JP5848815B2 - NOVEL CATALYST FOR PRODUCING VINYL-TERMINATE POLYMER AND USE THEREOF - Google Patents

Description

This application is a benefit and priority based on US Patent Application No. 13 / 072,280 filed on March 25, 2011 and European Patent Application No. 1170119.6 filed on May 23, 2011. Insist on the right.
The present invention relates to olefin polymerization, especially for producing vinyl-terminated polymers.

  Alpha-olefins, particularly those containing from about 6 to about 20 carbon atoms, are used as intermediates in the manufacture of detergents or other classes of commercial products. Such α-olefins are also used in particular as monomers for linear low density polyethylene. Commercially produced α-olefins are typically prepared by oligomerizing ethylene. Long chain α-olefins such as vinyl terminated polyethylene are also known and can be useful as building blocks that are later functionalized or as macromonomers.

Allyl terminated low molecular weight solids or liquids of ethylene or propylene are typically also prepared for use as branches in a polymerization reaction. 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 Please refer to.
Further, U.S. Pat. No. 4,814,540 discloses methylalum in toluene or hexane with or without hydrogen to prepare allylic vinyl terminated propylene homooligomers having a low degree of polymerization of 2-10. Bis (pentamethylcyclopentadienyl) hafnium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride and bis (tetramethyl n-butylcyclopentadienyl) hafnium dichloride together with xane are disclosed. These oligomers do not have large Mn and at least 93% allylic vinyl type unsaturation. Similarly, these oligomers lack comonomer and are produced with low productivity even with a large excess of alumoxane (molar ratio ≧ 600 Al / M; M = Zr, Hf). Furthermore, in all examples, there is more than 60% by weight of solvent (based on solvent + propylene).

Teuben et al. (J. Mol. Catal., 62, 1990, pp. 277-287), [Cp * ₂ MMe (THT)] + [BPh ₄ ] (M = Zr and Hf) for preparing propylene oligomers. Cp * = pentamethylcyclopentadienyl; Me = methyl; Ph = phenyl; THT = tetrahydrothiophene). When M = Zr, a broad product distribution of oligomers up to C ₂₄ (number average molecular weight (Mn) of 336) was obtained at room temperature. On the other hand, when M = Hf, only dimer 4-methyl-1-pentene and trimer 4,6-dimethyl-1-heptene were formed. The main chain termination mechanism appeared to be a β-methyl transfer from the growing chain back to the metal center, as demonstrated by deuterium labeling studies.
X. Yang et al. (Angew. Chem. Intl Ed. Engl., 31, 1992, pg. 1375-1377) discloses amorphous low molecular weight polypropylene prepared at low temperature, in which case the reaction has low activity. Shown by ¹ H-NMR, the product had 90% allylic vinyl based on the total number of unsaturations. Subsequently, Resconi et al. (J. Am. Chem. Soc., 114, 1992, pp. 1025-1032), bis (pentamethylcyclopentadienyl) zirconium and bis (pentamethylcyclopentadidi) for polymerizing propylene. Discloses the use of (enyl) hafnium and has achieved β-methyl type chain termination resulting in oligomers and low molecular weight polymers with “primarily allyl and iso-butyl terminated” chains. As in US Pat. No. 4,814,540, the resulting oligomer does not have at least 93% allylic chain ends and is about 500 to about 20,000 g / mol (as determined by ¹ H-NMR). ), And the catalyst productivity is low (1-12,620 g / mmol (metallocene) / hour;> 3000 ppm by weight of Al in the product).

Similarly, Small and Brookhart (Macromolecules, 32, 1999, pg. 2120-2130) reveal significant or exclusive 2,1 chain growth, chain termination due to β-hydride elimination, and large amounts of vinyl end groups. Discloses the use of pyridylbisamidoiron catalysts in low temperature polymerization to yield low molecular weight amorphous propylene materials.
Weng et al. (Macromol Rapid Comm. 2000, 21, pp. 1103-1107), using dimethylsilylbis (2-methyl, 4-phenyl-indenyl) zirconium dichloride and methylalumoxane in toluene at about 120 ° C. Disclosed are materials with up to about 81% vinyl ends prepared. This material has a Mn of about 12,300 (determined by ¹ H-NMR) and a melting point of about 143 ° C.
Macromolecules, 33, 2000, pp. 8541-8548 discloses the preparation of a branched block ethylene-butene polymer by reincorporation of vinyl-terminated polyethylene, said branched block polymer comprising CP ₂ ZrCL ₂ And TiCl ₂ activated with methylalumoxane (C ₅ Me ₄ SiMe ₂ NC ₁₂ H ₂₃ ).

Moscardi et al. (Organometallics, 20, 2001, pp. 1918-1931), Propylene for the production of “… allyl end groups are always higher than any other end group in any [propene]”. Discloses the use of rac-dimethylsilylmethylenebis (3-tert-butylindenyl) zirconium dichloride together with methylalumoxane. In these reactions, morphology control is limited and almost 60% of the chain ends are allylic.
Coates et al. (Macromolecules, 38, 2005, pp. 6259-6268), bis (phenoxyimine) titanium activated with modified methylalumoxane (MMAO) in a batch polymerization for 4 hours at −20 ° C. to + 20 ° C. Low molecular weight syndiotactic polypropylene ([rrrr] = 0.46-0.93) using dichloride ((PHI) ₂ TiCl ₂ ) (Al / Ti molar ratio = 200) with about 100% allyl end groups. The preparation of is disclosed. For these polymerizations, propylene was dissolved in toluene to give a 1.65 M toluene solution. The productivity of the catalyst was very low (0.95 to 1.14 g / mmol (Ti) / hour).

JP 2005-336092 discloses the production of vinyl-terminated propylene polymers using materials such as H ₂ SO ₄ treated montmorillonite, triethylaluminum, triisopropylaluminum, where liquid propylene is in toluene. Supplied in the catalyst slurry. This method results in a substantially isotactic macromonomer that does not contain significant amounts of amorphous material.

Rose et al. (Macromolecules, 41, 2008, pp. 559-567) disclose poly (ethylene-co-propylene) macromonomers that do not have significant amounts of iso-butyl chain ends. These macromonomers use bis (phenoxyimine) titanium dichloride ((PHI) ₂ TiCl ₂ ) (Al / Ti molar ratio range 150-292) activated with modified methylalumoxane (MMAO), and semi-batch polymerization (Addition of 30 psi of propylene to toluene at 0 ° C. for 30 minutes, followed by a polymerization time of 2.3 to 4 hours at about 0 ° C. in a 32 psi overpressure ethylene gas stream) and about 4,800-23 , An EP copolymer having a Mn of 300 is produced. In the four reported copolymers, the allyl chain ends are roughly given by the following formula:% allyl chain ends (relative to total unsaturation) = − 0.95 (mol% of ethylene incorporated) +100 , Ethylene incorporation increased and decreased.

For example, an EP copolymer containing 29 mol% ethylene reported 65% (based on total unsaturation) allyl. This is the maximum number of allyls achieved. With 64 mol% ethylene incorporation, only 42% of the unsaturation number is allylic. The productivity of these polymerizations was in the range of 0.78 × 10 ² g / mmol (Ti) / hour to 4.62 × 10 ² g / mmol (Ti) / hour. Prior to this study, Zhu et al. Used a geometrically constrained metallocene catalyst [C ₅ Me ₄ (SiMe ₂ N-tert-butyl) TiMe ₂ ] activated with B (C ₆ F ₅ ) ₃ and MMAO. Prepared ethylene-propylene copolymers with low terminal vinyl (about 38%) have been reported (Macromolecules, 35, 2002, pp. 10062-10070; and Macromolecules Rap. Commun., 24, 2003, pp. 311- 315).
Janiac and Blank summarize various studies related to olefin oligomerization (Macromol. Symp., 236, 2006, pp. 14-22).

  However, for propylene-based polymerizations, particularly propylene-ethylene copolymerization, catalysts that have been shown to provide high allylic chain unsaturation in high yields, in a wide range of molecular weights, and with high catalytic activity There is almost no. Accordingly, there is a need for new catalysts that provide vinyl terminated polymers in high yields, in a wide range of molecular weights, and with high catalytic activity. Further, there is a need for a propylene-based reactive material with a vinyl end that can be functionalized for further application or as a macromonomer for the synthesis of poly (macromonomers).

The present invention relates to a method for preparing a vinyl-terminated propylene polymer, preferably a homogeneous method, wherein the method comprises contacting propylene with a catalyst system comprising an activator and at least one metallocene compound. Wherein the metallocene compound has the formula:
In the formula,
M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, and these (Two Xs may form part of a fused ring or ring system); each R ₁ is independently a C ₁ -C ₁₀ alkyl group; R ₂ is independently a C ₁ -C ₁₀ alkyl group; each R ₃ is hydrogen; each R ₄ , R ₅ and R ₆ is independently hydrogen, or a substituted hydrocarbyl group, or unsubstituted A hydrocarbyl group or a heteroatom; T is a bridging group; provided that any of the adjacent R ₄ , R ₅ and R ₆ groups may form a condensed ring or a multi-centered condensed ring system This ring Aromatic, may be partially saturated or saturated; propylene polymer is produced having an allyl chain ends of at least 35% (relative to the total numbers of unsaturations).

In another embodiment, the invention relates to a catalyst system comprising an activator and at least one metallocene compound, wherein the metallocene compound has the formula:
In the formula,
M is hafnium or zirconium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, ether, and these (Two Xs may form part of a fused ring or ring system); each R ₁ is independently a C ₁ -C ₁₀ alkyl group; R ₂ is independently a C ₁ -C ₁₀ alkyl group; each R ₃ is hydrogen; each R ₄ , R ₅ and R ₆ is independently hydrogen, or a substituted hydrocarbyl group, or unsubstituted A hydrocarbyl group or a heteroatom; T is a bridging group; provided that any of the adjacent R ₄ , R ₅ and R ₆ groups may form a condensed ring or a multi-centered condensed ring system This ring Aromatic, or a partially saturated or saturated.

FIG. 6 shows the observed Mn and% vinyl trends for a typical vinyl terminated polymer of the present invention (Experiments 13-18) (2.3 M propylene).

The inventors have surprisingly discovered a new class of metallocene compounds used in the catalyst systems and methods of the present invention, wherein the catalyst system is useful for producing vinyl-terminated polymers. I found a compound. The catalyst system exhibits unexpectedly high activity, and in some embodiments results in an atactic propylene polymer. These vinyl-terminated polymers may provide utility as macromonomers and as additives for the synthesis of poly (macromonomer) block copolymers. Advantageously, the vinyl groups of these vinyl-terminated polymers provide a route to functionalization. These functionalized polymers may also be useful as additives.
For purposes of the present invention and claims thereto, a new numbering scheme for the periodic table family is used as described in Chemical and Engineering News, 63 (5), pg. 27 (1985). Thus, “Group 4 metal” is an element from Group 4 of the periodic table.

“Catalyst productivity” is a measure of how much polymer (P) (g) is produced during a T time using a polymerization catalyst containing W (g) catalyst (cat). : P / (T × W), and expressed in units of g (P) · g (catalyst) ⁻¹ · time− ¹ . Conversion is the amount of monomer converted to polymer product, reported as mol%, and is calculated based on the yield of polymer and the amount of monomer fed into the reactor. Catalytic activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used, ie [kg (P) / mol (catalyst)]. The

  An “olefin”, also referred to as an “alkene”, is a linear, branched, or cyclic compound that consists of carbon and hydrogen and has at least one double bond. For purposes of this specification and the claims appended hereto, such polymers or copolymers are referred to when the polymer or copolymer is referred to as including olefins, such as, but not limited to, ethylene, propylene, and butene. The olefin present therein is a polymerized form of the olefin. For example, if the copolymer is said to have an “ethylene” content of 35 wt% to 55 wt%, the monomer units in the copolymer are derived from ethylene during the polymerization reaction, and the derived units are It is understood that it is present at 35% to 55% by weight, based on weight. A “polymer” has two or more monomer units that are the same or different. A “homopolymer” is a polymer having monomer units that are identical. A “copolymer” is a polymer having two or more different monomer units. A “terpolymer” is a polymer having three different monomer units. “Different” when used to refer to a monomer unit indicates that the monomer units differ from one another by at least one atom or are isomerically different. Thus, the definition of copolymer includes terpolymer and the like as used herein. Oligomers typically have a low molecular weight (such as Mn less than 25,000 g / mol, preferably less than 2500 g / mol), or a polymer with a small number of monomer units (such as 75 or less monomer units). It is.

For the purposes of the present invention, ethylene shall be considered an α-olefin.
Catalyst System A “catalyst system” is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. For purposes of the present invention and claims thereto, if the catalyst system is described as including a component in a neutral and stable form, those skilled in the art will recognize that the component in ionic form reacts with the monomer to yield a polymer. You will fully understand that it is a form.

In the description herein, a metallocene catalyst can be described as a catalyst precursor, a pre-catalyst compound, or a transition metal compound, and these terms are used interchangeably. A polymerization catalyst system is a catalyst system capable of polymerizing monomers into a polymer. An “anionic ligand” is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A “neutral donor ligand” is a neutrally charged ligand that donates one or more pairs of electrons to a metal ion.
The metallocene catalyst comprises at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety) and more often two π-bonded cyclopentadienyl moieties, or substituted cyclopentadienyl moieties. Is defined as an organometallic compound having This includes other π-bonding moieties such as indenyl or fluorenyl or derivatives thereof.

  The present invention relates to at least one metallocene catalyst, at least one activator, an optional co-activator, and an optional support material, discussed below.

(I) Metallocene Catalyst For the purposes of the present invention and claims thereto, the term “substituted” means that the hydrogen group is replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group, ethyl alcohol is an ethyl group substituted with an —OH group, and “substituted hydrocarbyl” means that at least one hydrogen is a heteroatom or A group composed of carbon and hydrogen that is replaced by a heteroatom-containing group.

For purposes of the present invention and claims thereto, “alkoxide” includes those where the alkyl group is a C ₁ -C ₁₀ hydrocarbyl. The alkyl group may be straight chain, branched chain or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group can include at least one aromatic group.

In embodiments herein, the present invention relates to a catalyst system comprising an activator and at least one metallocene compound, wherein the metallocene compound has the formula:
In the formula,
M is hafnium or zirconium, preferably hafnium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, Selected from the group consisting of ethers, and combinations thereof (two Xs may form part of a fused ring or ring system), preferably each X is independently a halide and C _1- Selected from C ₅ alkyl groups, preferably each X is a methyl group; each R ₁ is independently a C ₁ -C ₁₀ alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl , or isomers thereof, preferably each R ₁ is a methyl group; each R ₂ is independently, C ₁ -C ₁₀ alkyl group, preferably, Chill, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof, preferably each R ₂ is n- propyl group; each R ₃ is hydrogen; each R _4, R ₅ And R ₆ is hydrogen, or a substituted hydrocarbyl group, or an unsubstituted hydrocarbyl group, or a heteroatom, preferably each R ₄ , R ₅ and R ₆ is hydrogen; T is a bridging group; Preferably T comprises Si, Ge or C, preferably T is dialkyl silicon or dialkyl germanium, preferably T is dimethyl silicon; provided that adjacent R ₄ , R ₅ and R ₆ Any of the groups may form a fused ring or a multi-centered fused ring system, which ring may be aromatic, partially saturated or saturated.

Examples of bridging groups T useful in the present invention are 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 C-O-CR' ₂ , R ' ₂ CR' ₂ C-O- CR ′ ₂ CR ′ ₂ , R ′ ₂ C—O—CR ′ ₂ CR ′ ₂ , R ′ ₂ C—O—CR ′ = CR ′, R ′ ₂ C—S—CR ′ ₂ , R ′ ₂ CR ′ ₂ C- _{-CR '2 CR' 2, R} '2 C-S-CR' 2 CR '2, R' 2 C-S-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 C-N = 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 C-P = CR', and R can be represented by _{'2 C-PR'-CR'} 2, wherein, R 'is hydrogen or 1 to 20, Is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent containing, optionally, two or more adjacent R ′ together are substituted or unsubstituted saturated, Partially unsaturated or aromatic Of, they may form a cyclic or polycyclic substituent. Preferably, T is a bridging group containing carbon or silica, such as dialkylsilyl, and preferably T is CH ₂ , CH ₂ CH ₂ , C (CH ₃ ) ₂ , SiMe ₂ , SiPh ₂ , SiMePh. , Silylcyclobutyl (Si (CH ₂ ) ₃ ), (Ph) ₂ C, (p- (Et) ₃ SiPh) ₂ C, and silylcyclopentyl (Si (CH ₂ ) ₄ ).

Preferably, T is represented by the formula R ₂ ^a J, where J is C, Si or Ge, and each R ^a is independently hydrogen, halogen, C ₁ -C ₂₀ hydrocarbyl, or substituted C ₁ -C ₂₀ hydrocarbyl and the two R ^a may form a cyclic structure containing an aromatic, partially saturated or saturated cyclic or fused ring system.

Metallocene compounds that are particularly useful in the present invention include one or more of the following compounds:
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,

rac-dimethylsilylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) hafnium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) zirconium dimethyl,

rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanyl bis (2,3-dimethyl) hafnium dimethyl, and rac-dimethylgermanyl bis (2,3-dimethyl) zirconium dimethyl.

  In an alternative embodiment, “dimethyl” after the transition metal in the list of catalyst compounds above is replaced with a dihalide (such as dichloride or difluoride) or bisphenoxide, especially when used with an alumoxane activator.

In certain embodiments, the metallocene compound has the formula:
Rac-dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dimethyl (I) or rac-dimethylsilylbis (2-methyl, 3-propylindenyl) zirconium dimethyl (II) represented by .

Activators The terms “cocatalyst” and “activator” are used interchangeably herein and refer to any one of the foregoing catalyst compounds for neutral catalyst compounds that are catalytically active. Defined as any compound that can be activated by conversion to a cation. Activators include, but are not limited to, alumoxanes, alkylaluminums, and ion-forming activators (which can be neutral or ionic common classes of cocatalysts). Preferred activators typically include non-coordination that abstracts alumoxane compounds, modified alumoxane compounds, and one reactive σ-binding metal ligand to make the metal complex cationic and charge-balanced. Ion-forming anionic precursor compounds that provide neutral or weakly coordinating anions.

In one embodiment, the alumoxane activator is utilized as an activator in the catalyst composition. The alumoxane is generally an oligomeric compound containing a subunit of —Al (R ¹ ) —O—, wherein R ¹ is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, especially when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of various alumoxanes and modified alumoxanes can also be used. It may be desirable to use a visually clear methylalumoxane. The cloudy or gelled alumoxane can be filtered to make a clear solution, or the clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methylalumoxane (MMAO) co-catalyst type 3A (available from Akzo Chemicals, Inc. under the trade name Modified Metalyloxane 3A, which is included in US Pat. No. 5,041,584) .

When the activator is an alumoxane (modified or unmodified), in some embodiments, a 5000 molar fold excess (per metal catalyst site) of Al / M maximum amount of activator relative to the catalyst precursor is present. Selected. The minimum molar ratio of activator: catalyst precursor is 1: 1. Alternative preferred ranges include 1: 1 to 500: 1, alternatively 1: 1 to 200: 1, alternatively 1: 1 to 100: 1, alternatively 1: 1 to 50: 1.
In a preferred embodiment, little or no alumoxane is used in the process of producing the vinyl terminated polymer. Preferably, the presence of alumoxane is 0 mol%, or the alumoxane is less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, or preferably less than 1: 1 molar ratio of aluminum to transition metal. Exists.
In an alternative embodiment, if an alumoxane is used to make the vinyl terminated polymer, the alumoxane is treated to remove free alkylaluminum compounds, especially trimethylaluminum.
Further, in a preferred embodiment, the activator used in the present invention to produce the vinyl terminated polymer is individual.

Examples of alkylaluminum or organoaluminum compounds that can be used as auxiliary activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.
In another embodiment, diethylzinc is used in a polymerization comprising 1, 2, 3 or more catalysts, at least one of which is a class of metallocenes described herein.
In a preferred embodiment, no or little scavenger is used in the process for producing the vinyl terminated polymer. Preferably, the presence of the scavenger is 0 mol%, or the scavenger is less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, or preferably less than 10: 1. Present in a molar ratio of transition metal.

Ionogenic activator tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, trisperfluorophenyl boron metalloid precursor or trisperfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anion (WO 98/43983) No.), boric acid (US Pat. No. 5,942,459), or combinations thereof, the use of neutral or ionic ion forming or stoichiometric activators is It is included in the range. The use of neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators is also within the scope of the present invention. A highly preferred activator is an ionic activator, not neutral borane.

  Examples of neutral stoichiometric activators include trisubstituted boron, tellurium, aluminum, gallium, and indium, or mixtures thereof. The three substituents are each independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy, and halide. Preferably, the three groups are independently selected from halogen, monocyclic or polycyclic (including halo substituted) aryl, alkyl, and alkenyl compounds, and mixtures thereof, preferably 1-20 An alkenyl group having a carbon atom, an alkyl group having 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 substituted aryl) is there. More preferably, the three groups are alkyl having 1 to 4 carbon groups, phenyl, naphthyl, or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated aryl groups. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds are associated with active protons or residual ions of ion-forming compounds, but are not coordinated or some other that are only loosely coordinated. Cations can be included. Such compounds are disclosed in European Patent Application Nos. 0570982, 0520732, 0495375, 0500944B1, 02777003, 0277704, U.S. Pat. Nos. 5,153,157 and 5,198. No. 5,401, No. 5,066,741, No. 5,206,197, No. 5,241,025, No. 5,384,299, No. 5,502,124, and August 3, 1994 All of which are incorporated herein by reference in their entirety, as described in US patent application Ser.
An ionic catalyst can be prepared by reacting a transition metal compound with a neutral Lewis acid such as B (C ₆ F ₆ ) ₃ , the neutral Lewis acid being a hydrolyzable coordination of the transition metal compound. An anion such as ([B (C ₆ F ₅ ) ₃ (X)] ⁻ ) is formed by reaction with the child (X), and the anion stabilizes the cationic transition metal species generated by the reaction. The catalyst can be prepared using an activator component that is an ionic compound or composition, and is preferably prepared.

  Compounds useful as activator components in the preparation of ionic catalyst systems used in the process of the present invention include cations that are preferably Bronsted acids capable of donating protons, and active catalyst species (Group 4). A relatively large (bulky) compatible non-coordinating anion capable of stabilizing the cation), the active catalytic species being formed when two compounds are combined, said anion being It is sufficiently unstable and is replaced by olefinic, diolefinic and acetylenically unsaturated substrates or other neutral Lewis bases such as ethers, amines. Two classes of compatible non-coordinating anions, 1) anionic coordination comprising a plurality of lipophilic groups covalently coordinated to and shielding the central charge carrying metal or metalloid core Complexes and 2) anions containing multiple boron atoms such as carborane, metal carborane and borane are disclosed in EP 0 277 0003 and 0 277 004.

In a preferred embodiment, the stoichiometric activator comprises a cation and an anion component, preferably the following formula (14):
(L−H) _d ⁺ (A ^d− ) (14)
Where L is a neutral Lewis base, H is hydrogen, (L—H) ⁺ is a Bronsted acid, and A ^d− is non-coordinating with a charge d−. An anion, d is an integer of 1 to 3;
A cationic component, (LH) _d ⁺ , has the ability to add a proton to a moiety such as alkyl or aryl from a bulky metallocene ligand containing a transition metal catalyst precursor to produce a cationic transition metal species. Bronsted acids, such as Lewis bases with protons added.

The activating cation (L—H) _d ⁺ is preferably a Bronsted acid capable of donating a proton to the transition metal catalyst precursor to form a transition metal cation, and is ammonium, oxonium, phosphonium, silylium, And mixtures thereof, preferably methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethyl. Aniline, ammonium of p-nitro-N, N-dimethylaniline; phosphonium from triethylphosphine, triphenylphosphine, and diphenylphosphine; dimethyl ether, diethyl ether, tetrahydrofuran, and Oxonium from ethers such as dioxane; sulfoniums from thioethers such as diethyl thioether and tetrahydrothiophene; and mixtures thereof.

Anionic components A ^d− include those having the formula [M ^{k +} Q _n ] ^d− , where k is an integer from 1 to 3; n is an integer from 2 to 6; = D; M is an element selected from group 13 of the periodic table of elements, preferably boron or aluminum; Q is independently hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, Hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo-substituted hydrocarbyl groups; wherein Q has up to 20 carbon atoms, provided that Q does not exceed one occurrence, Q is a halide, 2 Two Q groups may form a ring structure. Preferably, each Q is a fluorinated hydrocarbyl group having from 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl. It is a group. Examples of suitable A ^d- also include diboron compounds as disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety.

  Additional examples of useful activators include those disclosed in US Pat. Nos. 7,297,653 and 7,799,879.

Non-limiting examples of boron compounds that can be used as activation cocatalysts in the preparation of the catalyst system of the process of the present invention are the following compounds:
Trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (t-butyl) ammonium tetraphenylborate, N, N-dimethylanilinium tetraphenyl Borate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate, tropylium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenyl Phosphonium tetraphenylborate Triethylsilylium tetraphenylborate, benzene (diazonium) tetraphenylborate, trimethyla Ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ) Ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,

  N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl) borate, Triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, triethylsilylium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) B) borate, tripropylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis- (2,3,4,6-tetrafluoro-phenyl) borate, dimethyl (T-butyl) ammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N -Diethylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetra Fluorophenyl) borate, tropylium tetrakis- (2,3,4,6-tetrafluorophenyl) Borate, triphenylcarbenium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triphenylphosphonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate, triethylsilylium tetrakis- (2 , 3,4,6-tetrafluorophenyl) borate, benzene (diazonium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate,

  Trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate, tri (t-butyl) ammonium tetrakis (Perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium ) Tetrakis (perfluoronaphthyl) borate, Tropylium tetrakis (perfluoronaphthyl) borate, Triphenylcarbe Umtetrakis (perfluoronaphthyl) borate, Triphenylphosphonium tetrakis (perfluoronaphthyl) borate, Triethylsilylium tetrakis (perfluoronaphthyl) borate, Benzene (diazonium) tetrakis (perfluoronaphthyl) borate, Trimethylammonium tetrakis (perfluorobiphenyl) borate, Triethylammonium Tetrakis (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl Anilinium Tetrakis (Perfluorobife L) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluorobiphenyl) borate , Triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate,

  Trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tripropylammonium tetrakis (3,5-bis (trifluoromethyl) ) Phenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tri (t-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, N, N -Dimethyl- ( , 4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tropylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (3 , 5-bis (trifluoromethyl) phenyl) borate, triphenylphosphonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, triethylsilylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate , Benzene (diazonium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, and dialkylammonium salts such as di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicycl Hexylammonium tetrakis (pentafluorophenyl) borate and further trisubstituted phosphonium salts such as tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate .

  Most preferably, the activator is N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (3,5- Bis (trifluoromethyl) phenyl) borate, triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylcarbeniumtetrakis (perfluorobiphenyl) borate, triphenylcarbeniumtetrakis (3,5-bis (trifluoromethyl) phenyl) Borate or triphenylcarbenium tetrakis (perfluorophenyl) borate.

In one embodiment, there is also an activation method using ion-forming ionic compounds that do not contain active protons, but whose ligands are capable of providing bulky metallocene-catalyzed cations and their non-coordinating anions. And are described in European Patent Application Publication Nos. 0426637, 0573403, and US Pat. No. 5,387,568, all of which are incorporated herein by reference.
The term “non-coordinating anion” (NCA) does not coordinate to the cation or only weakly coordinates to the cation and is therefore unstable enough to be replaced by a neutral Lewis base. Means an anion that remains. A “compatible” non-coordinating anion is one that does not degrade to neutrality when the initially formed complex degrades. Furthermore, the anion does not transfer an anionic substituent or fragment to the cation, resulting in the formation of a neutral four-coordinated metallocene compound and a neutral byproduct from the anion. Useful non-coordinating anions according to the present invention are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge by +1, and can be replaced by ethylenically or acetylenically unsaturated monomers during polymerization. An anion that retains sufficient instability to make it possible.

In addition to these activator compounds or cocatalysts, scavengers such as trimethylaluminum, triethylaluminum, tri-isobutylaluminum, and / or tri-octylaluminum can be used. Preferably, tri-isobutylaluminum and / or tri-octylaluminum is used.
The process of the present invention is also a neutral Lewis acid, initially a co-catalyst compound that forms a cationic metal complex and a non-coordinating anion or zwitterionic complex by reaction with the compound of the present invention or An activator compound can be employed. For example, tris (pentafluorophenyl) boron or aluminum abstracts the hydrocarbyl or hydride ligand, yields the cationic metal complex of the present invention, and acts to stabilize non-coordinating anions. For examples of similar Group 4 metallocene compounds, see European Patent Publication Nos. 0427697 and 0520732. See also the methods and compounds of EP-A-0495375. See US Pat. Nos. 5,624,878, 5,486,632, and 5,527,929 for the formation of zwitterionic complexes using similar Group 4 compounds.

Another suitable activating cocatalyst that is ion forming is of formula (16):
(OX ^{e +} ) _d (A ^d- ) _e (16)
Wherein OX ^{e +} is a cationic oxidant having a charge of e +; e is from 1 to 3; and a salt of a cationic oxidant and a non-coordinating compatible anion D is an integer of 1 to 3; A ^d− is a non-coordinating anion having a charge of d−. Examples of cationic oxidants include ferrocenium, hydrocarbyl substituted ferrocenium, Ag ⁺ , or Pb ⁺² . A preferred embodiment of A ^d- is an anion as defined above, in particular tetrakis (pentafluorophenyl) borate.

  A typical non-alumoxane activator: catalyst ratio, preferably NCA activator: catalyst ratio, is a 1: 1 molar ratio. An alternative preferred range is 0.1: 1 to 100: 1, or 0.5: 1 to 200: 1, alternatively 1: 1 to 500: 1, alternatively 1: 1 to 1000: 1. A particularly useful range is 0.5: 1 to 10: 1, preferably 1: 1 to 5: 1.

Bulky activators We have found that the hafnocene catalysts described herein typically have a higher amount of allyl chain ends under the same polymerization conditions than similar zirconocenes. However, the inventors have also surprisingly found that in the presence of a bulky activator, zirconocene provides a similar amount of allyl chain ends as hafnocene.

A “bulky activator” as used herein has the formula:
Wherein each R ₁ is independently a halide, preferably a fluoride;
Each R ₂ is independently a halide, substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl Preferably R ₂ is a fluoride or a perfluorinated phenyl group;
Each R ₃ is a halide, a substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. Preferably R ₃ is a fluoride or a perfluorinated C ₆ aromatic hydrocarbyl group;
Here, R ₂ and R ₃ can form one or more saturated or unsaturated substituted or unsubstituted rings, preferably R ₂ and R ₃ form a perfluorinated phenyl ring. And;
L is a neutral Lewis base; (L—H) ⁺ is a Bronsted acid; d is 1, 2 or 3;
The anion has a molecular weight of more than 1020 g / mol; and at least three of the substituents on the B atom have a molecular volume of more than 250 cubic cubic, or more than 300 cubic cubic, or more than 500 cubic cubic, respectively. Have.

In the present specification, “molecular volume” is used as an approximation of the spatial steric size of an activator molecule in solution. Comparing substituents with different molecular volumes allows a substituent with a smaller molecular volume to be considered "less bulky" in comparison to a substituent with a larger molecular volume . Conversely, a substituent having a larger molecular volume can be considered “larger in bulk” than a substituent having a smaller molecular volume.
Molecular volume is 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 Can be calculated as is. Molecular volume in cubic Å Units (MV) has the formula: is calculated using the MV = 8.3 V _s, wherein, V _s is the estimated volume. 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 volumes in the following table. For fused rings, V _s decreases by 7.5% per fused ring.

Typical bulky substituents of activators suitable in the present invention and their respective estimated volumes and molecular volumes are shown in the table below. The bond in the interrupted line indicates the bond to boron as in the general formula.

Typical bulky activators that are useful in the catalyst systems herein include the following compounds:
Trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate, tri (t-butyl) ammonium tetrakis (Perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium ) Tetrakis (perfluoronaphthyl) borate, Tropylium tetrakis (perfluoronaphthyl) borate, Triphenylcarbe Umtetrakis (perfluoronaphthyl) borate, Triphenylphosphonium tetrakis (perfluoronaphthyl) borate, Triethylsilylium tetrakis (perfluoronaphthyl) borate, Benzene (diazonium) tetrakis (perfluoronaphthyl) borate, Trimethylammonium tetrakis (perfluorobiphenyl) borate, Triethylammonium Tetrakis (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl Anilinium Tetrakis (Perfluorobife L) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluorobiphenyl) borate , Triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, [4-t-butyl- PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B], and a class disclosed in US Pat. No. 7,297,653.

Combinations of activators It is within the scope of the present invention that the catalyst compound can be combined with one or more activators or activation methods described above. For example, combinations of activators are described in US Pat. Nos. 5,153,157, 5,453,410, EP 0573120, WO 94/07928, and 95/14044. Has been. These references all discuss the use of alumoxane in combination with an ionogenic activator.

Optional coactivators and scavengers In addition to these activator compounds, scavengers or coactivators can be used. Alkyl aluminum or organoaluminum compounds that can be used as co-activators (or scavengers) include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylzinc Is mentioned.
Optional Support Material In embodiments of the present invention, the catalyst system can include an inert support material. Preferably, the support material is a porous support material, such as talc and inorganic oxides. Other carrier materials include zeolite, clay, organic clay, or any other organic or inorganic carrier material, or mixtures thereof.

Preferably, the support material is an inorganic oxide in finely ground form. Inorganic oxide materials suitable for use in the metallocene catalyst system of the present invention include Group 2, 4, 13 and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be employed alone or in combination with silica or alumina are magnesia, titania, zirconia, and the like. However, other suitable carrier materials can be employed, such as finely divided functional polyolefins such as finely divided polyethylene. Particularly useful carriers include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolite, talc, clay and the like. Also, combinations of these carrier materials, such as silica-chromium, silica-alumina, silica-titania, etc. can be used. 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 .

The support material, most preferably the inorganic oxide, has a surface area in the range of about 10 to about 700 m ² / g, a pore volume in the range of about 0.1 to about 4.0 cc / g, and a range of about 5 to about 500 μm. It is preferable to have an average particle size of More preferably, the support material has a surface area of about 50 to about 500 m ² / g, a pore volume of about 0.5 to about 3.5 cc / g, and an average particle size in the range of about 10 to about 200 μm. Most preferably, the support material has a surface area of about 100 to about 400 m ² / g, a pore volume of about 0.8 to about 3.0 cc / g, and an average particle size in the range of about 5 to about 100 μm. The average pore size of the support material useful in the present invention is in the range of 10 to 1000 mm, preferably 50 to about 500 mm, and most preferably 75 to about 350 mm. In some embodiments, the support material is high surface area amorphous silica (surface area = 300 m ² / g; pore volume = 1.65 cm ³ / g). The preferred silica is W.W. R. It is marketed by Davison Chemical Division of Grace and Company under the trade name DAVISON 952 or DAVISON 955. In other embodiments, DAVISON 948 is used.

  The carrier material must be dry, i.e. not contain absorbed water. Drying of the support material can be carried out by heating or calcination at about 100 ° C to about 1000 ° C, preferably at least about 600 ° C. When the support material is silica, it is at least up to 200 ° C, preferably about 200 ° C to about 850 ° C, most preferably about 600 ° C, about 1 minute to about 100 hours, about 12 hours to about 72 hours, or Heat for about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups in order to create the supported catalyst system of the present invention. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one metallocene compound and an activator.

Method for preparing a supported catalyst system A support material having reactive surface groups, typically hydroxyl groups, is slurried in a nonpolar solvent and the resulting slurry is contacted with a solution of a metallocene compound and an activator. In some embodiments, the carrier material slurry is first mixed with an activator (preferably an alumoxane) for about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Contact for a range of hours. The solution of the metallocene compound is then contacted with the isolated carrier / activator. In some embodiments, the supported catalyst system is formed in situ.
The mixture of metallocene, activator, and carrier is heated to about 0 ° C to about 70 ° C, preferably about 23 ° C to about 60 ° C, preferably at room temperature. Contact times are typically in the range of about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

  Suitable non-polar solvents are materials in which all of the reactants used in the present invention, ie, the activator and metallocene compound, are at least partially soluble and are liquid at the reaction temperature. Preferred non-polar solvents are alkanes such as isopentane, hexane, n-heptane, octane, nonane and decane, but various other materials such as cycloalkanes such as cyclohexane, aromatics such as benzene, toluene and ethylbenzene. It can also be adopted.

  In an embodiment of the present invention, a supported polymerization catalyst is formed by contacting a support material with a solution of a metallocene compound and an activator such that reactive groups on the support material are titrated. The time for contact between the metallocene compound, the activator and the support material is the length required to titrate the reactive groups on the support material. “Titrating” means reacting with available reactive groups on the surface of the support material, thereby reducing surface hydroxyl groups by at least 80%, at least 90%, at least 95%, or at least 98%. It is. The concentration of surface reactive groups can be determined based on the calcination temperature and the type of support material used. The calcination temperature of the support material affects the number of surface-reactive groups on the support material that can be used to react with the metallocene compound and the activator; the higher the drying temperature, the fewer the number of sites. For example, typical if the support material is silica that is dehydrated by fluidizing it with nitrogen and heating it at about 600 ° C. for about 16 hours prior to its use in the initial catalyst system synthesis step. A surface hydroxyl group concentration of about 0.7 mmol (mmol / g) per gram is achieved. Thus, the exact molar ratio of activator to surface reactive groups on the carrier varies. Preferably, this ratio is determined individually to ensure that only as much activator is added to the solution as is deposited on the support material without leaving excess activator in the solution. Is done.

The amount of activator deposited on the support material without leaving an excess in solution can be determined in any conventional manner, for example, the activator is added to the slurry of the support in a solvent. Can be determined by adding by any technique known in the art, such as < ¹ > H-NMR, until the activator is detected as a solvent solution. For example, for a silica support material heated at about 600 ° C., the amount of activator added to the slurry is such that the molar ratio of boron: hydroxyl groups (OH) on silica is about 0.5: 1 to about The amount is 4: 1, preferably about 0.8: 1 to about 3: 1, more preferably about 0.9: 1 to about 2: 1, most preferably about 1: 1. The amount of boron on the silica can be measured using ICPES (Inductively Coupled Plasma Emission Spectroscopy), which is edited by CR Brundle, CA Evans, Jr. and S. Wilson, Encyclopedia of Materials Characterization, Butterworth- Heinemann, Boston, Mass., 1992, pp. 633-644, JW Olesik, “Inductively Coupled Plasma-Optical Emission Spectroscopy”. In another embodiment, an amount of activator is added such that it is present in excess of the amount deposited on the support, and then any excess activator is removed, for example, by filtration and washing. It is also possible.
The inventors have surprisingly found that the catalyst system described herein, in particular hafnocene, exceeds 150 kg / g (catalyst) time ⁻¹ at temperatures above 90 ° C., 300 kg / g (catalyst) time. more than ^1, or 450 kg / g were found to have a productivity of more than (catalyst) time ^-1.

Catalytic Process In an embodiment of the present invention, the present invention relates to a method for preparing a vinyl terminated propylene polymer, the method comprising propylene and an optional comonomer, a catalyst system comprising an activator and at least one metallocene compound. Wherein the metallocene compound is a compound described herein, typically of the formula:

A compound represented by the formula:
M is hafnium or zirconium, preferably hafnium; each X is independently a hydrocarbyl group having 1 to 20 carbon atoms, hydride, amide, alkoxide, sulfide, phosphide, halide, diene, amine, phosphine, Selected from the group consisting of ethers, and combinations thereof (two Xs may form part of a fused ring or ring system), preferably each X is independently a halide and C _1- Selected from C ₅ alkyl groups, preferably each X is a methyl group; each R ₁ is independently a C ₁ -C ₁₀ alkyl group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl , or isomers thereof, preferably each R ₁ is a methyl group; each R ₂ is independently, C ₁ -C ₁₀ alkyl group, preferably, Chill, ethyl, propyl, butyl, pentyl, hexyl or isomers thereof, preferably each R ₂ is n- propyl group; each R ₃ is hydrogen; each R _4, R ₅ And R ₆ is hydrogen, or a substituted hydrocarbyl group, or an unsubstituted hydrocarbyl group, or a heteroatom, preferably each R ₄ , R ₅ and R ₆ is hydrogen; T is a bridging group; Preferably, T is dialkyl silicon or dialkyl germanium, preferably T is dimethyl silicon; provided that any of the adjacent R ₄ , R ₅ and R ₆ groups are fused or multi-centered fused ring systems The ring may be aromatic, partially saturated or saturated; where at least 35% (based on total unsaturation), preferably at least 50%, at least 6 %, At least 70%, at least 80%, propylene polymer having at least 90%, or at least 95% allyl chain ends occur.

  If desired, other additives such as one or more scavengers, promoters, modifiers, chain transfer agents, reducing agents, oxidizing agents, hydrogen, alkylaluminums, or silanes can also be used.

Optional comonomers useful for preparing vinyl terminated polymers in the present invention include ethylene and / or C ₄ -C ₄₀ olefins, preferably ethylene and / or C ₅ -C ₂₅ olefins, or preferably ethylene and And / or C ₆ -C ₁₈ olefins. C ₄ -C ₄₀ olefin monomers can be linear, branched, or cyclic. C ₄ -C ₄₀ cyclic olefins may be monocyclic or polycyclic not distorted or distorted, which may contain a hetero atom and / or one or more functional groups. Typical C ₄ -C ₄₀ olefin monomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, Cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1 -Hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and the respective Homologues and derivatives, preferably norbornene as shown below, norbornadiene, and dicyclopentadiene:

Is mentioned.

In some embodiments where butene is a comonomer, the butene source may be a mixed butene stream comprising various isomers of butene. The 1-butene monomer is expected to be preferentially consumed by the polymerization process. The use of such mixed butene streams is often a waste stream from the purification process, such as a C ₄ raffinate stream, and is therefore substantially less expensive than pure 1-butene. So providing economic benefits.

  The method of the present invention can be performed in any manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such methods can be performed in batch, semi-batch, or continuous mode. Homogeneous polymerization and slurry processes are preferred (homogeneous polymerization is defined as a process in which at least 90% by weight of the product is soluble in the reaction medium). The bulk homogeneous method is particularly preferred (the bulk method is defined as a method in which the monomer concentration in all feeds into the reactor is 70% by volume or more). Alternatively, no solvent or diluent is present or added in the reaction medium (small amounts or typically found with monomers used as a support for the catalyst system or other additives, Excluding the amount of propane in propylene). In another embodiment, the method is a slurry method. As used herein, the term “slurry polymerization method” means a polymerization method that employs a supported catalyst and polymerizes monomers on the supported catalyst particles. At least 95% by weight of the polymer product derived from the supported catalyst is present in the form of granules as solid particles (not dissolved in the diluent).

Suitable diluents / solvents for the polymerization include non-coordinating inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as Cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof as can be found commercially (Isopar ™); perhalogenated hydrocarbons such as perfluorinated C _4-10 alkanes, chlorobenzene And aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, mesitylene, and xylene. Suitable solvents are also liquid olefins which can act as monomers or comonomers, such as ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-octene, 1-decene, and mixtures thereof. In preferred embodiments, aliphatic hydrocarbon solvents such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof Cyclic and alicyclic hydrocarbons such as are used as solvents. In another embodiment, the solvent is not aromatic, preferably the aromatic is in the solvent less than 1 wt%, preferably less than 0.5 wt%, preferably 0 wt%, based on the weight of the solvent. Present in less than%.

In a preferred embodiment, the monomer and comonomer feed concentrations for polymerization are 60% or less, preferably 40% or less, or preferably 20% or less by volume of solvent, based on the total volume of the feed stream. Preferably the polymerization is carried out in a bulk process.
In some embodiments, the productivity is 4500 g / mmol / hour or more, preferably 5000 g / mmol / hour or more, preferably 10,000 g / mmol / hour or more, preferably 50,000 g / mmol / hour or more. . In other embodiments, the productivity is at least 80,000 g / mmol / hour, preferably at least 150,000 g / mmol / hour, preferably at least 200,000 g / mmol / hour, preferably at least 250,000 g / mmol / hour. Time, preferably at least 300,000 g / mmol / hour.

Preferred polymerizations can be carried out at any temperature and / or pressure suitable to obtain the desired vinyl terminated polymer. Typical temperatures and / or pressures are for example about 0 ° C. to about 300 ° C., preferably about 20 ° C. to about 200 ° C., preferably about 35 ° C. to about 150 ° C., preferably about 40 ° C. to about 120 ° C., Preferably, the temperature is in the range of about 45 ° C. to about 80 ° C., the pressure is in the range of about 0.35 MPa to about 10 MPa, preferably about 0.45 MPa to about 6 MPa, or preferably about 0.5 MPa to about 4 MPa.
In a typical polymerization, the reaction run time is in the range of up to 300 minutes, preferably about 5 to 250 minutes, or preferably about 10 to 120 minutes.
In a preferred embodiment, hydrogen is 0.001 to 50 psig (0.007 to 345 kPa), preferably 0.01 to 25 psig (0.07 to 172 kPa), more preferably 0.1 to 10 psig in the polymerization reactor. It exists at a partial pressure of (0.7-70 kPa). In the system of the present invention, it has been found that hydrogen can be used to provide enhanced activity without significantly compromising the ability of the catalyst to provide allylic chain ends. Preferably, the catalytic activity (calculated as g / mmol (catalyst) / hour) is at least 20%, preferably at least 50%, preferably at least 100% higher than the same reaction without hydrogen.

In an alternative embodiment, the activity of the catalyst is at least 50 g / mmol / hour, preferably 500 g / mmol / hour or more, preferably 5000 g / mmol / hour or more, preferably 50,000 g / mmol / hour or more. In an alternative embodiment, the conversion of the olefin monomer 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 monomer entering the reaction zone. Preferably it is 80% or more.
In a preferred embodiment, little or no alumoxane is used in the process for producing the vinyl terminated polymer. Preferably, the presence of alumoxane is 0 mol%, or alternatively the alumoxane is less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1 moles of aluminum: transition metal. Exist in ratio.
In an alternative embodiment, when alumoxane was used to produce the vinyl terminated polymer, the alumoxane was treated to remove free alkylaluminum compounds, especially trimethylaluminum.
Further, in a preferred embodiment, the activator used to make the vinyl terminated polymer in the present invention is a bulky activator as defined herein and is separate.

  In a preferred embodiment, little or no scavenger is used in the process for producing the vinyl terminated polymer. Preferably the presence of a scavenger (such as trialkylaluminum) is 0 mol% or the scavenger is less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1. Present in a molar ratio of scavenger metal: transition metal.

  In a preferred embodiment, the polymerization is carried out at a temperature of 1) 0 to 300 ° C., preferably 25 to 150 ° C., preferably 40 to 120 ° C., preferably 45 to 80 ° C. 2) Atmospheric pressure to 10 MPa, preferably Carried out at a pressure of 0.35 to 10 MPa, preferably 0.45 to 6 MPa, preferably 0.5 to 4 MPa. 3) Isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and these In an aliphatic hydrocarbon solvent such as a mixture; in cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof (preferably, wherein Aromatics are preferably less than 1% by weight, preferably less than 0.5% by weight, based on the solvent weight. 4) the catalyst system used in the polymerization comprises less than 0.5 mol%, preferably 0 mol% alumoxane, or the alumoxane is less than 500: 1, preferably Is present in an aluminum: transition metal molar ratio of less than 300: 1, preferably less than 100: 1, preferably less than 1: 1, 5) the polymerization is carried out in one reaction zone, and 6) of the catalyst compound Productivity is at least 80,000 g / mmol / hour, preferably at least 150,000 g / mmol / hour, preferably at least 200,000 g / mmol / hour, preferably at least 250,000 g / mmol / hour, preferably at least 300 7) Optionally, a scavenger (trialkylalumination) Is not present (0 mol%) or the capture agent is less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1 metal: transition 8) Optionally, hydrogen is present in the polymerization reactor in the polymerization reactor from 0.001 to 50 psig (0.007 to 345 kPa), preferably 0.01 to 25 psig (0.07 to 172 kPa). More preferably, it is present at a partial pressure of 0.1 to 10 psig (0.7 to 70 kPa). In a preferred embodiment, the catalyst system used in the polymerization contains no more than one catalyst compound. A “reaction zone”, also referred to as a “polymerization zone”, is a vessel in which polymerization occurs, such as a batch reactor. When multiple reactors are used in a series or parallel arrangement, each reactor is considered a separate polymerization zone. In the case of multi-stage polymerization in both batch reactors and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone. The room temperature is 23 ° C. unless otherwise specified.

Vinyl-terminated polymer In an embodiment of the present invention, the homogeneous process produces a vinyl-terminated propylene polymer. In some embodiments, the vinyl terminated propylene polymer is, for example, a copolymer of propylene and ethylene. In certain embodiments, the vinyl terminated propylene polymer is, for example, a terpolymer of propylene, ethylene, and a C ₄ -C ₄₀ olefin.

Useful vinyl-terminated polymers made in the present invention include propylene homopolymers comprising propylene and less than 0.5% by weight comonomer, preferably 0% by weight comonomer, wherein the polymer is ( i) at least 93%, preferably at least 95%, preferably at least 97%, preferably at least 98% of allyl chain ends; (ii) 100 g / mol or more, preferably from about 150 to about 60,000 g / mol, preferably Is 200 to 45,000 g / mol, preferably 250 to 25,000 g / mol, preferably 300 to 10,000 g / mol, preferably 400 to 9,500 g / mol, preferably 500 to 9,000 g / mol, preferably the number average molecular weight in the range of 750~9,000g / mol is (Mn, ¹ H (Iii) (iii) isobutyl chain end: allylic vinyl group ratio of 0.8: 1 to 1.3: 1.0, and (iv) less than 1400 ppm, preferably less than 1200 ppm, preferably Has less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm aluminum.

Useful vinyl-terminated polymers produced in the present invention are also 100 g / mol or higher, preferably about 150 to about 60,000 g / mol, preferably 200 to 45,000 g / mol, preferably 250 to 25, 000 g / mol, preferably 300~10,000g / mol, preferably 400~9,500g / mol, preferably 500~9,000g / mol, preferably in the range of 750~9,000g / mol Mn ⁽¹ H A propylene copolymer having (as measured by NMR), said copolymer comprising (i) 10 to 90 mol%, preferably 15 to 85 mol%, preferably 20 to 80 mol%, preferably 30 to 75 mol%, preferably 50-90 mol% propylene, and (ii) 10-90 mol%, preferably 85-15 mol%, preferably 20-80 mol%, preferably 25-70 mol%, preferably 10-50 mol% of one or more α-olefin comonomers, preferably ethylene, butene, hexene or octene, preferably ethylene Wherein the polymer has at least X% (based on total unsaturation) allyl chain ends, wherein 1) when 10 to 60 mol% ethylene is present in the copolymer, X = (− 0.94 (mol% of ethylene incorporated) +100, or 1.20 (−0.94 (mol% of ethylene incorporated) +100, or 1.50 (−0.94 (incorporated)) Mol% of ethylene) +100, and 2) when more than 60 mol% to less than 70 mol% ethylene is present in the copolymer, X = 45, alternatively 50, or 60, and 3) if 70-90 mol% ethylene is present in the copolymer, X = 1.83 × (mol% of incorporated ethylene) −83, or 1.20. [1.83 × (mol% of incorporated ethylene) −83], or 1.50 [1.83 × (mol% of incorporated ethylene) −83], or X is 80% or more , Preferably 85% or more, preferably 90% or more, preferably 95% or more.

  In an alternative embodiment, the vinyl terminated polymer has at least 80%, preferably at least 85%, preferably at least 90% isobutyl chain ends, based on the sum of isobutyl and n-propyl saturated chain ends. Alternatively, the polymer is 0.8: 1 to 1.35: 1.0, preferably 0.9: 1 to 1.20: 1.0, preferably 0.9: 1.0 to 1.1: 1. An isobutyl chain end to allylic vinyl group ratio of 0.0.

Useful vinyl-terminated polymers produced in the present invention further include more than 90 mol%, preferably 95-99 mol%, preferably 98-99 mol% propylene, and less than 10 mol%, preferably 1-4 mol%, Or preferably a propylene polymer comprising 1-2 mol% ethylene, wherein the polymer comprises (i) at least 93%, preferably at least 95%, preferably at least 97%, preferably at least 98% allyl. The chain end is (ii) 100 g / mol or more, preferably about 150 to about 60,000 g / mol, preferably 200 to 45,000 g / mol, preferably 250 to 25,000 g / mol, preferably 300 to 10 000 g / mol, preferably 400 to 9,500 g / mol Preferably 500~9,000g / mol, or preferably in the range of 750~9,000g / mol Mn to (as determined by ¹ H-NMR), and (iii) 0.8: 1~1.35: An isobutyl chain end to allylic vinyl group ratio of 1.0 and an aluminum of less than 1400 ppm, preferably less than 1200 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, or preferably less than 100 ppm.

Useful vinyl-terminated polymers produced in the present invention further include (i) at least 50 mol%, preferably 60-90 mol%, preferably 70-90 mol% propylene, and 10-50 mol%, preferably 10- Mention may be made of propylene polymers comprising 40 mol%, preferably 10-30 mol% ethylene, wherein the polymer comprises (ii) at least 90%, preferably at least 91%, preferably at least 93%, preferably at least 95%. Or preferably at least 98% allyl chain ends; measured by ¹ H-NMR, 100 g / mol or more, preferably about 150 to about 60,000 g / mol, preferably 200 to 45,000 g / mol, preferably 250-25,000 g / mol, preferably 300- Mn in the range of 0.0 000 g / mol, preferably 400 to 9,500 g / mol, preferably 500 to 9,000 g / mol, or preferably 750 to 9,000 g / mol, and (iii) 0.8: Having an isobutyl chain end: allylic vinyl group ratio of 1-1.3: 1.0, wherein the monomer having 4 or more carbon atoms is 0-3 mol%, preferably less than 1 mol%, preferably Is present at less than 0.5 mol%, or preferably at 0 mol%.

Useful vinyl-terminated polymers produced in the present invention also include (i) at least 50 mol%, preferably at least 60 mol%, preferably 70-99.5 mol%, preferably 80-99 mol%, preferably 90- 98.5 mol% propylene, (ii) 0.1-45 mol%, preferably at least 35 mol%, preferably 0.5-30 mol%, preferably 1-20 mol%, preferably 1.5-10 mol% ethylene, and (iii) 0.1 to 5 mol%, of propylene preferably comprising 0.5 to 3 mol%, preferably 0.5～1Mol% of C ₄ -C ₁₂ olefins, e.g., butene, hexene or octene, preferably butene Polymer, wherein the polymer is (a) at least 90%, preferably Without even 91%, preferably at least 93%, preferably at least 95%, preferably at least 98% allyl chain ends, as determined by ^{(b) 1 H-NMR,} 100g / mol or more, preferably about 150 to about 60,000 g / mol, preferably 200-45,000 g / mol, preferably 250-25,000 g / mol, preferably 300-10,000 g / mol, preferably 400-9,500 g / mol, preferably 500- Mn in the range of 9,000 g / mol, preferably 750 to 9,000 g / mol, and (c) isobutyl chain end: allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0 .

Useful vinyl-terminated polymers produced in the present invention also include (i) at least 50 mol%, preferably at least 60 mol%, preferably 70-99.5 mol%, preferably 80-99 mol%, preferably 90- 98.5 mol% propylene, (ii) 0.1-45 mol%, preferably at least 35 mol%, preferably 0.5-30 mol%, preferably 1-20 mol%, preferably 1.5-10 mol% ethylene, And (iii) 0.1 to 5 mol%, preferably 0.5 to 3 mol%, preferably 0.5 to 1 mol% of a diene (C ₄ -C ₁₂ α-ω diene, such as butadiene, hexadiene, octadiene) , Norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, and disi Propylene polymers, such as lopentadiene), wherein the polymer comprises (a) at least 90%, preferably at least 91%, preferably at least 93%, preferably at least 95%, preferably at least 98%. Allyl chain end, (b) 100 g / mol or more, preferably about 150 to about 60,000 g / mol, preferably 200 to 45,000 g / mol, preferably 250 to 25,000 g / mol as measured by ¹ H-NMR Mn, preferably 300 to 10,000 g / mol, preferably 400 to 9,500 g / mol, preferably 500 to 9,000 g / mol, preferably 750 to 9,000 g / mol, and (c) Having an isobutyl chain end: allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0 And propylene polymers.

Useful vinyl-terminated polymers that can be produced using the catalyst systems described herein include 200 g / mol or more, preferably 300 to 60,000 g / mol, 400 as measured by ¹ H-NMR. 50,000 g / mol, preferably 500 to 35,000 g / mol, preferably 300 to 15,000 g / mol, preferably 400 to 12,000 g / mol, or preferably 750 to 10,000 g / mol of Mn. And (i) about 20-99.9 mol%, preferably about 25 to about 90 mol%, about 30 to about 85 mol%, about 35 to about 80 mol%, about 40 to about 75 mol%, or about 50 to about at least one C ₅ -C ₄₀ olefins 95 mol%, preferably C ₅ -C ₃₀ alpha-olefins, more preferably C ₅ -C ₂₀ alpha- Olefins, preferably C ₅ -C ₁₂ alpha-olefin, preferably pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, Cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1,5-cyclooctadiene, 1- Hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and each of these Homologues and derivatives thereof, preferably norbornene, norbornadiene, and dicyclopentadiene, and (ii) about 0.1-80 mol%, preferably about 5-70 mol%, about 10-about 65 mol%, about 15-about 55 mol% , About 25 to about 50 mol%, or about 30 to about 80 mol% of propylene, wherein the vinyl-terminated polymer is at least 40%, preferably at least 50%, at least 60%, at least 70%. %, At least 80%, at least 90%, at least 95% of allyl chain ends, and optionally less than 0.70: 1, preferably less than 0.65: 1, less than 0.60: 1, 0.50: An isobutyl chain end: allylic chain end ratio of less than 1 or less than 0.25: 1, and optionally ¹ H An allyl chain end: vinylidene chain end ratio of greater than 2: 1, preferably greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1 as measured by NMR; Further optionally, having an allyl chain end: vinylene chain end ratio of greater than 10: 1, preferably greater than 15: 1, or greater than 20: 1, and optionally, preferably substantially isobutyl chain ends. Has no or preferably has less than 0.1% by weight of isobutyl chain ends. For further information on such vinyl-terminated polymers, see US Patent Application No. 13 / 072,249, filed March 25, 2011, entitled “Vinyl Terminated Higher Olefin Copolymers and Methods to Produce Therof”. I want.

Useful vinyl-terminated polymers that can be produced using the catalyst systems described herein are also 200 g / mol or higher, preferably 300-60,000 g / mol as measured by ¹ H-NMR. 400 to 50,000 g / mol, preferably 500 to 35,000 g / mol, preferably 300 to 15,000 g / mol, preferably 400 to 12,000 g / mol, or preferably 750 to 10,000 g / mol. It has a Mn, and (i) about 80~99.9mol%, preferably 85~99.9mol%, more preferably at least one C ₄ olefin 90~99.9mol%, preferably 1-butene; And (ii) about 0.1-20 mol%, preferably 0.1-15 mol%, more preferably 0.1-10 mol% Polymers comprising propylene; wherein the vinyl-terminated polymer is at least 40%, preferably at least 50%, at least 60%, at least 70%, or at least 80% allyl chain ends; and optionally, Isobutyl chain end: allyl chain end ratio of less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1, and optionally further More than 2: 1, more than 2.5: 1, more than 3: 1, more than 5: 1 or more than 10: 1 allyl chain end: vinylidene chain end ratio, optionally 10: Having an allyl chain end: vinylene chain end ratio of greater than 1, preferably greater than 15: 1, or greater than 20: 1, and optionally, preferably substantially free of isobutyl chain ends, Good Preferably it has an isobutyl chain end of less than 0.1% by weight. For further information on such vinyl-terminated polymers, see US Patent Application No. 13 / 072,249, filed March 25, 2011, entitled “Vinyl Terminated Higher Olefin Copolymers and Methods to Produce Therof”. I want.

Useful vinyl-terminated polymers that can be produced using the catalyst systems described herein are also at least 200 g / mol, preferably 200 to 100,000 g / mol as measured by ¹ H-NMR. Having an Mn of 200 to 75,000 g / mol, preferably 200 to 60,000 g / mol, preferably 300 to 60,000 g / mol, or preferably 750 to 30,000 g / mol; Multiple, preferably 2 or more, 3 or more, 4 or more C ₄ -C ₄₀ , preferably C ₄ -C ₃₀ , C ₄ -C ₂₀ , or C ₄ -C ₁₂ olefin derived units, preferably Is butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopenta Ene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxa-norbornene, 7-oxa norbornadiene, substituted derivatives thereof, and include polymers containing these isomers, where, C ₄ -C ₄₀ the vinyl-terminated polymers comprising olefin derived units, contain no units derived from propylene in substantially, preferably comprises propylene less than 0.1 wt%; and wherein the polymer containing a C ₄ -C ₄₀ olefin-derived units , 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; and optionally, An allyl chain end: vinylidene chain end ratio greater than 1: 1, preferably greater than 2.5: 1, greater than 3: 1, greater than 5: 1, or greater than 10: 1; Having an allyl chain end: vinylene chain end ratio of greater than 1, preferably greater than 15: 1, or greater than 20: 1; more optionally, preferably substantially free of isobutyl chain ends, or preferably Has less than 0.1% by weight of isobutyl chain ends. In some embodiments, these vinyl terminated polymers are ethylene derived units, preferably at least 5 mol%, preferably at least 15 mol%, preferably at least 25 mol%, preferably at least 35 mol%, preferably at least 45 mol%, preferably May comprise at least 60 mol%, preferably at least 75 mol%, or preferably at least 90 mol% ethylene. For further information on such vinyl-terminated polymers, see US Patent Application No. 13,072,288, filed March 25, 2011 entitled “Vinyl Terminated Higher Olefins Polymers and Methods to Produce Therof”. I want.

The vinyl-terminated propylene polymer produced in the present invention is preferably 100 g / mol or more, preferably about 150 to about 60,000 g / mol, preferably 200 to 45,000 g / mol, as measured by ¹ H-NMR. mol, preferably 250 to 25,000 g / mol, preferably 300 to 10,000 g / mol, preferably 400 to 9,500 g / mol, preferably 500 to 9,000 g / mol, preferably 750 to 9,000 g / mol. Mn in the range of mol. Furthermore, the desired molecular weight range may be any combination of the above arbitrary upper molecular weight and arbitrary lower molecular weight.

  In another embodiment, the vinyl-terminated propylene polymer produced in the present invention is about 1,000 to about 60,000 g / mol, preferably about 2,000 to about 5,000, as measured using the GPC-DRI method. Mw in the range of 50,000 g / mol, preferably about 3,000 to 35,000 g / mol, and / or about 1,700 to about 150,000 as measured using GPC-DRI method as described below. Having an Mz in the range of about 000 g / mol, or preferably about 800 to 100,000 g / mol.

  The molecular weight distribution (Mw / Mn) is also measured by the GPC-DRI method described later. In some embodiments, the copolymer of the present invention has a Mw / in the range of 1.0-20 (alternatively about 1.2-20, alternatively about 1.5-10, alternatively about 1.7-5.5). Mn (both measured by GPC-DRI).

In certain embodiments, the vinyl terminated propylene polymer produced in the present invention is 100 g / mol or more, preferably from about 150 to about 60,000 g / mol, preferably from 200 to ¹ , as measured by ¹ H-NMR. 45,000 g / mol, preferably 250-25,000 g / mol, preferably 300-10,000 g / mol, preferably 400-9,500 g / mol, preferably 500-9,000 g / mol, preferably 750-500 Mn in the range of 9,000 g / mol; about 1,000 to about 60,000 g / mol, preferably about 2,000 to 50,000 g / mol, preferably about 3,000 to 35,000 g / mol. Mw, and about 1,700 to about 150,000 g / mol, or preferably about 800 to 100,000 g Having a Mz of the range of mol.

As used herein, Mn is the number average molecular weight measured by ¹ H-NMR unless otherwise specified, Mw is the weight average molecular weight measured by gel permeation chromatography (GPC), and Mz Is the z-average molecular weight measured by GPC. Mn, Mw and Mz are measured using the GPC method using a high temperature size exclusion chromatograph (from SEC, Waters Corporation or Polymer Laboratories) equipped with a differential refractive index detector (DRI). Details of the experiment are described in T. Sun, P. Brant, RR Chance, and WW Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Polymer Laboratories PLgel 10 mm Mixed-B columns are used. The nominal flow rate is 0.5 cm ³ / min and the nominal injection volume is 300 μL. The various transfer lines, columns and differential refractometer (DRI detector) are housed in an oven maintained at 135 ° C. The solvent for the SEC experiment is prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 L of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 μm glass pre-filter followed by a 0.1 μm Teflon filter. The TCB is then degassed using an online degasser prior to entering the SEC. The polymer solution is prepared by placing the dried polymer into a glass container, adding the desired amount of TCB, and then heating the mixture at 160 ° C. for about 2 hours with continuous stirring. All quantities are measured by weight. The density of TCB used to express polymer concentration in mass / volume units is 1.463 g / mL at room temperature and 1.324 g / mL at 135 ° C. The injection concentration is 1.0-2.0 mg / mL, with smaller concentrations being adopted for larger molecular weight samples. Prior to running each sample, the DRI detector and injector are purged. The flow rate in the apparatus is then increased to 0.5 mL / min and the DRI is allowed to stabilize for 8-9 hours before injecting the first sample. The concentration c at each time point in the chromatogram can be calculated from the DRI signal, I _DRI minus the baseline:
c = K _DRI × I _DRI / (dn / dc)
_Where K _DRI is a constant determined by calibrating the DRI and (dn / dc) is the increment in refractive index for the system. The refractive index of TCB is 135 ° C. and λ = 690 nm, and n = 1.500. For purposes of the present invention and claims thereto, for propylene polymers, (dn / dc) = 0.104, otherwise 0.1. Concentrations are expressed in g / cm ³ , molecular weights are expressed in g / mol, and intrinsic viscosities are expressed in dL / g with respect to the parameter units used throughout this description for the SEC method.

Vinyl-terminated polymers, preferably vinyl-terminated propylene polymers, have saturated chain ends (or ends) and / or unsaturated chain ends (or ends). Unsaturated chain ends include “allyl chain ends”. “Allyl chain end” has the formula:
(Wherein M represents a polymer chain), it is represented by CH ₂ CH—CH ₂ —.

The percentage of allylic chain ends is reported as the mole percentage of allylic vinyl groups relative to the total number of moles of unsaturated chain ends. In some embodiments, the vinyl terminated propylene polymer has at least 35%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% allyl chain ends. The number of allyl chain ends was measured with a 250 MHz NMR spectrometer using deuterated tetrachloroethane as the solvent and using ¹ H-NMR at 120 ° C., and in selected cases, ¹³ C-NMR It is confirmed. Resconi reports proton and carbon assignments for vinyl-terminated polymers in J. American Chemical Soc., 114, 1992, pp. 1025-1032 (useful in the present invention). Uses raw perdeuterated tetrachloroethane, and for the carbon spectrum uses a 50:50 mixture of normal tetrachloroethane and perdeuterated tetrachloroethane, all spectra are 500 MHz for protons and for carbon (Recorded at 100 ° C. using a Bruker spectrometer operating at 125 MHz).

Vinyl terminated polymers such as vinyl terminated propylene polymers also have saturated chain ends that may include isobutyl chain ends. "Isobutyl chain end" is the following formula:
(Wherein M represents a polymer chain) is defined as the end or end of the polymer represented.

The polymer structure in the vicinity of the saturated chain end may vary depending on the type and amount of monomer used and the insertion method during the polymerization process. In some preferred embodiments, the polymer structure involving the four carbons of the isobutyl chain end is:
(Wherein M represents a polymer chain).

The percentage of isobutyl end groups is given by ¹³ C-NMR (as described in the Examples section), as well as Resconi et al, J Am. Chem. Soc., 1992, 114, pp. 1025-1032 for 100% propylene polymer. It is determined using the chemical shift assignments shown in FIG. 2 in and in WO2009 / 155471.
The percentage of isobutyl chain ends is given by ¹³ C-NMR (as described in the Examples section), as well as Resconi et al, J. Am. Chem. Soc., 114, 1992, pp. 1025- for 100% propylene polymer. It is determined using the chemical shift assignments in 1032 and reported herein for vinyl terminated propylene polymers.

  “Isobutyl chain end: allyl chain end ratio” is defined as the ratio of the percentage of isobutyl chain ends to the percentage of allyl chain ends. In some embodiments, the ratio of isobutyl chain ends: allyl chain ends is in the range of about 0.8: 1 to about 1.35: 1. In other embodiments, the ratio of isobutyl chain ends: allyl chain ends is in the range of about 1: 1 to about 1.2: 1. The ratio of isobutyl chain ends: allyl chain ends is a representation of the number of vinyl groups present per polymer chain. For example, an isobutyl chain end: allylic vinyl group ratio of about 1: 1 indicates that on average, there is about one allylic vinyl group per polymer chain.

In some embodiments, the propylene polymer produced in the present invention is atactic. The inventors have surprisingly found that the catalyst system of the present invention results in atactic vinyl-terminated propylene polymers. Although the metallocene compounds of the present invention are racemic isomers and are theoretically capable of yielding isotactic polypropylene, the inventors have found that the inventive catalyst system disclosed herein is surprisingly high. It has been found to result in atactic propylene polymers having a level of vinyl chain ends. The atacticity of propylene polymers can be determined from ¹³ C-NMR by the lack of regularity in the chiral structure of the repeating units, where regularity is determined by Zambelli et al. Macromolecules, 8, pp. 687- As described in 689 (1975) and Macromolecules, 13, pp. 267-270 (1980), it is characterized by a triple of mm, mr, rm and rr.

  Any polymer prepared in the present invention preferably has less than 1400 ppm, preferably less than 1000 ppm, preferably less than 500 ppm, preferably less than 100 ppm, preferably less than 50 ppm, preferably less than 20 ppm, preferably less than 5 ppm aluminum. ICPES (Inductively Coupled Plasma Emission Spectroscopy) was used to determine the amount of elements in the material, and ICPES was edited by CR Brundle, CA Evans, Jr. and S. Wilson, Encyclopedia of Materials Characterization, Butterworth-Heinemann, JW Olesik, "Inductively Coupled Plasma-Optical Emission Spectroscopy" in Boston, Mass., 1992, pp. 633-644.

In preferred embodiments, the vinyl-terminated propylene polymer is based on the weight of the polymer selected from hydroxide, aryl and substituted aryl, halogen, alkoxy, carboxylate, ester, acrylate, oxygen, nitrogen, and carboxyl, Less than 3 wt%, preferably less than 2 wt%, more preferably less than 1 wt%, more preferably less than 0.5 wt%, more preferably less than 0.1 wt%, more preferably 0 wt% Including.
In another embodiment, the vinyl terminated propylene polymer is at least 50% by weight, preferably at least 50% by weight, based on the weight of the copolymer composition, as measured by ¹ H-NMR and assuming one unsaturation per chain. 75% by weight, preferably at least 90% by weight, of olefins having at least 36, preferably at least 51, preferably at least 102 carbon atoms.

  In another embodiment, the vinyl terminated propylene polymer is less than 20 wt%, preferably less than 10 wt%, preferably 5 wt%, as measured by gas chromatograph (GC), based on the weight of the copolymer composition. Less than, more preferably less than 2% by weight of dimers and trimers. The product is analyzed by gas chromatography (Agilent 6890N with automatic injector) using 38 cm / sec helium as carrier gas. A 60 m long column (J & W Scientific DB-1, 60 m × 0.25 mm (inner diameter)) configured with a flame ionization detector (FID), an injector temperature of 250 ° C., and a detector temperature of 250 ° C. X film thickness of 1.0 μm). The sample was injected into a column in an oven at 70 ° C. and then heated to 275 ° C. over 22 minutes (up to 100 ° C. at 10 ° C./min up to 275 ° C. at a rate of 30 ° C./min and maintained. ). An internal standard, usually a monomer, is used to derive the amount of dimer or trimer product obtained. The yields of dimer and trimer products are calculated from the data recorded on the spectrometer. The amount of dimer or trimer product is calculated relative to the internal standard from the area under the corresponding peak on the GC graphic.

In another embodiment, any of the vinyl-terminated polyolefins useful in the invention or described herein, 3-alkyl vinyl end group (wherein alkyl is C ₁ -C ₃₈ alkyl) have , “3-alkyl chain ends” or “3-alkyl vinyl ends”
In expressed, where "..." represents a polyolefin chain, R ^b is, C ₁ -C ₃₈ alkyl group, preferably C ₁ -C ₂₀ alkyl group, e.g., methyl, ethyl, propyl, butyl Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.). The amount of 3-alkyl chain ends is measured using ¹³ C-NMR as described below.

  In preferred embodiments, any vinyl terminated polyolefin described herein or useful in the present invention is at least 5%, preferably at least 10%, at least 20%, at least 30%, based on the total number of unsaturations, Having at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95% of 3-alkyl chain ends.

In preferred embodiments, any vinyl terminated polyolefin described herein or useful in the present invention is at least 5%, preferably at least 10%, at least 20%, at least 30%, based on the total number of unsaturations, At least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95% of 3-alkyl + allyl chain ends (eg, all 3-alkyl chain ends + all allyl chains) End).
In another embodiment, the vinyl-terminated propylene polymer is less than 25 ppm, preferably less than 10 ppm, preferably less than 5 ppm hafnium, as measured by ICPES, based on the resulting polymer yield plus the weight of catalyst employed. Contains zirconium.
In yet other embodiments, the vinyl terminated propylene polymer is a liquid at 25 ° C.
In another embodiment, the vinyl-terminated propylene polymer described herein has a melting point ( _Tm , first melting at DSC) in the range of 60C to 130C, alternatively 50C to 100C. In another embodiment, the vinyl-terminated propylene polymers described herein do not have a DSC detectable melting point after storage for at least 48 hours at ambient temperature (23 ° C.).
The vinyl-terminated propylene polymer is preferably 0 ° C. or lower, preferably −10 ° C. or lower, more preferably −20 ° C. or lower, more preferably −30 ° C. or lower, more preferably when measured by the differential scanning calorimetry described later. Has a glass transition temperature (Tg) of −50 ° C. or lower.

Melting temperature (T _m ) and glass transition temperature (Tg) are measured utilizing differential scanning calorimetry (DSC) using commercially available equipment such as TA Instruments Model 2920 DSC. Typically, 6-10 mg of sample stored at room temperature for at least 48 hours is sealed in an aluminum pan and loaded into the room temperature apparatus. The sample is equilibrated at 25 ° C. and then cooled to −80 ° C. at a cooling rate of 10 ° C./min. The sample is held at −80 ° C. for 5 minutes and then heated to 25 ° C. at a heating rate of 10 ° C./min. The glass transition temperature is measured from the heating cycle. Alternatively, the sample is equilibrated at 25 ° C. and then heated to 150 ° C. at a heating rate of 10 ° C./min. The endothermic melting transition, if present, is analyzed for the onset and peak temperatures of the transition. The reported melting temperature is the peak melting temperature from the first heating unless otherwise specified. For samples that exhibit multiple peaks, the melting point (or melting temperature) is defined as the peak melting temperature from the DSC melting diagram (ie, associated with the maximum endothermic calorimetric response in that temperature range).
In another embodiment, the vinyl-terminated polymer described herein has a viscosity at 60 ° C. of greater than 1000 cP, greater than 12,000 cP, or greater than 100,000 cP. 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 is measured using a Brookfield digital viscometer.

Uses of vinyl-terminated polymers The vinyl-terminated polymers prepared in the present invention can be functionalized by reacting allyl groups and heteroatom-containing groups of the polymer with or without a catalyst. . Examples include catalytic hydrosilylation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydroamination, with or without an activator such as a free radical generator (eg, peroxide), or Maleation is included.

  In some embodiments, the vinyl-terminated polymer produced in the present invention is a US Pat. 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 US patent application Ser. No. 12 / 487,739 filed Jun. 19, 2009 (WO 2009/155472). Functionalized as described in the publication.

Functionalized polymers can be used in oil additives and many other applications. Preferred applications include lubricants and / or fuel additives. Preferred heteroatom-containing groups include amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and maleic anhydride.
In certain embodiments of the invention, the vinyl-terminated polymers disclosed herein or functionalized analogs thereof are useful as additives. In some embodiments, the vinyl terminated polymers disclosed herein or functionalized analogs thereof are useful as additives to lubricating oils. Certain embodiments relate to lubricating oils comprising the vinyl terminated polymers disclosed herein or functionalized analogs thereof.

In other embodiments, the vinyl-terminated polymers disclosed herein can be used as monomers for preparing polymer products. Methods that can be used to prepare these polymer products include coordination polymerization and acid catalyzed polymerization. In some embodiments, the polymer product may be a homopolymer. For example, using vinyl terminated polymer (A) as a monomer, it is possible to form a homopolymer product having the formula (A) _n , where n is the degree of polymerization.
In other embodiments, the polymer product formed from a mixture of monomeric vinyl terminated polymers can be a mixed polymer comprising two or more different repeating units. For example, copolymerizing a vinyl terminated polymer (A) and a different vinyl terminated polymer (B) yields the formula (A) _n (B) _m where n is a vinyl terminated polymer present in the mixed polymer product. It is possible to form a mixed polymer product having a number of molar equivalents of type polymer (A) and m is the number of molar equivalents of vinyl terminated polymer (B).

In yet other embodiments, the polymer product can be formed from a mixture of a vinyl terminated polymer and another alkene. For example, when vinyl terminated polymer (A) and alkene (B) are copolymerized, formula (A) _n (B) _m (where n is the mole of vinyl terminated polymer present in the mixed polymer product). It is possible to form mixed polymer products having the number of equivalents, where m is the number of molar equivalents of alkene.

In another embodiment, the present invention relates to a functionalized polyolefin comprising a reaction product of a heteroatom-containing group and any vinyl terminated polyolefin described herein, wherein preferably the functional group is P , O, S, N, Br, Cl, F, I, and / or B, containing one or more heteroatoms and the functionalized polyolefin is 0.60 to 1.2 per chain Or preferably 0.75 to 1.10 functional groups (preferably Mn is modified by more than 15% compared to Mn of vinyl-terminated polyolefins prior to functionalization and optional derivatization Assuming it is not). The number of functional groups per chain (= F / Mn) was measured by ¹ H-NMR as described in WO 2009/155472 (VDRA is VRDA, about 4.65 to 4.85 ppm See paragraphs [00111]-[00114] on page 26-27, including normalized integrated signal intensity for vinylidene resonances and for about 5.15-5.6 ppm vinylene resonances. I want to be) Preferred heteroatom-containing groups include one or more of sulfonates, amines, aldehydes, alcohols, or acids, preferably heteroatom-containing groups include epoxides, succinic acid, maleic acid, or maleic anhydride. Alternatively, the heteroatom-containing group includes one or more of acids, esters, anhydrides, acid-esters, oxycarbonyl, carbonyl, formyl, formylcarbonyl, hydroxyl, and acetyl halide.

Percent functionalization of polyolefin = (F × 100) / (F + VI + VE). The number of vinyl groups / 1000 carbons (VI *) and the number of vinylidene groups / 1000 carbons (VE *) for the functionalized polyolefins were calculated from the ¹ H-NMR spectrum of the functionalized polyolefins from VI and VE for the unfunctionalized polymers. Measured in the same manner as Preferably, the percent functionalization of the polyolefin is 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more.

In another embodiment, the functionalized polyolefin described herein is the same as the original vinyl-terminated polyolefin or greater than 15%, preferably greater than 10% Mn and / or Mw and And / or Mz, “identical” is defined to mean within 5%.
In another embodiment, the vinyl terminated polyolefin described herein is used in any method, blend or product disclosed in WO 2009/155472, which is incorporated herein by reference. be able to.

In another embodiment, the present invention provides:
1. Preparation of vinyl terminated propylene polymer:
The method comprises contacting propylene (i) with a catalyst system (ii) under polymerization conditions;
The catalyst system (ii)
(A) Activators comprising anions and cations, preferably non-coordinating anions, preferably boron compounds, preferably of the formula:

A bulky activator represented by the formula:
Each R ₁ is independently a halide, preferably a fluoride;
Each R ₂ is independently a halide, substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl Group), preferably a fluoride or C ₆ perfluorinated aromatic hydrocarbyl group;
Each R ₃ is a halide, a substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. ), Preferably a fluoride or C ₆ perfluoroaromatic hydrocarbyl group;
L is a neutral Lewis base;
H is hydrogen;
B is boron;
(L—H) ⁺ is a Bronsted acid;
d is 1, 2 or 3;
Here, the anion of the activator has a molecular weight greater than 1020 g / mol; and at least three of the substituents on the B atom are each greater than 250 cubic liters, alternatively greater than 300 cubic liters, or 500 Preferably, the bulky activator is trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri ( n-butyl) ammonium tetrakis (perfluoronaphthyl) borate, tri (t-butyl) ammonium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate, tropyliumtetrakis (perfluoronaphthyl) borate, triphenylcarbeniumtetrakis (Perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethyl silyllium tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, triethylammonium tetrakis ( Perfluorobiphenyl) borate, tripropylammonium tetrakis ( Rufluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, tropyliumtetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (Perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (pe Rufluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, [4-t-butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (where Ph Is phenyl or Me is methyl)];
(B) Formula:

At least one metallocene compound represented by the formula:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof ( The two X may form part of a fused ring or ring system);
Each R ₁ is independently a C ₁ -C ₁₀ alkyl group, preferably methyl, ethyl, propyl, and butyl, and isomers thereof;
Each R ₂ is independently a C ₁ -C ₁₀ alkyl group, preferably methyl, ethyl, propyl, and butyl, and isomers thereof;
Each R ₃ is hydrogen;
Each R ₄ , R ₅ and R ₆ is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group, or a heteroatom;
T is a bridging group preferably comprising silicon or germanium;
Provided that any of the adjacent R ₄ , R ₅ and R ₆ groups may form a fused ring or a multi-centered fused ring system, which ring may be aromatic, partially saturated or saturated;

Preferably, the metallocene compound is
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,

rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,

rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) hafnium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,

rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2,3-dimethyl) hafnium dimethyl, and rac-dimethylgermanylbis (2,3-dimethyl) zirconium dimethyl);
At least one of the above];
(C) optionally comprising a carrier material; and (d) optionally comprising a co-activator:
2. The process of claim 1 further comprising contacting a comonomer, preferably ethylene, with propylene and a catalyst system, wherein the process yields a vinyl terminated propylene copolymer, wherein the vinyl terminated propylene copolymer is 0.1-50 mol. % Having a comonomer content in the range of%):
3. M is hafnium and the activator is dimethylanilinium tetrakis (perfluoronaphthyl) borate, dimethylanilinium tetrakis (perfluorobiphenyl) borate, or [4-t-butyl-PhNMe ₂ H] [(C ₆ F ₃ ( C ₆ F ₅ ) ₂ ) ₄ B], wherein the catalyst system has an activity exceeding 150 kg / g (catalyst) time ⁻¹ at a temperature of 90 ° C. or higher:
4). There is no or little alumoxane, preferably the presence of alumoxane is 0 mol%, or the alumoxane is less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably 1: 4. The method of paragraphs 1-3, wherein the method is present in an aluminum: transition metal molar ratio of less than 1.
5. The presence of the scavenger is 0 mol% or the scavenger is less than 100: 1, preferably less than 50: 1, preferably less than 15: 1, preferably less than 10: 1 mole of scavenger metal: transition metal. The method according to items 1 to 4, which is present in a ratio:
6.1 Catalyst systems useful in the process of paragraphs 5-5:
7). 7. Use of the catalyst system according to claim 6 for polymerizing olefin monomers to produce polymers having allyl chain ends.

Product characterization The product was characterized by ¹ H-NMR, ¹³ C-NMR, and GPC as follows.
¹ H-NMR
¹ H-NMR data was collected at room temperature or 120 ° C. (for purposes of the claims, 120 ° C. should be used) in a 5 mm probe using a spectrometer with a ¹ H frequency of at least 400 MHz. . Data was recorded using a 45 ° maximum pulse width, an 8 second pulse interval, and a signal averaged over 120 accumulations. Spectral signals were integrated and the number of unsaturated species per 1000 carbons was calculated. Mn was calculated by multiplying the total number of unsaturated species per 1000 carbons by 14,000.

The region of chemical shift for olefin species is defined to exist between the next spectral regions.

¹³ C-NMR
¹³ C-NMR data were collected at 120 ° C. using a spectrometer with a ¹³ C frequency of at least 100 MHz. To provide a pulse capture delay of at least 10 seconds with continuous wideband proton decoupling using a 90 ° pulse, swept square wave modulation without gating to give a digital resolution of 0.1-0.12 Hz A controlled uptake time was employed for all uptake periods. The spectra were acquired at a time that averaged to provide a signal-to-noise level sufficient to measure the signal of interest. The sample was dissolved in tetrachloroethane-d ₂ (TCE) at a concentration of 10 to 15% by weight and then inserted into the spectrometer magnet.
Prior to data analysis, the spectra were collated by setting the chemical shift of the TCE solvent signal to 74.39 ppm.

The chain ends involved in quantification were confirmed using the signals shown in the table below. N-butyl and n-propyl were not reported due to their low abundance (less than 5%) relative to the chain ends shown in the table below.

GPC
Mn, Mw and Mz were measured using the GPC method with a high temperature size exclusion chromatograph (from SEC, Waters Corporation or Polymer Laboratories) equipped with a differential refractive index detector (DRI). Details of the experiment are described in T. Sun, P. Brant, RR Chance, and WW Graessley, Macromolecules, Volume 34, Number 19, pp. 6812-6820, (2001) and references therein. Three Polymer Laboratories PLgel 10 mm Mixed-B columns were used. The nominal flow rate was 0.5 cm ³ / min and the nominal injection volume was 300 μL. The various transfer lines, columns and differential refractometer (DRI detector) were housed 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 L of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7 μm glass pre-filter followed by a 0.1 μm Teflon filter. The TCB was then degassed using an online degasser prior to entering the SEC. The polymer solution was prepared by placing the dried polymer in a glass container, adding the desired amount of TCB, and then heating the mixture at 160 ° C. for about 2 hours with continuous stirring. All amounts were measured by weight. The density of TCB used to express polymer concentration in units of mass / volume was 1.463 g / mL at room temperature and 1.324 g / mL at 135 ° C. The injection concentration was 1.0 to 2.0 mg / mL, and a smaller concentration was adopted for a sample having a larger molecular weight. Prior to running each sample, the DRI detector and injector were purged. The flow rate in the apparatus was then increased to 0.5 mL / min and the DRI was allowed to stabilize for 8-9 hours before injecting the first sample.

The concentration c at each time point in the chromatogram is calculated from the DRI signal (I _DRI ) after baseline subtraction:
c = K _DRI × I _DRI / (dn / dc)
Calculated using _Where K _DRI is a constant determined by calibrating the DRI, and (dn / dc) is the refractive index increment for the system. The refractive index of TCB is 135 ° C. and λ = 690 nm, and n = 1.500. For purposes of the present invention and claims thereto, (dn / dc) = 0.104 for propylene polymers and 0.1 for others. Concentrations are expressed in g / cm ³ , molecular weights are expressed in g / mol, and intrinsic viscosities are expressed in dL / g with respect to the parameter units used in this description for the SEC method.

Metallocenes used in the examples The following metallocenes were used in the examples below.

Activators used The following activators were used in the examples below.

Synthesis of metallocene building blocks Synthesis of metallocene E and metallocene F:
Metallocene E and metallocene F were synthesized from precursor compound 5 (see Scheme 1). The synthesis of precursor compound 5 consists of three different synthetic routes as shown in Scheme 1 below: route A (A → 1a + 1b → 4 + 1b → 5), route B (A → 1a + 1b → 2 → 3 → 4 → 5), And route C (B → 8 → 5).

Here, nBu is n-butyl, Me is methyl, equiv is equivalent, and THF is tetrahydrofuran.

Synthesis path A (A → 1a + 1b → 4 + 1b → 5)
Synthesis route A is illustrated in Scheme 2 below.
Here, nBu is n-butyl, Me is methyl, and equiv is equivalent.

Synthesis of Compound 1a + 1b: Compound A (2-methylindene, 10 g, 76.9 mmol) was dissolved in diethyl ether (150 mL) and deprotonated with nBuLi (10 M / hexane, 77 mmol). After 4 hours, propyl bromide (CH ₃ CH ₂ CH ₂ Br, 18 g, 146 mmol) was added to the reaction mixture followed by tetrahydrofuran (THF, 50 mL) and the reaction was stirred at room temperature for an additional 12 hours. The reaction was quenched with water and the organic layer was dried over anhydrous magnesium sulfate (MgSO ₄ ). Volatiles were removed to give an isomeric mixture of 1a and 1b as a yellow oil (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 hexane (200 mL), and deprotonated with n-butyllithium (nBuLi, 6.1 mL of 10M hexane solution, 61 mmol). After 12 hours at room temperature, the solid was collected on a glass filter, washed with additional hexane (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 of the lithiated ligand compound 2 was dissolved in THF (100 mL) and reacted with dichlorodimethylsilane (Me ₂ SiCl ₂ , 3.8 g, 29 mmol) at room temperature for 10 hours. ¹ H-NMR showed the formation of 4 and 1b. 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 / hexane) to obtain a solid. The white solid product 5 was filtered on a glass filter, washed with hexane (2 × 30 mL) and dried in vacuo (84% based on 9.1 g, 1a, 1b).

Compound 5; ¹ H-NMR (THF-d8, 250 MHz) δ ppm; 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 path B (A → 1a + 1b → 2 → 3 → 4 → 5)
Synthesis route B is illustrated in Scheme 3 below.
Here, nBu is n-butyl, Me is methyl, and equiv is equivalent.

  Synthesis of Compound 1a + 1b: 2-Methylindene (20 g, 154. mmol) was dissolved in diethyl ether (200 mL) and reacted with nBuLi (12.3 g, 10 M / hexane) at room temperature for 12 hours. The ether was removed under a stream of nitrogen. The white deprotonated product (2-methylindenyllithium) was filtered, washed with hexane and dried in vacuo to give a quantitative yield. 2-Methylindenyllithium (5.4 g, 39.7 mmol) was slurried in diethyl ether (60 mL) and reacted with propyl bromide (10 g, 81 mmol) at room temperature for 12 hours. Volatiles were removed in vacuo and the crude reaction was extracted with hexane (2 × 30 mL). The extract was reduced in volume to give compound 1a + 1b as a yellow oil (4.5 g, 66% yield).

Synthesis of Compound 2: Compound 2 was obtained by deprotonation with nBuLi as described above.
Synthesis of Compound 3: Compound 2 was dissolved in diethyl ether (100 mL) and reacted with excess Me ₂ SiCl ₂ (6 g, 46.5 mmol). After 12 hours, analysis by ¹ H-NMR revealed that compound 3 was synthesized. The next step was taken without purification of compound 3. Compound 3: ¹ H NMR (C ₆ D ₆ , 500 MHz) δ ppm; 7.5 to 7.05 (multiple-line complex d, C ₆ H ₄ ring), 3.22 (m, C ₅ H ring), 2.40 (t, C ₅ -CH _2- ), 1.95 (s, C ₅ -Me), 1.48 (m, C ₅ -CH ₂ -CH _2- ), 0.85 (t, -C ₂ H ₄ -Me), 0.11, -0.13 ( s, Si-Me, diastereotopic).

Synthesis of Compound 4: All volatiles were removed from the crude mixture of Compound 3 (including unreacted Me ₂ SiCl ₂ ) and fresh diethyl ether (100 mL) was added to the reaction mixture. Additional compound 2 (6.0 g, 33.7 mmol) was added and the reaction was stirred at room temperature for 2 days. An aliquot was taken and analyzed by ¹ H-NMR and formation of 4 was observed. Volatiles were removed and the crude reaction was extracted with hexane (2 × 40 mL). In the next step, the hexane extract was used without further purification.
Synthesis of Compound 5: A hexane extract containing Compound 4 was reacted with nBuLi (5 g, 10 M / hexane) at room temperature to obtain a solid. The white solid product 5 was filtered on a glass filter, washed with hexane (2 × 30 mL) and dried in vacuo (9.1 g, 84% based on 1a + 1b).

Synthesis route C (B → 8 → 5)
Synthesis route C is illustrated in Scheme 4 below.
Here, nBu is n-butyl, Me is methyl, and equiv is equivalent.
Synthesis of Compound 8: 2-Methylindenyllithium (2.0 g, 14.7 mmol) was dissolved in ether (60 mL) and cooled to −30 ° C. Me ₂ SiCl ₂ (0.949 g, 7.35 mmol) was added and the reaction was stirred at room temperature overnight. An aliquot was analyzed by ¹ H-NMR to find a diastereomeric mixture of μ-dimethylsilyl, bis-2-methylindene (1.3 g, 4.1 mmol, 56% yield). All was dissolved in ether (30 mL) and cooled to −30 ° C. n-Butyllithium (2 eq, 4 mL, 10 mmol, 2.5 M / hexane) was added to the reaction mixture and then the reaction mixture was allowed to warm to room temperature. The reaction mixture was stirred at room temperature for 12 hours and the white solid product was filtered, washed with hexane (30 mL) and dried in vacuo (1.8 g, quantitative yield).

Synthesis of Compound 5: Compound 8 was redissolved in ether (100 mL) and cooled to −30 ° C. To the reaction mixture was added 1-bromopropane (4 eq, 2.2 g, 17.9 mmol). Aliquots were taken at 4 hours and analyzed by ¹ H-NMR and found to have low conversion to the desired product. THF (100 mL) was added and the reaction mixture was stirred at room temperature overnight. After 12 hours, volatiles were removed by N ₂ purge. The reaction mixture was extracted with hexane (100 mL), filtered on a glass filter and dried in vacuo (2.23 g, quantitative yield). The dried mixture was dissolved in 100 mL ether and cooled to −30 ° C. n-Butyllithium (2 eq, 1.6 M / hexane, 8.5 mL, 13.6 mmol) was added and the solution was allowed to warm to room temperature and stirred at room temperature for 12 hours. Compound 5 was found when an aliquot of the reaction mixture was analyzed by ¹ H-NMR. The white solid product 5 was filtered on a glass filter, washed with hexane (2 × 30 mL) and dried in vacuo to give a white solid in quantitative yield.

Synthesis of metallocene E The synthesis of metallocene E is shown in Scheme 5 below.

Synthesis of Compound 6: Compound 5 (6.6 g, 16.0 mmol) was slurried in diethyl ether (100 mL) and reacted with hafnium tetrachloride (HfCl ₄ , 4.2 g, 13.1 mmol). After 1 hour, about 50 mL of diethyl ether was removed, and the metallocene compound 6 [dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dichloride] was collected on a glass filter as a light yellow solid (4. 2g, 49.5%).

Synthesis of metallocene E: Compound 6 was slurried in diethyl ether (50 mL) + toluene (80 mL) and reacted with methylmagnesium iodide (MeMgI, 5.6 g, 3.0 M / diethyl ether) at room temperature for 16 hours. Dimethoxyethane (DME, 6 g) was added to the crude reaction mixture, the mixture was filtered through a medium glass filter and the filtrate was collected. The filtrate was reduced in volume, pentane (30 mL) was added and the filtrate was cooled to -35 ° C. Metallocene E [rac-dimethylsilylbis (2-methyl, 3-propylindenylhafnium dimethyl)], first crop of crystals (pure rac-E, 0.6 g, 16%), and second crop (5% meso-E + 95% rac-E, 0.7 g, 19%). Metallocene E; ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ ppm; 7.4 (d), 7.3 (d), 7.08 (t), 6.75 (t), 2.68-2.22 (complex m), 1.87 (s) , 1.41 (m), 0.97 (s), 0.81 (t), -1.95 (s).

Here, Me is methyl.
Synthesis of Compound 9: Compound 5 (8.2 g, 19.9 mmol) was slurried in diethyl ether (150 mL) and reacted with ZrCl ₄ (4.2 g, 17.9 mmol) at room temperature. After 4 hours, the orange solid was collected on a medium filter and washed with additional diethyl ether (2 × 30 mL). The product was dried in vacuo to give pure rac-9 (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 (m d), 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 reacted with MeMgI (1.7 g, 4.5 mmol, 3.0 M) at room temperature. The reaction mixture was stirred at room temperature for 48 hours. Volatiles were removed in vacuo and the crude reaction mixture was extracted with hexane (3 × 20 mL). The hexane solution was reduced to 20 mL and cooled to −35 ° C. to give F as a yellow crystalline solid (0.8 g, 77%). ¹ H NMR (CD ₂ Cl ₂ , 500MHz) 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 H 2-Methylindene (15 g, 11.5 mmol) was dissolved in diethyl ether (300 mL) and reacted with butyllithium (13.8 mL, 1.2 eq, 10 M) for 3 hours. The white solid product was collected on a filter, washed with hexane and slurried in fresh diethyl ether (300 mL). MeI (32.7 g, 23 mmol) was added slowly and the reaction mixture was stirred for 2 h. The reaction mixture was washed with water, dried over MgSO ₄ and reduced in volume under N ₂ to give an oil (13.9 g, 96.5 mmol, 85% yield).

The oil was dissolved in hexane (300 mL) and deprotonated with excess nBuLi (10 mL, 1.2 eq, 10 M) at room temperature. After 12 hours, the product was filtered, washed with hexane (2 × 60 mL) and dried in vacuo to give a white solid (11.6 g, 77.4 mmol, 80% yield). ¹ H NMR (THF-d8, 500 MHz) δ ppm; 7.1 (m, 2H), 6.36 (m, 2H), 5.52 (s, 1H), 2.24, 2,20 (s, 3H each).
The white solid was slurried in diethyl ether (200 mL) and reacted with Me ₂ SiCl ₂ (4.5 g, 34.9 mmol) at room temperature for 48 hours. Volatiles were removed in vacuo and the crude reaction was extracted with hexane (2 × 60 mL). The extract was reduced in volume to an oil (9.1 g, 26.4 mmol). The oil was dissolved in diethyl ether (100 mL) and deprotonated with butyllithium (5.8 mL, 58 mmol, 10M). After 2 hours, 100 mL of hexane was added and the solid was filtered on a filter, washed with hexane and dried in vacuo to give a solid dianion (7.5 g, 21.1 mmol).

The dianion (4.0 g) was slurried in Et ₂ O (80 mL) and reacted with HfCl ₄ (3.3 g, 10.3 mmol). After 20 minutes, the yellow solid was isolated on a glass filter and recrystallized from CH ₂ Cl _{2 at} −30 ° C. to give rac-Me ₂ Si-bis (2,3-dimethylindenyl) HfCl ₂ (2.7 g, 4.6 mmol) was obtained. ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ ppm; 7.65 (d), 7.46 (d), 7.37 (t), 6.97 (t), 2.17 (s), 2.07 (s), 1.42 (s).
rac-Me ₂ Si-bis (2,3-dimethylindenyl) HfCl ₂ (1.4 g, 2.37 mmol) was slurried in toluene (40 mL) and 1.6 mL MeMgI (4.73 mmol, 3.0 M). ) For 48 hours. The crude reaction mixture was filtered, the filtrate was reduced in volume and cooled to −30 ° C. to give metallocene H as a yellow solid (0.72 g, 1.3 mmol, 55% yield). ¹ H NMR (CD ₂ Cl ₂ , 500 MHz) δ ppm; 7.55 (m), 7.46 (m), 7.31 (m), 6.77 (m), 2.16 (s), 1.99 (s), 1.12 (s),- 1.82 (s).

Possible synthetic schemes for preparing the general precursor G5:
Compound 5 should be prepared as shown in Scheme 7.

The reducing agent in Scheme 7 may be any known in the art, such as lithium aluminum hydride, or selectrides such as L-selectride, K-selectride or N-selectride. Select lid is a formula:
Have

Polymerization reaction (Examples 1 and 2):
Batch or continuous polymerization of propylene polymer was carried out using a 2 L stirred autoclave reactor.

Scavengers and cocatalysts Triisobutylaluminum (TIBAL) is available from Akzo Chemicals, Inc. (Chicago, Illinois) and used without further purification. Tri-n-octylaluminum (TNOAL) is available from Akzo Chemicals, Inc. And used without further purification.

The catalyst solution was added in approximately equimolar amounts (typically 1.00: 1.05) of metallocene in 4 mL of dry toluene in a 10 mL glass vial in a Vacuum Atmospheres ™ dry box purged with dry nitrogen. And was prepared by charging the activator. The mixture was stirred for several minutes and then transferred to a clean catalyst tube dried in an oven. An example of a basic polymerization procedure is as follows: The reactor was charged with 2 mL of 25 wt% TNOAL / hexane (0.037 g Al) and 100 mL propylene as a scavenger. The reactor was then heated to the selected polymerization temperature and the catalyst / activator flowed from the catalyst tube into the reactor containing 100 mL of propylene. Additional propylene was optionally added up to a total of 1000 mL. The polymerization was carried out for 10-60 minutes, then the reactor was cooled, the pressure was reduced and opened. At this point, the collected product typically contained some residual monomer. The residual monomer concentration in the product was first reduced by “weathering”. In many cases, samples were heated in an oven while purging with nitrogen or evacuating briefly. Some amount of the lowest molecular weight polymer product may be lost along with residual monomer. In some cases, residual monomers are still detected in the product in the ¹ H-NMR spectrum recorded at 30 ° C. (but not when the spectrum is recorded at 120 ° C.).

Example 1 Comparison of Propylene Polymerization Results Metallocene E and F (at a concentration of 1.6 × 10 ⁻⁶ M) were combined with activator III (1) under the conditions of propylene solution polymerization in a 2 L batch reactor. At a concentration of 6 × 10 ⁻⁶ M). TIBAL (2.5 × 10 ⁻⁴ M) was used as a scavenger. The reactor temperature was varied between 1-12 polymerization experiments as shown in Table 1A below.

The polymer products of Experiments 1-12 are characterized by ¹ H-NMR and GPC, and the results of the characterization are reported in Table 1B below:

  Hafnocene E is a vinyl-terminated atactic propylene polymer with consistently higher vinyl levels (> 90% vinyl) compared to zirconocene F (71-88% vinyl) even under conditions of high propylene conversion. Brought. Surprisingly, hafnocene E also showed both higher thermal stability and unusually higher activity when compared to zirconocene analog F. Polymerization using hafnocene E was studied under continuous solution polymerization conditions as shown in Example 2.

Example 2: Propylene polymerization using metallocene E Continuous solution polymerization was carried out using metallocene E as catalyst and activator III as activator. Metallocene E was premixed with activator III in a 1: 1 ratio and fed into the reactor at a rate of 3.3 × 10 ⁻⁷ mol / min. Propylene (C ₃ ) was fed into the reactor at a rate of 15 g / min, isohexane at a rate of 59.4 g / min, and TNOAL at a rate of 5.2 × 10 ⁻⁶ mol / min.

The reactor temperature during the polymerization experiment was varied as shown in Table 2A below.

The polymer products of experiments 13-18 were characterized by ¹ H-NMR and GPC. The characterization results are reported in Table 2B below:
FIG. 1 shows the observed Mn and% vinyl trends as a function of temperature (Experimental Examples 13-18). We observed a trend towards higher vinyl at higher reactor temperatures. The inventors have also observed that Mn decreases with increasing reactor temperature.

Example 3: Copolymerization of propylene Copolymerization conditions of ethylene / propylene: Continuous polymerization of the polymer was carried out using isohexane as a solvent in a tank reactor with a continuous flow stirring with an internal volume of 1 L. The liquid-filled reactor had a variable residence time of approximately 15-45 minutes and the pressure was maintained at 320 psig (2,206 KPa). The mixed feed of isohexane, ethylene and propylene enters the reactor after being pre-cooled to approximately −30 ° C. The precooling temperature was adjusted to maintain the specified solution polymerization temperature. Polymerization was initiated by allowing the toluene solution of catalyst / activator and the isohexane solution of scavenger to enter the reactor individually and continuously.

Isohexane, ethylene and propylene were fed to the reactor at the rates shown in Table 3A. Metallocene E was activated in vitro using the activator III shown in the table below at a molar ratio of 1: 1.02 and introduced into the polymerization reactor at a rate of 3.298 × 10 ⁻⁷ mol / min. A dilute solution of TNOAL was introduced into the reactor at a rate of approximately 5.16 × 10 ⁻⁶ mol / min. After a stable polymerization of 5 times the residence time, a representative sample of the polymer produced during this polymerization was collected. The polymer solution was withdrawn from the top and then steam distilled to isolate the polymer. The product was collected for the specified time and the conversion was calculated as reported in Table 3A. The polymer produced during the polymerization was analyzed for ethylene content by FT-IR and reported in Table 3A below.

The polymer produced during this polymerization was analyzed by GPC for molecular weight (Mw, Mn and Mz). The number and type of unsaturated chain ends were determined by ¹ H-NMR. Data for this characterization is reported in Table 3B below.

(Examples 4 and 5)
Polymerization conditions A series of columns using dry grade 3 sieve molecular sieves purchased from a series of columns: 2250 cc Oxyclear cylinder from Labclear (Oakland, Calif.) Followed by Aldrich Chemical Company (St. Louis, Mo.). 2250 cc column, two 500 cc columns packed with dry 5 cm molecular sieves purchased from Aldrich Chemical Company, ALCOA Selexsorb CD (7 × 14 mesh) purchased from Coastal Chemical Company (Abbabil, LA) One column of 500cc, and whether it is Coastal Chemical Company Purified by passing through one column of 500 cc packed with ALCOA Selexsorb COS (7 × 14 mesh) purchased from the company.

Polymer grade hexane was further purchased from a series of columns: two 500 cc Oxyclear cylinders from Labclear, followed by two 500 cc columns packed with dry 3Å molecular sieves purchased from Aldrich Chemical Company, and Aldrich Chemical Company. Purification and use by passing through two 500 cc columns packed with dry 5Å molecular sieves.
Description and preparation of the reactor The polymerization was carried out in an inert atmosphere (N ₂ ) dry box, external heater for temperature control, glass insert (reactor internal volume = 22.5 mL), septum inlet, nitrogen This was carried out using a 48-cell parallel pressure resistant reactor (PPR) equipped with a gas and propylene feed control and a disposable PEEK (polyetheretherketone) mechanical stirrer (800 RPM). The PPR was prepared for polymerization by purging with dry nitrogen at 150 ° C. for 5 hours and then at 25 ° C. for 5 hours.

Example 4 Comparison of Activators The experiment time was varied as shown in Tables 4A-I; the experiment time was 5 minutes; activator: metallocene ratio = 1: 1; reaction temperature 85 ° C .; metallocene (MCN) = 8 × 10 ⁻⁵ mol / L; and TNOAL = 1.2 × 10 ⁻⁴ mol / L.

  The inventors have surprisingly found that bulky activators, such as activators V and II, where at least three molecular volumes of substituents on the boron atom each have a molecular volume of greater than 250 cubic liters. , At least three molecular volumes of substituents on the boron atom have more vinyl compared to activators such as activators I, II, IV and VII, each having a molecular volume of less than 250 cubic cubic It has been found to result in a vinyl terminated propylene polymer.

  The inventors also surprisingly found that a catalyst system comprising a zirconocene catalyst (such as a metallocene F) and a bulky activator is compared with a comparative catalyst system comprising a zirconocene catalyst and a less bulky activator. In comparison, it has been found to result in a larger% vinyl. The inventors further surprisingly found that a catalyst system comprising a zirconocene catalyst of the present invention (such as a metallocene F) and a bulky activator provides a hafnocene analog (such as a metallocene E) and a bulky activator. It has been found that it results in% vinyl that is relatively similar to the catalyst system it contains.

Example 5: Propylene polymerization using metallocene H The experimental time was changed as shown in Table 4A-I; the experimental time was 5 minutes; ratio of activator III: metallocene H = 1: 1; metallocene (MCN) = 8 × 10 ⁻⁵ mol / L; and TNOAL = 1.2 × 10 ⁻⁴ mol / L.

  The inventors have surprisingly found that metallocene H results in an extremely large% allyl chain end here of over 96%.

All documents mentioned herein, including any prior literature, related applications and / or test methods, are to the extent that they do not contradict the text for all purposes of control that allow such practice. , Incorporated herein by reference, but prior documents not listed in the originally filed application or document are not incorporated herein by reference. While the invention has been illustrated and described, as obvious from the general description and specific embodiments so far, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the present invention is not construed as limited thereby. Similarly, the term “comprising” is considered synonymous with the term “including” for the purposes of Australian law. Similarly, whenever a composition, element or group of elements is preceded by the transitional expression “comprising”, we also precede the detailed description of the composition, element or group of elements. Assuming a composition or element group similar to the migratory expression “consisting essentially of”, “consisting of”, “selected from the group consisting of” or “is” and vice versa Is understood to be the same.
The present invention may further be the following aspects.
[1] A method for preparing a vinyl-terminated propylene polymer,
Propylene, under polymerization conditions, activator and formula:
[Where:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof ( The two X may form part of a fused ring or ring system);
Each R ₁ is independently a C ₁ -C ₁₀ alkyl group;
Each R ₂ is independently a C ₁ -C ₁₀ alkyl group;
Each R ₃ is hydrogen;
Each R ₄ , R ₅ and R ₆ is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group, or a heteroatom;
T is a bridging group;
Provided that any of the adjacent R ₄ , R ₅ and R ₆ groups may form a fused ring or a multi-centered fused ring system, which ring may be aromatic, partially saturated or saturated.]
Contacting with a catalyst system comprising at least one metallocene compound represented by:
Obtaining a propylene polymer having an allyl chain end of at least 50% (based on the total number of unsaturations)
A preparation method comprising:
[2] The method according to [1], wherein the catalyst system further comprises a support material.
[3] The method according to [1] or [2] above, wherein the catalyst system further comprises an auxiliary activator.
[4] The method according to [1], 2 or 3 above, wherein the activator is a boron-containing non-coordinating anion.
[5] The activator has the formula:
[Where:
Each R ₁ is independently a halide;
Each R ₂ is independently a halide, a substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of the formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group Is);
Each R ₃ is a halide, a substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbylsilyl group. Is;
L is a neutral Lewis base;
H is hydrogen;
B is boron;
(L—H) ⁺ is a Bronsted acid;
d is 1, 2 or 3;
The anion has a molecular weight of more than 1020 g / mol; and at least three of the substituents on the B atom have a molecular volume of more than 250 cubic cubic, or more than 300 cubic cubic, or more than 500 cubic cubic, respectively. The method according to [1], 2 or 3 above, wherein the activator is a bulky activator containing an anion and a cation.
[6] Bulky activators are trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) Borate, tri (t-butyl) ammonium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate, tropyliumtetrakis (perfluoronaphthyl) bore Triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilylium tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) ) Borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate, N, N-dimethylanilinium tetra Su (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluoro Biphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, [4-t -Butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (where Ph is phenyl and Me is methyl) The method according to [5] above, which is one or more of the following.
[7] The method further comprises contacting the comonomer with propylene and a catalyst system to produce a vinyl terminated propylene copolymer, and the vinyl terminated propylene copolymer has a comonomer content in the range of 0.1 to 50 mol%. The method according to any one of [1] to [6].
[8] The method according to [7] above, wherein the comonomer is ethylene.
[9] The metallocene compound is
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) hafnium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2,3-dimethyl) hafnium dimethyl, and
rac-dimethylgermanylbis (2,3-dimethyl) zirconium dimethyl
The method according to any one of [1] to [7], which is one or more of the above.
[10] M is hafnium, and the activator is dimethylanilinium tetrakis (perfluoronaphthyl) borate, dimethylanilinium tetrakis (perfluorobiphenyl) borate, or [4-t-butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (where Ph is phenyl and Me is methyl) and the catalyst system is 150 kg / g (catalyst) time at a temperature of 90 ° C. or higher. The method according to [1], 2, 3, 7 or 8 above, which has an activity exceeding ^-1 .
[11] A catalyst system comprising an activator and at least one metallocene compound, wherein the metallocene compound has the formula:
[Where:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof ( The two X may form part of a fused ring or ring system);
Each R ₁ is independently a C ₁ -C ₁₀ alkyl group;
Each R ₂ is independently a C ₁ -C ₁₀ alkyl group;
Each R ₃ is hydrogen;
Each R ₄ , R ₅ and R ₆ is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group, or a heteroatom;
T is a bridging group;
Provided that any of the adjacent R ₄ , R ₅ and R ₆ groups may form a fused ring or a multi-centered fused ring system, which ring may be aromatic, partially saturated or saturated. A catalyst system.
[12] The catalyst system according to [11], wherein M is hafnium.
[13] The catalyst according to [11] or [12], wherein each R ₁ and R ₂ is independently one or more of methyl, ethyl, propyl, and butyl, or isomers thereof. system.
[14] The metallocene compound is
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-ethyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-isopropylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-propylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) hafnium dimethyl,
rac-dimethylsilylbis (2,3-dimethyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-methylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-ethylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-propyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) hafnium dimethyl,
rac-dimethylgermanylbis (2-methyl, 3-butylindenyl) zirconium dimethyl,
rac-dimethylgermanylbis (2,3-dimethyl) hafnium dimethyl, and
rac-dimethylgermanylbis (2,3-dimethyl) zirconium dimethyl
The catalyst system according to [11], which is at least one of the above.
[15] The catalyst system according to [11], 12, 13 or 14, further comprising a support material.
[16] The catalyst system according to [11], 12, 13, 14 or 15, further comprising an auxiliary activator.
[17] The catalyst system according to any one of [11] to [16], wherein the activator is a boron-containing non-coordinating anion.
[18] The activator is represented by the formula:
[Where:
Each R ₁ is independently a halide;
Each R ₂ is independently a halide, substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl Group);
Each R ₃ is a halide, a substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. );
L is a neutral Lewis base;
H is hydrogen;
B is boron;
(L—H) ⁺ is a Bronsted acid;
d is 1, 2 or 3;
The anion has a molecular weight of greater than 1020 g / mol; and at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic liters] The catalyst system according to any one of [11] to [16], which is an activator.
[19] Bulky activators are trimethylammonium tetrakis (perfluoronaphthyl) borate, triethylammonium tetrakis (perfluoronaphthyl) borate, tripropylammonium tetrakis (perfluoronaphthyl) borate, tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) Borate, tri (t-butyl) ammonium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate, tropylium tetrakis (perfluoronaphthyl) borate , Triphenylcarbenium tetrakis (perfluoronaphthyl) borate, triphenylphosphonium tetrakis (perfluoronaphthyl) borate, triethylsilylium tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluoro Biphenyl) borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tripropylammonium tetrakis (perfluorobiphenyl) borate, tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate, tri (t-butyl) ammonium tetrakis (perfluorobiphenyl) borate N, N-dimethylanilinium teto Kis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluoro Biphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, [4-t -Butyl-PhNMe ₂ H] [(C ₆ F ₃ (C ₆ F ₅ ) ₂ ) ₄ B] (where Ph is phenyl and Me is methyl) The catalyst system according to the above [18], which is at least one of the above.
[20] T is the formula R ₂ ^a J, wherein J is C, Si or Ge, and each R ^a is independently hydrogen, halogen, C ₁ -C ₂₀ hydrocarbyl or substituted C ₁ -C ₂₀ The two R ^a may be aromatic, partially saturated or saturated cyclic or may form a cyclic structure containing a fused ring system), [1] 2, 3, The method according to 4, 5, 6, 7, 8 or 10.
[21] T is the formula R ₂ ^a J, wherein J is C, Si or Ge, and each R ^a is independently hydrogen, halogen, C ₁ -C ₂₀ hydrocarbyl or substituted C ₁ -C ₂₀ Wherein the two R ^a are represented by the above-mentioned [11], 12, 13, which may form a cyclic structure containing an aromatic, partially saturated or saturated cyclic or condensed ring system) The catalyst system according to 15, 16, 17, 18 or 19.

Claims (10)

A method for preparing a vinyl terminated propylene polymer comprising:
Propylene, under polymerization conditions, activator and formula:
[Where:
M is hafnium or zirconium;
Each X is independently selected from the group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof ( The two X may form part of a fused ring or ring system);
Each R ₁ is independently a C ₁ -C ₁₀ alkyl group;
Each R ₂ is independently a C ₁ -C ₁₀ alkyl group;
Each R ₃ is hydrogen;
Each R ₄ , R ₅ and R ₆ is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group, or a heteroatom;
T is a dialkyl silicon bridging group or a dialkyl germanium bridging group;
Provided that any of the adjacent R ₄ , R ₅ and R ₆ groups may form a fused ring or a multi-centered fused ring system, which ring may be aromatic, partially saturated or saturated.]
Contacting with a catalyst system comprising at least one metallocene compound represented by: and obtaining a propylene polymer having an allyl chain end of at least 50% (based on total unsaturation), and said activation The agent has the formula:
[Where:
Each R ₁ is independently a halide;
Each R ₂ is independently a halide, a substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of the formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group Is);
Each R ₃ is a halide, a substituted C ₆ -C ₂₀ aromatic hydrocarbyl group, or _a siloxy group of formula —O—Si—R _a where R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbylsilyl group. Is;
L is a neutral Lewis base;
H is hydrogen;
B is boron;
(L—H) ⁺ is a Bronsted acid;
The anion has a molecular weight of greater than 1020 g / mol; and at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic liters] A preparation method, which is an activator. The method of claim 1, wherein the catalyst system further comprises a support material. The method of claim 1, wherein the catalyst system further comprises a co-activator. The method of claim 1, wherein the activator is a boron-containing non-coordinating anion.   The method of claim 1, wherein at least three of the substituents on the B atom of the activator each have a molecular volume in excess of 300 cubic cubic meters. The bulky activators are N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate, N, N-dimethyl- (2,4,6-trimethyl) Anilinium) tetrakis (perfluoronaphthyl) borate, tropylium tetrakis (perfluoronaphthyl) borate, N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate, N, N - dimethyl - (2,4,6-trimethyl anilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluorobiphenyl) borate, [4-t-butyl -PhNMe ₂ H] [ _{C 6 F 3 (C 6 F} 5) 2) 4 B] ( where, Ph is phenyl, Me is one or more of the methyl), The method of claim 5. The method further comprises contacting the comonomer with propylene and a catalyst system, resulting in a vinyl terminated propylene copolymer, wherein the vinyl terminated propylene copolymer has a comonomer content ranging from 0.1 to 50 mol%. The method described in 1.   The method of claim 7, wherein the comonomer is ethylene. M is hafnium, the activator, dimethylanilinium tetrakis (perfluoronapthyl) borate, dimethylanilinium tetrakis (perfluorobiphenyl) borate or [4-t-butyl _{-PhNMe 2 H], [(C} 6 F 3 _{(C 6 F 5) 2)} 4 B] ( where, Ph is phenyl, Me is a is) methyl, and the catalyst system, 90 ° C. at a temperature above 150 kg / g (catalyst) time ^{- 2.} The method of claim 1, having an activity of greater than ¹ . T is the formula R ₂ ^a J where J is C, Si or Ge and each R ^a is independently hydrogen, halogen, C ₁ -C ₂₀ hydrocarbyl or substituted C ₁ -C ₂₀ hydrocarbyl. 2. The method of claim 1, wherein two R ^a are represented by a cyclic structure comprising an aromatic, partially saturated or saturated cyclic or fused ring system.