is from about 5 Up to about 100 microns. The carrier material useful in the present invention has an average pore size in the range of from 10 to 1000 angstroms, preferably from 50 to about 500 angstroms, and most preferably from 75 to about 350 angstroms. In some specific cases The carrier material is a large surface area amorphous yttrium oxide (surface area = 300 square meters / gram; 1.65 cubic meters / gram of pore volume), and examples include Davison 952 or DAVISON by WR Grace and Company's Davison Chemical Division 955 is the material sold under the trade name. In other specific examples, DAVIDSON 948 is used.

The carrier material should be dry, i.e., without absorbed water. Drying of the support material can be accomplished by heating or calcining at a temperature of from about 100 ° C to about 1000 ° C, preferably at least about 600 ° C. When the support material is cerium oxide, it is heated to at least 200 ° C, preferably from about 200 ° C to about 850 ° C, and most preferably at about 600 ° C and for from about 1 minute to about 100 hours, from about 12 hours to Approximately 72 hours, or from about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl groups (OH) to make the catalyst system of the present invention. The calcined support material is then contacted with at least one polymeric catalyst comprising at least one metallocene compound and an activator.

Method of making a supported catalyst system

The support material having a reactive surface group (typically a hydroxyl group) is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a metallocene compound and an activator. The slurry of the carrier material in the solvent is prepared by introducing the carrier material into a solvent and heating the mixture to a temperature of from about 0 ° C to about 70 ° C, preferably from about 25 ° C to about 60 ° C, preferably at room temperature. The contact time is typically from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are all the reactants used herein (also That is, the activator and the metallocene compound are at least partially soluble in the material, and they are liquid at the reaction temperature. Preferred non-polar solvents are paraffins such as isopentane, hexane, n-heptane, octane, decane and decane, although various other materials may be used, including naphthenes such as cyclohexane. , aromatic (such as benzene, toluene and ethylbenzene).

In a specific example herein, the support material is contacted with a solution of a metallocene compound and an activator such that the reactive groups on the support material are titrated to form a supported polymeric catalyst. The period of contact between the metallocene compound, the activator and the support material is the time required to titrate the reactive groups on the support material. The titration of hydrazine means reacting with an effective reactive group on the surface of the support material to reduce at least 80%, at least 90%, at least 95%, or at least 98% of the surface hydroxyl groups. The surface reactive group concentration can be determined based on the calcination temperature used and the type of the support material. The calcination temperature of the support material affects the amount of surface reactive groups on the support material that are effective to react with the metallocene compound and the activator: the higher the drying temperature, the less the number of positions. For example, when the support material is cerium oxide, prior to its use in the first catalyst system synthesis step, it is dehydrated by flowing with nitrogen and heating at about 600 ° C for about 16 hours, typically about 0.7 per gram. Surface hydroxyl concentration of millimolar (milligrams per gram). Thus, the actual molar ratio of the activator to the surface reactive groups on the support will vary. This is preferably determined on a case-by-case basis to ensure that only as much activator as is deposited on the support material is added to the solution without leaving excess activator in solution.

The amount of activation that will be deposited on the support material without leaving an excess in solution can be determined in any conventional manner, such as by adding an activator to the carrier slurry in the solvent while stirring the slurry until known in the art. Any technique, such as ¹ H NMR, detects an activator that becomes a solution in a solvent. For example, with respect to the cerium oxide support material heated at about 600 ° C, the activation dose added to the slurry is such that the hydroxyl (OH) molar ratio of B to cerium oxide is from about 0.5:1 to about 4:1, preferably. It is from about 0.8:1 to about 3:1, more preferably from about 0.9:1 to about 2:1, and most preferably about 1:1. The amount of B on yttrium oxide can be determined using ICPES (Inductively Coupled Plasma Emission Spectroscopy) as described in JWO Lesik, "Inductively Coupled Plasma-Optical Emission Spectroscopy," in the Encyclopedia of Materials Characterization, CR Brundle, CAEvans, Jr. And S. Wilson, eds., Butterworth-Heinemann, Boston, Mass., 1992, pp. 633-644. In another embodiment, it is also possible to add more than this amount of activation deposited on the carrier, and then remove any excess activator by, for example, filtration and washing.

In another embodiment, the invention relates to:

A compound having at least 200 g/mole (preferably 200 to 100,000 g/mole, preferably 200 to 75,000 g/mole, preferably 200 to 60,000 g/m, preferably 300 to 60,000 a higher olefin polymer of gram (measured by ¹ H NMR) of gram/mole, or preferably 750 to 30,000 gram/mole, comprising: (i) one or more (preferably two or more) , three or more, four or more, and similar amounts) C ₄ to C ₄₀ (preferably C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C ₄ to C ₁₂ , preferably butene, Pentene, hexene, heptene, octene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, ring a unit of higher olefin derived from octene, cyclooctadiene, cyclododecene, 7-oxa decene, 7-oxa decadiene, substituted derivatives thereof and isomers thereof The polymer of the vinyl-terminated higher olefin does not substantially comprise propylene-derived units (preferably less than 0.1% by weight of propylene, preferably 0% by weight of propylene); wherein the higher olefin polymer has at least 5 % (at least 10%, at least 15%, at least 20% , at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% or 100% by mole of allyl chain ends; optionally 1 : 1 or greater allyl chain end to vinylidene chain end ratio (preferably greater than 2:1, greater than 2.5:1, greater than 3:1, greater than 5:1, or greater than 10:1); More optionally and preferably substantially free of isobutyl chain ends (preferably less than 0.1% by weight of isobutyl chain ends); and more optionally, the polymers of such vinyl terminated higher olefins may comprise at least 5 Molar% (preferably at least 15 mol%, at least 25 mol%, at least 35 mol%, at least 45 mol%, at least 60 mol%, at least 75 mol%, or at least 90 mol%) Ethylene derived unit.

2. The polymer of the vinyl-terminated higher olefin of paragraph 1, wherein the polymer of the vinyl-terminated higher olefin comprises at least 36 carbons having at least 36 carbons based on the weight of the polymer composition. Atoms (measured by ¹ H NMR, assuming one unsaturated per chain) of olefins.

3. The polymer of the vinyl-terminated higher olefin of paragraphs 1 and 2, wherein the polymer of the vinyl-terminated higher olefin comprises dimerization of less than 20% by weight based on the weight of the copolymer composition. Preferably, the trimer and the trimer are less than 10% by weight, preferably less than 5% by weight, or more preferably less than 2% by weight, as measured by GC.

4. The polymer of a vinyl-terminated higher olefin of paragraphs 1 to 3, wherein the copolymer of higher olefin has a viscosity of greater than 1000 cP at 60 ° C, greater than 12,000 cP, or greater than 100,000 cP (or less than 200,000 cP, less than 150,000 cP, or less than 100,000 cP).

5. A vinyl-terminated higher olefin having at least 200 gram/mole (measured by ¹ H NMR) and containing at least 5 mole % of one or more C ₅ to C ₄₀ higher olefin derived units a polymer wherein the polymer of a higher olefin terminated with a vinyl group does not substantially comprise ethylene, propylene or butene derived units; and wherein the polymer of the higher olefin has at least 5% of allyl chain ends (relative to Totally unsaturated).

6. A polymer of a vinyl-terminated higher olefin of paragraph 5 which additionally has an allyl chain end to vinylidene chain end ratio of 1:1 or greater and/or substantially no isobutyl chain end .

7. The polymer of a vinyl-terminated higher olefin according to paragraph 5 or 6, wherein the polymer is a homopolymer (such as homopentene, homopolyhexene, homo-octene, homo-decene, Polydodecene).

8. 5 or 6 segments vinyl polymer of higher olefins terminal, wherein the polymer is substantially a copolymer (such as a copolymer of hexene and octene from C ₅ to C ₄₀ olefins consisting of octyl a copolymer of an alkene and a terpene, a copolymer of octene, decene and dodecene).

9. A polymer of a vinyl-terminated higher olefin of paragraph 5, 6 or 8 wherein the polymer comprises at least 5 mole percent (preferably at least 10 mole percent, at least 15 mole percent, at least 20 moles) Ear %, at least 30 mole %, at least 40 mole %, at least 50 mole %, at least 60 mole %, at least 70 mole %, at least 80 mole %, at least 90 mole %, or at least 95 moles %) of C ₅ to C ₄₀ olefins (such as pentene, hexene, octene or decene), the balance being complemented by different C ₅ to C ₄₀ olefins.

10. A method of making a polymer of a vinyl-terminated higher olefin of paragraphs 1 to 9, wherein the method comprises contacting: (i) one or more (preferably two or more, three or more , four or more, and similar amounts) C ₄ to C ₄₀ (preferably C ₄ to C ₃₀ , C ₄ to C ₂₀ , or C ₄ to C ₁₂ , preferably butene, pentene, hexene, Heptene, octene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctane a olefin, a cyclododecene, a 7-oxa decene, a 7-oxa decadiene, a substituted derivative thereof, and an isomer thereof; (ii) substantially free of propylene (preferably Less than 0.1% by weight of propylene) monomer; (iii) at least 5 mol% (preferably at least 15 mol%, at least 25 mol%, at least 35 mol%, at least 45 mol%, at least 45 mol%, at least) 60 mole %, at least 75 mole %, or at least 90 mole % of ethylene monomer; wherein the contact system occurs in the presence of a catalyst system comprising an activator and at least one of the following formulas A representative of a metallocene compound: (i) Or (ii) Or (iii) Or (iv) Wherein: M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbon groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halogens, a diene, an amine, a phosphine, an ether, and combinations thereof (two X may form part of a fused ring or ring system); each Q system is independently a carbon or a hetero atom; each R ¹ is independently a C ₁ to C ₈ alkyl group , R ¹ and R ² may be the same or different; each R ² is independently a C ₁ system to C ₈ alkyl; each R ³ is independently hydrogen or a system substituted by from 1 to 8 carbon atoms or unsubstituted hydrocarbon group of , but the prerequisite is that at least three R ³ groups are not hydrogen; each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; R ⁵ is hydrogen or C ₁ To a C ₈ alkyl group; R ⁶ is hydrogen or C ₁ to C ₈ alkyl; each R ⁷ is independently hydrogen or C ₁ to C ₈ alkyl, provided that at least 7 R ⁷ groups are not hydrogen; T is a bridging group; each R ^a is independently hydrogen, halogen or a C ₁ to C ₂₀ hydrocarbyl group; two R ^a may form a cyclic structure, including an aromatic, partially saturated or saturated cyclic or fused ring system; And the other prerequisites are any two Adjacent R groups may form a fused ring or multicenter fused ring system (wherein such rings may be aromatic, partially saturated or saturated ring); or (v) Wherein: M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbon groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halides , a diene, an amine, a phosphine, an ether, and combinations thereof (two X may form part of a fused ring or ring system); each R ⁸ is independently a C ₁ to C ₁₀ alkyl group; each R ⁹ system is independently C ₁ To a C ₁₀ alkyl group; each R ¹⁰ is hydrogen; each R ¹¹ , R ¹² and R ¹³ are independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; T is a bridging group. And other prerequisites are that any adjacent R ¹¹ , R ¹² and R ¹³ groups may form a fused ring or a polycentric fused ring system (wherein the rings may be aromatic, partially saturated or saturated) Or (vi) Wherein: M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbon groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halogens, a diene, an amine, a phosphine, an ether or a combination thereof; each of R ¹⁵ and R ¹⁷ is independently a C ₁ to C ₈ alkyl group; and each of R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen or a substituted or unsubstituted hydrocarbon group having from 1 to 8 carbon atoms; and a C ₄ to C ₄₀ higher olefin system thereof From butene, pentene, hexene, heptene, octene, decene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, ring Heptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxapentene, 7-oxa decadiene, substituted derivatives thereof and isomers thereof.

11. The method of paragraph 10, wherein the activator is a large activator represented by the formula: Wherein each R ₁ is independently a halide, preferably a fluoride; each R ₂ is independently a halide, a C ₆ to C ₂₀ substituted aromatic hydrocarbon group or _a decyloxy group of the formula -O-Si-R _a Wherein R _a is a C ₁ to C ₂₀ hydrocarbyl or hydrocarbyl alkyl group, preferably a fluoride or a C ₆ perfluorinated aromatic hydrocarbon group; each R ₃ is a halide, a C ₆ to C ₂₀ substituted aromatic hydrocarbon group or _a decyloxy group of the formula -O-Si-R _a wherein R _a is a C ₁ to C ₂₀ hydrocarbyl or hydrocarbyl alkyl group, preferably a fluoride or a C ₆ perfluorinated aromatic hydrocarbon group; and wherein L is a neutral Lewis a base; H is hydrogen; (LH) ⁺ is Brinell; d is 1; wherein the anion has a molecular weight greater than 1020 g/mole; and at least three of the substituents on the B atom each have greater than 250 The molecular volume of angstroms is greater than 300 cubic angstroms, or greater than 500 cubic angstroms.

12. The method of paragraphs 10 to 11, wherein the large activator is at least one of the following: trimethylammonium (perfluoronaphthyl)borate, triethylammonium (perfluoronaphthyl)borate, lanthanum (all) Fluoronaphthyl)tripropylammonium borate, tris(n-butyl)ammonium hydride (perfluoronaphthyl)borate, tris(tert-butyl)ammonium phthalate (perfluoronaphthyl)borate, fluorene (perfluoronaphthyl) N,N-dimethylanilinium borate, N,N-diethylanilinium borate, 肆(perfluoronaphthyl)boronic acid N,N-dimethyl-(2,4, 6-trimethylanilinium), fluorene (perfluoronaphthyl)boronic acid cycloheptatriene fluorene, fluorene (perfluoronaphthyl)boronic acid triphenylcarbenium, fluorene (perfluoronaphthyl)boronic acid triphenylsulfonium, Barium (perfluoronaphthyl) borate triethyl hydrazine, hydrazine (perfluoronaphthyl) boric acid benzene (diazonium salt), hydrazine (perfluorobiphenyl) borate trimethyl ammonium, hydrazine (perfluorobiphenyl) Triethylammonium borate, tripropylammonium hydride (perfluorobiphenyl)borate, tris(n-butyl)ammonium hydride (perfluorobiphenyl)borate, tris(perfluorobiphenyl)borate Tributyl)ammonium, hydrazine (perfluorobiphenyl)boronic acid N,N-dimethylanilinium, fluorene (perfluorobiphenyl)boronic acid N,N-diethylanilinium, hydrazine (perfluorobiphenyl) Base) N,N-dimethyl-borate (2,4,6-trimethyl) Benzolammonium), fluorene (perfluorobiphenyl)boronic acid cycloheptatriene fluorene, fluorene (perfluorobiphenyl)boronic acid triphenylcarbenium, fluorene (perfluorobiphenyl)boronic acid triphenylsulfonium, hydrazine (perfluorobiphenyl) triethyl sulfonium borate, hydrazine (perfluorobiphenyl) boric acid benzene (diazonium salt), [4-tert-butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (wherein Ph is a phenyl group and Me is a methyl group).

13. A composition comprising a higher olefin copolymer of paragraphs 1 to 9 or a method of paragraphs 10 to 12, preferably a lubricating blend.

14. Use of the composition of paragraph 13 as a lubricant.

Product characteristics

The product was characterized by ¹ H NMR and ¹³ C NMR as follows:

¹³ C NMR

^{The 13} C NMR data was collected using a Bruker 400 MHz NMR spectrometer at 120 ° C and at a frequency of at least 100 MHz. Use a 90-degree pulse throughout the acquisition to adjust the acquisition time to obtain a digital resolution between 0.1 and 0.12 Hz, with at least 10 seconds of pulse acquisition with continuous broadband proton decoupling without sweeping using sweeping square wave modulation delay. The spectrum is acquired over the average time to provide a signal that is capable of measuring the signal of interest relative to the noise value. The sample was dissolved in tetrachloroethane-d ₂ with a concentration between 10 and 15% by weight prior to insertion of the spectrometer magnet.

Prior to analyzing the data, the spectra were quoted by setting the chemical shift of the TCE solvent signal to 74.39 ppm.

The ends of the chains used for quantification were identified using the signals shown in the table below. N-butyl and n-propyl groups are not described as they are low abundance (less than 5%) relative to the chain ends shown in the table below.

¹ H NMR

^{The 1} H NMR data was collected at room temperature or at 120 ° C (120 ° C for the purposes of the patent application) using a Varian spectrometer with a frequency of ¹ H of at least 250 MHz in a 5 mm probe. The data was recorded using a maximum pulse width of 45 ° C with an average signal of 8 seconds and 120 transients between pulses. The spectral signal is integrated and the number of unsaturation types per 1000 carbons is calculated by multiplying the different groups by 1000 and dividing the result by the total carbon number. Mn is calculated by dividing the total number of unsaturated species by 14,000 and has units of grams per mole.

The chemical shift region of the olefin type is limited between the following spectral regions.

Viscosity

Viscosity was measured using a Brookfield Digital Viscometer.

Instance

All experiments were carried out using a nitrogen filled glove box and a Schlenk line in the absence of air and without moisture. Toluene, 1-decene and 1-hexene were purchased from Sigma Aldrich (Milwaukee, WI) and dried with alumina beads previously calcined at 300 °C.肆(Perfluoronaphthyl)boronic acid dimethylanilinium was purchased from Albemarle (Baton Rouge, LA) and used as received. 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2-ylidene (yliddene) [2-(isopropoxy)-5-(N,N- Dimethylaminosulfonyl)phenyl]methylene ruthenium(II) dichloride was purchased from Strem Chemicals (Newburyport, MA) and received as received It looks like it is used.

Scavenger and auxiliary catalyst

Triisobutylaluminum (TIBAL) was obtained from Akzo Chemicals, Inc. (Chicago, IL) and used without further purification. Tri-n-octyl aluminum (TNOAL) was obtained from Akzo Chemicals, Inc. and used without further purification.

The metallocene used in the examples

The following metallocenes A to C were synthesized. A typical drying oven procedure for the synthesis of air sensitive compounds, including the use of dry glassware (90 ° C, 4 hours) and anhydrous solvent from Sigma Aldrich (St. Louis, MO), through a 3A screen Further drying.

Synthesis of metallocene E and metallocene F:

The metallocenes E and F are synthesized as indicated below.

Synthesis of Compound 1a+1b: Compound A (2-methylindole, 10 g, 76.9 mmol) was dissolved in diethyl ether (150 mL) and taken to nBuLi (10M, hexane, 77 mmol) Protonation. After 4 hours, propyl bromide (CH ₃ CH ₂ CH ₂ Br, 18 g, 146 mmol) was added to the reaction mixture, then tetrahydrofuran (THF, 50 mL) was added and the reaction was stirred at room temperature. 12 hours. The reaction was quenched with water and the organic layer was dried over anhydrous magnesium sulfate (MgSO ₄₎ and dried. The volatiles were removed to give a yellow oily mixture of 1a and 1b (10.5 g, 83% yield). ¹ H NMR (C ₆ D ₆ , 500 MHz) δ ppm; Compound 1a: 6.22 (s), 3.05 (m), 1.79 (s) 0.75 (t). Compound 1b: 2.91 (s), 2.36 (t), 1.79 (s), 0.85 (t).

Synthesis of Compound 2: A mixture of 1a and 1b was dissolved in hexanes (200 ml) and de-protonated with n-butyllithium (nBuLi, 6.1 mL of a 10 M solution in hexanes, 61 mM). After 12 hours at room temperature, the solid was collected on a glass frit, washed with additional hexanes (2×50 mL) and dried in vacuo to give compound 2 as a white solid (10.8 g, quantitative yield ). ¹ H NMR (THF-d8, 500 MHz) δ ppm; Compound 2: 7.09 (m, C ₆ H ₄ ring), 6.30 (m, C ₆ H ₄ ring), 5.47 (s, C ₅ H ring), 2.70 (t, C ₅ -CH ₂ -), 2.17 (s, C ₅ -Me), 1.50 (m, C ₅ -CH ₂ -CH ₂ -), 0.89 (t, -C ₂ H ₄ -Me).

Synthesis of Compound 4+1b: All lithiated Ligand Compound 2 was dissolved in THF (100 mL) and dichlorodimethylsilane (Me ₂ SiCl ₂ , 3.8 g, 29 mmol) at room temperature The reaction was carried out for 10 hours. ¹ H NMR showed formation of 4 and 1 b. Compound 4 was purified by column chromatography (75% hexane / 25% ethyl acetate v/v) on silica gel (200-400 mesh).

Synthesis of Compound 5: A hexane extract containing Compound 4 was reacted with nBuLi (5 g, 10 M solution in hexane) to supply a solid. The white solid product 5 was filtered on a glass frit, washed with hexane (2.times.30 mL) and dried in vacuo (9.1 g, 84% based on 1a, 1b). Compound ^{5: 1 H NMR δ ppm (} THF-d8,250 MHz); 7.57 (m), 7.12 (m), 6.30 (m), 3.55 (t), 2.70 (t), 2.34 (s), 1.46 (m ), 0.85 (t), 0.59 (s).

Synthesis method of metallocene E:

The synthesis of the metallocene E is exemplified below.

The synthesis of Compound 6: Compound 5 (6.6 g, 16.0 mmol) prepared in diethyl ether (100 ml) and the slurry with hafnium tetrachloride (HfCl _4, 4.2 g, 13.1 mmol) the reaction. After 1 hour, about 50 ml of diethyl ether was removed and compound 6 (dimethylammonium bis(2-methyl, 3-propyldecyl) ruthenium dichloride was collected as a bright yellow solid on the glass frit. ) (4.2 grams, 49.5%).

Synthesis of metallocene E: Compound 6 was slurried in diethyl ether (50 ml) and toluene (80 ml) and with methylmagnesium iodide (MeMgI, 5.6 g, 3M in diethyl ether) The reaction was carried out for 16 hours at room temperature. Dimethoxyethane (DME, 6 grams) was added to the crude reaction mixture, the mixture was filtered through a medium glass frit and the filtrate collected. The volume of the filtrate was reduced, pentane (30 mL) was added and the filtrate was cooled to -35 °C. Collected as the first harvest crystal (pure rac-7, 0.6 g, 16%) and became the second crop (5% meso-7 and 95% rac-7, 0.7 g, 19%) of compound 7 (rac - Dimethyldecyl bis(2-methyl, 3-propylindenyl) fluorenyl dimethyl). Compound 7: ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ ppm; 7.4 (d), 7.3 (d), 7.08 (t), 6.75 (t), 2.68 to 2.22 (complex m), 1.87 (s) ), 1.41 (m), 0.97 (s), 0.81 (t), -1.95 (s).

Wherein Me is a methyl group.

Synthesis of Compound 9: Compound 5 (8.2 g, 19.9 mmol) prepared in diethyl ether (150 ml) and the slurry of ZrCl ₄ (4.2 g, 17.9 mmol) at room temperature. After 4 hours, the orange solid was collected on a medium melt and washed with additional diethyl ether (2 x 30 mL). The product was dried in vacuo to give pure EtOAc (3.8 g, 38%). ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ ppm; 7.63 (d), 7.41 (d), 7.3 (m), 6.96 (m), 2.57 (d of m), 2.04 (s), 1.42 (m) ), 1.31 (s), 0.88 (t).

Synthesis of metallocene F: Compound 9 (1.12 g, 2.0 mmol) was slurried in diethyl ether (80 ml) and with MeMgI (1.7 g, 4.5 mmol, 3.0 M) at room temperature reaction. The reaction mixture was stirred at room temperature for 48 hours. The volatiles were removed in vacuo and the crude mixture was extracted with EtOAc (3 <RTIgt; The hexane solution was reduced to 20 mL and cooled to -35 ° C to give F (0.8 g, 77%) as a yellow crystalline solid. ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ ppm; 7.38 (m), 7.15 (t), 6.78 (t), 2.52 (d of m), 1.85 (s), 1.57 (m), 1.06 (s) ), 0.86(t), -1.71(s).

Synthesis of metallocene C

3H-benzo[e]indole (benzo(4,5)indole) was purchased from Boulder Scientific (Boulder, Colorado). Pentamethylcyclopentadiene was purchased from Norquay. All other reagents were purchased from Sigma-Aldrich.

Synthesis of [Li][1,3-dimethylbenzo[e]茚]

[Li][benzo[e]茚] is obtained by adding 3H-benzo[e]pyrene (12.0 g, 0.072 mol) with 1.1 equivalents of n-BuLi (7.90 ml of 10 M/hexane, slowly added). 0.079 moles of reaction is produced in ether. After 2 hours, [Li][benzo[e]indole] was isolated by removing the ether under vacuum. The residue was triturated with hexanes to afford a white solid. The solid was collected by vacuum filtration on a medium-sized glass frit, washed with hexanes and dried in vacuo to afford pure [Li][benzo[e]indole] (12.0 g, 97%) as an off white solid. The product was characterized by ¹ H NMR: (THF-d ₈ , 250 MHz). δ ppm : 8.02 (d, J = 10 Hz, C ₁₀ H ₆ , 1H), 7.47 (t, J = 6.3 Hz, C ₁₀ H ₆ , 2H), 7.09 (t, J = 6.2 Hz, C ₁₀ H ₆ , 1H), 6.91 (t, J = 1 Hz, C ₁₀ H ₆ , 1H), 6.74 (d, J = 10 Hz, C ₁₀ H ₆ , 1H), 6.59 (s, 茚 matrix, 1H), 6.46 (s, 茚 茚, 1H), 6.46 (s, 茚 茚, 1H), 6.09 (s, 茚 茚, 1H).

[Li][Benzo[e]indole] (12.0 g, 0.070 mol) was dissolved in ether, cooled to -35 ° C and reacted with 6.0 equivalents of MeI (59.34 g, 0.418 mmol). Allow the reaction to warm to ambient temperature. After 12 hours, the reaction was quenched with water and extracted with ether. The organics were concentrated to give a crude oil which was distilled using a Kugelrohr apparatus to give a succinic oil which was 3-methyl-3H-benzo[e]indole and 1-methyl-1H-benzo[e] A pure mixture of hydrazine isomers (7.58 grams, 58%). The product was characterized by ¹ H NMR: (CD ₂ Cl ₂ , 250 MHz). δ ppm: 8.25-7.42 (m, C ₁₀ H ₆ , 10H), 7.15 (d, J = 6.3 Hz, C ₁₀ H ₆ , 2H), 7.09 (t, J = 6.2 Hz, C ₁₀ H ₆ , 1H) , 6.91 (t, J = 1 Hz, C ₁₀ H ₆ , 1H), 6.74 (d, J = 10 Hz, C ₁₀ H ₆ , 1H), 6.59 (s, 茚 matrix, 1H), 6.46 (s,茚 茚 ,, 1H), 6.46 (s, 茚 茚 ,, 1H), 6.09 (s, 茚 茚, 1H).

Similarly, [Li][methylbenzo[e]oxime] is obtained by isomerization of 3-methyl-3H-benzo[e]indole with 1-methyl-1H-benzo[e]indole The mixture of the mixture (7.58 g, 0.041 mol) was reacted with a slow addition of 1.1 equivalents of n-BuLi (4.45 ml of a 10 M/hexane solution, 0.045 mol) to give the ether. After 2 hours, [Li][methylbenzo[e]indole] was isolated by removing the ether under vacuum. The residue was triturated with hexanes to afford a white solid. The solid was collected by vacuum filtration on a medium size glass frit, washed with excess hexane and in vacuo Dry to provide pure [Li][methylbenzo[e]indole] (6.97 g, 85%) as an off-white solid.

[Li][Methylbenzo[e]indene] (6.97 g, 0.037 mol) was dissolved in ether, cooled to -35 ° C and reacted with 3.7 equivalents of MeI (19.52 g, 0.138 mmol). Allow the reaction to warm to ambient temperature. After 12 hours, the reaction was quenched with water and extracted with ether. The organic matter is concentrated to give a yellow oily substance which is 1,3-dimethyl-3H-benzo[e]indole, 1,3-dimethyl-1H-benzo[e]indole, 3,3-di A mixture of methyl-3H-benzo[e]indole and 1,1-dimethyl-1H-benzo[e]indole isomer (6.63 g, 91%).

Similarly, [Li][1,3-dimethylbenzo[e]fluorene] is obtained by adding the above mixture of dimethylbenzoindole isomers (6.63 g, 0.034 mol) with 1.1 equivalents added slowly. n-BuLi (3.74 ml of a 10 M/hexane solution, 0.037 mol) was reacted in ether. After 2 hours, [Li][1,3-dimethylbenzo[e]indole] was isolated by removing the ether under vacuum. The residue was triturated with hexanes to give a white solid. The solid was collected by vacuum filtration on a medium sized glass frit, washed with excess hexanes and dried in vacuo to afford pure [Li][1,3-dimethylbenzo[e]indole as an off-white solid. (5.43 grams, 79%). The product was characterized by ¹ H NMR: (THF-d ₈ , 250 MHz). δ ppm: 8.19 (d, J = 7.5 Hz, 1H), 7.48 (d, J = 7.5 Hz, 1H), 7.33 (d, J = 7.5 Hz, 2H), 7.09 (t, J = 1.4 Hz, 1H) , 6.91 (t, J = 1.2 Hz, 1H), 6.67 (d, J = 8.5 Hz, 1H), 5.98 (s, 1H), 2.65 (s, 3H), 2.34 (s, 3H).

Synthesis of (CpMe ₅ )(1,3-Me ₂ benzo[e]indenyl)HfMe ₂ (metallocene C)

CpMe ₅ HfCl ₃ (3.8 g) was reacted with [Li][1,3-Me ₂ benzo[e]indenyl] (2.5 g, 4.3 mmol) in Et ₂ O (80 mL) for 48 h. (Crowther, D.; Baenziger, N.; Jordan, R.; J. Journal of the American Chemical Society (1991), 113(4), pp. 1455-1457). The pale yellow product was collected by filtration on a glass frit and dried to give crude (CpMe ₅ )( 1,3-Me ₂ benzo[e] decyl)HfCl ₂ (3.2 g) as a mixture. ¹ H NMR (CD ₂ Cl ₂ , 250 MHz). δ ppm; 8.13, 7.80 (d, Ha, Ha' _, 1H), 7.59 to 7.36 (multiple peaks, Hb, Hb', Hc, Hc', 4H) 6.10 (s, Hd, 1H), 2.62, 2.45 (s , 1,3Me ₂ C ₉ H ₅ , 3H), 2.10 (s, CpMe ₅ ).

(CpMe ₅ )(1,3-Me ₂ benzo[e]indenyl)HfCl ₂ (2.5 g) was slurried in toluene (100 mL) with MeMgI (4.2 g, 2.1 eq. in Et ₂ O The reaction in the 3.0 M solution). The reaction mixture was heated to 80 ° C for 3 hours. After cooling, the volatiles were removed in vacuo to give a solid, which was taken in hexane (4×40 mL). Hexane removed from the combined extracts to give a yellow solid _{(CpMe 5) (1,3-Me} 2 C 9 H 5) HfMe 2 (1.6 g). ¹ H NMR (C ₆ D ₆ , 300 MHz) δ ppm; 7.55-7.48 (m, C ₆ H ₄ , 2H), 7.20-7.16 (m, C ₉ H ₅ , 3H), 2.00 (s, 1,3Me) ₂ C ₉ H ₅ , 6H), 1.76 (s, CpMe ₅ , 15H), -0.95 (s, Hf-Me, 6H).

The metallocenes A, B and C were used in the following examples.

Synthesis of ^13- C-labeled 1-decene

A 2.0 gram amount of 1-decene was placed in a 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2-arylene equipped with a magnetic stir bar and 5.0 mg. A 125 ml pressurized reaction vessel of [2-(isopropoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methylene ruthenium (II) dichloride. The solution was placed in a liquid nitrogen bath and placed under vacuum. ¹³ C-labeled ethylene (500 ml, 1 atm) was condensed into a pressurized reaction vessel. Remove the liquid nitrogen bath. After the solution was thawed, the bottle was heated to 50 ° C with stirring for 2 hours. The bottle was depressurized and the solution was filtered through 1 gram of cerium oxide to remove catalyst residue. 1-decene is distilled by short-path distillation. The separation of the metathesis product 9-octadecene (about 30 mol%, measured by NMR) was not obtained. ¹ H NMR of the sample revealed approximately 60% of the incorporated ¹³ C label. ¹ H NMR (500 MHz, CD ₂ ClCD ₂ Cl), δ ppm: 5.78 (m, 1H), 5.4 (m, derived from the octadecene in the sample), 5.2.-4.8 (m, 2H; ¹³ C-labeled vinyl J _HC = 154 Hz) 1.99 (m, 2H), 1.3 (m, 12H), 0.88 (t, 3H).

Polymerization of ¹³ C-labeled 1-decene

1.0 g of ¹³ C-labeled 1-decene was placed in a 20 ml scintillation vial equipped with a stir bar. Two drops of TIBAL were added to 1-decene. A separate solution of the activated catalyst was prepared by combining 16 mg of metallocene A with 27 mg of dimethyl(perfluoronaphthyl)borate dimethylanilinium in 11.0 g of toluene. The metallocene E solution (100 mg) was combined with 1-decene at 50 ° C for 2 hours. The resulting oligomers were characterized by NMR spectroscopy. ¹³ C NMR (500 MHz, CD ₂ ClCD ₂ Cl), δ ppm: 115 (labeled vinyl carbon, Figure 1).

Polymerization of 1-decene Example 1

The activated catalyst solution was prepared by combining 15 mg of the metallocene E with 32 mg of dimethyl(perfluoronaphthyl)borate dimethylanilinium in 7.0 g of toluene. The activated metallocene solution (100 mg) was added to 10.0 g of 1-decene in a 20 ml scintillation vial pre-heated to 85 ° C and containing 2 drops of TIBAL. After 2 hours, unreacted 1-decene was removed under a stream of nitrogen. The yield of poly(1-decene) was 8.3 grams. The polymer was analyzed by ¹ H NMR spectroscopy: Mn = 5,644 g/mole (measured by ¹ H NMR); end group analysis: vinyl = 42 mol%, vinylidene = 43 mol %, ethylene Base = 15 mole %.

Example 2

1-decene (40 grams, 285 millimoles) and TIBAL (about 60 mg, 0.23 millimoles) were placed in a 100 ml round bottom flask dried in an oven with a stir bar and heated to 50 °C. While stirring the solution, add metallocene C (422 μg, 0.78 μm) and dimethyl (perfluoronaphthyl)borate dimethyl benzyl ammonium (650 μg, 0.57 μm) to toluene (400 μl) Solution in. After 6 hours, the reaction was quenched with 1 mL of 10% (v/v) isopropanol in pentane mixture. More volatile components of the mixture were removed by heating the solution to 160 °C under a vacuum of 1500 mTorr. After the distillation, 32.5 grams (80%) of the heavy oil remained in the distillation pot. The polymer was analyzed by ¹ H NMR spectroscopy: Mn = 12,700 g/mole; end group analysis: vinyl = 36 mol%.

Reactor description and preparation

The polymerization was carried out using an internal heater equipped for temperature control, a glass insert (reactor internal volume = 22.5 ml), a septum inlet, a regulated nitrogen supply, and a disposable PEEK ( The polyetheretherketone) mechanical agitator (800 RPM) was carried out in a 48-chamber parallel pressure reactor (PPR) inert gas (N ₂ ) drying oven. The PPR was prepared for polymerization by rinsing with dry nitrogen at 150 ° C for 5 hours and then at 25 ° C for 5 hours.

Polymerization of 1-hexene/1-octene

1-octene and 1-hexene were added as indicated in the following table and then isohexane was added so that the total volume of the solution was 5.0 ml. TNOAL was used as a scavenger at a concentration of 1 M. A solution of hydrazine (perfluoronaphthyl)borate dimethylanilinium in toluene was first added, followed by the addition of the metallocene solution such that the activator to metallocene ratio was 1:1. The chamber was heated to 85 ° C and the reaction was allowed to continue for 1 hour. The reaction was quenched with air and the unreacted monomer was removed in vacuo. The analysis of some of the chamber products is listed in Table 1.

The inventors have surprisingly produced vinyl-terminated octene/hexene copolymers in the absence of propylene.

All documents described herein are incorporated herein by reference, and include any priority documents, related applications, and/or testing procedures that are not inconsistent with the present subject matter, but the conditions precedent are not in the original application or filing Any priority documents named are not incorporated herein by reference. Various modifications may be made without departing from the spirit and scope of the inventions. Accordingly, it is not intended that the invention be limited thereby. Similarly, for the purposes of Australian law, the term "comprising" is considered to be synonymous with the term "including". Similarly, 〝 contains 〝 〝 〝 〝 〝 basically consists of 〞, 〝 is (is) 〞 and 〝 is composed of ..., and can be basically composed of... ... constitutes 〞, 〝 is (is) 〞 and 〝 is composed of 〞 to replace 〝 containing 〞 in any place.

Figure 1 is an NMR spectrum of poly(1-decene) in which the 1-decene starting material is rich in isotopes.

Claims (23)

a polymer having at least 200 grams per mole of Mn (measured by ¹ H NMR) of a vinyl-terminated higher olefin comprising one or more C ₄ to C ₄₀ higher olefin derived units, wherein The polymer of the higher olefin does not substantially comprise propylene-derived units; wherein the polymer of the higher olefin has at least 5% of allyl chain ends; and wherein the polymer of the higher olefin has 1:1 or greater olefin The ratio of the end of the base chain to the end of the vinylidene chain. A polymer of a higher olefin according to the first aspect of the invention, wherein the polymer of the higher olefin has an Mn in the range of 200 to 100,000 g/mole. The polymer of the higher olefin according to claim 1, wherein the C ₄ to C ₄₀ higher olefin is selected from the group consisting of butene, pentene, hexene, heptene, octene, decene, decene, undecene. , dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxapentene, 7-oxanorbornadiene, substituted derivatives thereof and isomers thereof. A polymer of a higher olefin according to claim 1 of the patent application, which additionally comprises at least 5 mole % of ethylene derived units. The polymer of the higher olefin according to claim 1, wherein the copolymer of the higher olefin comprises at least 50% by weight based on the weight of the copolymer composition, having at least 36 carbon atoms (measured by ¹ H NMR, Assume an unsaturated olefin per chain. a polymer of a higher olefin according to item 1 of the patent application, The copolymer of the higher olefin comprises less than 20% by weight, based on the weight of the copolymer composition, of a dimer and a trimer. The higher olefin copolymer according to claim 1, wherein the copolymer of the higher olefin has a viscosity of more than 1000 cP at 60 °C. A process for the manufacture of a polymer of a vinyl-terminated higher olefin according to claim 1 of the patent application, wherein the process comprises one or more C ₄ to C ₄₀ higher olefin derived units (where substantially no propylene is present Provided) contacting a catalyst system comprising an activator and at least one metallocene compound represented by at least one of the following formula: (i) Or (ii) Or (iii) Or (iv) Wherein: M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbon groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halogens, a diene, an amine, a phosphine, an ether, and combinations thereof (two X may form part of a fused ring or ring system); each Q system is independently a carbon or a hetero atom; each R ¹ is independently a C ₁ to C ₈ alkyl group , R ¹ and R ² may be the same or different; each R ² is independently a C ₁ system to C ₈ alkyl; each R ³ is independently hydrogen or a system substituted by from 1 to 8 carbon atoms or unsubstituted hydrocarbon group of , but the prerequisite is that at least 3 R ³ groups are not hydrogen; each R ⁴ is independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; R ⁵ is hydrogen or C ₁ To a C ₈ alkyl group; R ⁶ is hydrogen or C ₁ to C ₈ alkyl; each R ⁷ is independently hydrogen or C ₁ to C ₈ alkyl, provided that at least 7 R ⁷ groups are not hydrogen; T is a bridging group; each R ^a is independently hydrogen, halogen or a C ₁ to C ₂₀ hydrocarbyl group; two R ^a may form a cyclic structure, including an aromatic, partially saturated or saturated cyclic or fused ring system; And the other prerequisites are any two Adjacent R groups may form a fused ring or a polycentric fused ring system (wherein the rings may be aromatic, partially saturated or saturated); or (v) Wherein: M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbon groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halides , a diene, an amine, a phosphine, an ether, and combinations thereof (two X may form part of a fused ring or ring system); each R ⁸ is independently a C ₁ to C ₁₀ alkyl group; each R ⁹ system is independently C ₁ To a C ₁₀ alkyl group; each R ¹⁰ is hydrogen; each R ¹¹ , R ¹² and R ¹³ are independently hydrogen or a substituted or unsubstituted hydrocarbon group, a hetero atom or a hetero atom-containing group; T is a bridging group. Additional prerequisites are that any adjacent R ¹¹ , R ¹² and R ¹³ groups may form a fused ring or a polycentric fused ring system (wherein the rings may be aromatic, partially saturated or saturated); Or (vi) Wherein: M is cerium or zirconium; each X is independently selected from the group consisting of hydrocarbon groups having from 1 to 20 carbon atoms, hydrides, decylamines, alkoxides, sulfides, phosphides, halogens, a diene, an amine, a phosphine, an ether or a combination thereof; each of R ¹⁵ and R ¹⁷ is independently a C ₁ to C ₈ alkyl group; and each of R ¹⁶ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are independently hydrogen or a substituted or unsubstituted hydrocarbon group having from 1 to 8 carbon atoms. The method of claim 8 further comprising contacting at least 5 mole % of the ethylene monomer with the catalyst system. According to the method of claim 8, wherein the C ₄ to C ₄₀ higher olefin is selected from the group consisting of butene, pentene, hexene, heptene, octene, decene, decene, undecene, dodecene. , norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxapentene, 7-oxa Decalin, its substituted derivatives and its isomers. According to the method of claim 8, wherein the activator is a large activator represented by the following formula: Wherein each R ₁ is independently a halide, preferably a fluoride; each R ₂ is independently a halide, a C ₆ to C ₂₀ substituted aromatic hydrocarbon group or _a decyloxy group of the formula -O-Si-R _a Wherein R _a is a C ₁ to C ₂₀ hydrocarbyl or hydrocarbyl alkyl group, preferably a fluoride or a C ₆ perfluorinated aromatic hydrocarbon group; each R ₃ is a halide, a C ₆ to C ₂₀ substituted aromatic hydrocarbon group or _a decyloxy group of the formula -O-Si-R _a wherein R _a is a C ₁ to C ₂₀ hydrocarbyl or hydrocarbyl alkyl group, preferably a fluoride or a C ₆ perfluorinated aromatic hydrocarbon group; wherein L is a neutral Lewis a base; H is hydrogen; (LH) ⁺ is a Bronsted acid; d is 1; wherein the anion has a molecular weight greater than 1020 g/mole; and at least three of the substituents on the B atom each have greater than A molecular volume of 250 cubic angstroms, or greater than 300 cubic angstroms, or greater than 500 cubic angstroms. The method of claim 8, wherein the large activator is at least one of the following: trimethylammonium (perfluoronaphthyl)borate, triethylammonium (perfluoronaphthyl)borate, hydrazine ( Perfluoronaphthyl)tripropylammonium borate, tris(n-butyl)ammonium phthalate (perfluoronaphthyl)borate, tris(t-butyl)ammonium phthalate (perfluoronaphthyl)borate, fluorene (perfluoronaphthyl) N,N-dimethylanilinium borate, N,N-diethylanilinium borate, fluorene (perfluoronaphthyl)boronic acid N,N-dimethyl-(2,4 ,6-trimethylanilinium), fluorene (perfluoronaphthyl)boronic acid cycloheptatriene fluorene, fluorene (perfluoronaphthyl)boronic acid triphenylcarbenium, fluorene (perfluoronaphthyl)boronic acid triphenylsulfonium , 肆(perfluoronaphthyl)boronic acid triethyl hydrazine, hydrazine (perfluoronaphthyl)boronic acid benzene (diazonium salt), hydrazine (perfluorobiphenyl)boronic acid trimethylammonium, hydrazine (perfluorobiphenyl) Triethylammonium borate, tripropylammonium hydride (perfluorobiphenyl)borate, tris(n-butyl)ammonium hydride (perfluorobiphenyl)borate, tris(perfluorobiphenyl)borate Tertiary butyl)ammonium, hydrazine (perfluorobiphenyl)boronic acid N,N-dimethylanilinium, fluorene (perfluorobiphenyl)boronic acid N,N-diethylanilinium, hydrazine (perfluorinated Phenyl)boronic acid N,N-di Base-(2,4,6-trimethylanilinium), fluorene (perfluorobiphenyl)boronic acid cycloheptatrienyl fluorene, fluorene (perfluorobiphenyl)boronic acid triphenylcarbenium, hydrazine (perfluoro Biphenyl)boronic acid boronic acid triphenylsulfonium, fluorene (perfluorobiphenyl)boronic acid triethylsulfonium, hydrazine (perfluorobiphenyl)boronic acid benzene (diazonium salt), [4-tert-butyl- PhNMe ₂ H][(C ₆ F ₃ (C ₆ F ₅ ) ₄ B] (wherein Ph is a phenyl group and Me is a methyl group). A composition comprising at least one polymer having at least 200 gram/mol of Mn (measured by ¹ H NMR) of a vinyl-terminated higher olefin comprising one or more C ₄ to C ₄₀ a higher olefin-derived unit; wherein the polymer of the vinyl-terminated higher olefin does not substantially comprise propylene-derived units; wherein the higher olefin polymer has at least 5% allylic chain ends; The polymer of olefin has a ratio of allyl chain end to vinylidene chain end of 1:1 or greater. A composition according to claim 13 wherein the composition is a lubricating blend. The composition according to claim 13 wherein the polymer of the higher olefin has an Mn in the range of 200 to 100,000 g/mole. The composition according to claim 13 wherein the C ₄ to C ₄₀ higher olefin is selected from the group consisting of butene, pentene, hexene, heptene, octene, decene, decene, undecene, and twelve. Alkene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxapentene, 7-oxo Pyridinium, its substituted derivatives and isomers thereof. The composition according to claim 13 of the patent application, which additionally comprises at least 5 mol% of ethylene derived units. A use according to the composition of claim 14 of the patent application, which is used as a lubricant. a vinyl terminated high olefin polymer having at least 200 grams per mole of Mn (as measured by ¹ H NMR) and comprising at least 5 mole % of one or more C ₅ to C ₄₀ higher olefins derived a unit wherein the polymer of the vinyl-terminated higher olefin does not substantially comprise ethylene, propylene or butene derived units; and wherein the polymer of the higher olefin has at least 5% allylic chain ends (relative Totally unsaturated). A polymer of a vinyl-terminated higher olefin according to claim 19 of the patent application, which additionally has a ratio of 1:1 or greater allyl chain end to vinylidene chain end and/or substantially no difference The end of the butyl chain. a polymer of a vinyl-terminated higher olefin according to claim 19, wherein the polymer is a homopolymer (such as homopolypentene, homopolyhexene, homo-octene, homo-decene, Homododecene). a polymer of a vinyl-terminated higher olefin according to claim 19, wherein the polymer is a copolymer consisting essentially of a C ₅ to C ₄₀ olefin (such as a copolymer of hexene and octene, a copolymer of octene and decene, a copolymer of octene, decene and dodecene). A polymer of a vinyl-terminated higher olefin according to claim 19, wherein the polymer comprises at least 5 mol% (preferably at least 10 mol%, at least 15 mol%, at least 20 mol) %, at least 30 mol%, at least 40 mol%, at least 50 mol%, at least 60 mol%, at least 70 mol%; at least 80 mol%, at least 90 mol%, or at least 95 mol% A C ₅ to C ₄₀ olefin such as pentene, hexene, octene or decene, the balance being complemented by different C ₅ to C ₄₀ olefins.