JP2014508848A - Branched vinyl-terminated polymer and process - Google Patents

Abstract

The present invention comprises (i) contacting one or more monomers comprising ethylene and / or propylene with a catalyst system comprising a metallocene catalyst compound and an activator at a temperature greater than 35 ° C., and (ii) at least 50 mole percent of the monomers. It relates to a polymerization process comprising converting to a polyolefin and (iii) obtaining a branched polyolefin having an allylic chain end of greater than 50% relative to the total unsaturated chain ends. The invention also relates to branched polyolefins and functionalized branched polyolefins.
[Selection] Figure 1

Description

Inventors: Peijun Jiang and Patrick Brant
Priority This application claims the priority and benefit of US Patent Application No. 61 / 467,681, filed March 25, 2011, and EP 11165831.6, filed May 12, 2011.
The present invention relates to olefin polymerization, particularly for producing vinyl-terminated polymers.

Alpha-olefins, particularly those containing from about 6 to about 20 carbon atoms, have been used as intermediates in the manufacture of detergents or other types of goods. Such alpha-olefins have also been used as comonomers, especially in linear low density polyethylene. Commercially produced alpha-olefins are typically made by oligomerizing ethylene. Long chain alpha-olefins such as vinyl terminated polyethylene are also known and may be useful as functionalized building blocks or macromonomers.
Allyl-terminated low molecular weight solids and liquids of ethylene or propylene have also been produced, typically for use as branches in polymerization reactions. For example, Rulhoff, Sascha and Kaminsky, (“Synthesis of specific branched poly (propylene) with different microstructures by copolymerization of propylene and linear ethylene oligomers (C _n = 26-28) with metallocene / MAO catalyst and Characterization "Macromolecules, 16, 2006, pp. 1450-1460), and Kaneyoshi, Hiromu et al. (" Block copolymers and grafts with linear polyethylene segments by a combination of degenerative transfer coordination polymerization and atom transfer radical polymerization " See "Synthesis of copolymers" Macromolecules, 38, 2005, pp. 5425-5435).
Furthermore, U.S. Pat.No. 4,814,540 uses bis (pentamethylcyclohexane) with methylalumoxane in toluene or hexane with or without hydrogen to make allylic vinyl-terminated propylene homooligomers with low degrees of polymerization of 2-10. Pentadienyl) hafnium dichloride, bis (pentamethyl cyclopentadienyl) zirconium dichloride and bis (tetramethyl n-butylcyclopentadienyl) hafnium dichloride are disclosed. These oligomers do not have high Mn and at least 93% allylic vinyl unsaturation. Similarly, these oligomers lack comonomer and are produced with low excess of alumoxane (molar ratio ≧ 600 Al / M; M = Zr, Hf). Furthermore, more than 60% by weight of solvent (solvent + propylene basis) is present in all examples.

Teuben et al. (J. Mol. Catal., 62, 1990, pp. 277-287) [Cp * ₂ MMe (THT)] + [BPh ₄ ] (M = Zr and Hf; Cp * = Pentamethylcyclopentadienyl; Me = methyl, Ph = phenyl; THT = tetrahydrothiophene). A broad product distribution (336 number average molecular weight (Mn)) with oligomers up to C ₂₄ was obtained at room temperature for M = Zr. On the other hand, for M = Hf, only dimer 4-methyl-1-pentene and trimer 4,6-dimethyl-1-heptene were produced. It was clear that the dominant termination mechanism was a beta-methyl transition from the growing chain to the metal center, as demonstrated by deuterium labeling studies.
X. Yang, et al. (Angew. Chem. Intl Ed. Engl., 31, 1992, pp. 1375) discloses amorphous, low molecular weight polypropylene made at low temperatures, where the reaction is less active. And the product had 90% allylic vinyl based on total unsaturation by ¹ H NMR. Resconi et al. (J. Am. Chem. Soc., 114, 1992, pp. 1025-1032) then described bis (pentamethylcyclopentadienyl) zirconium and bis (pentamethylcyclopentadiene) for polymerizing propylene. Discloses the use of (enyl) hafnium, and the resulting beta-methyl termination resulted in oligomers and low molecular weight polymers having "primarily allyl-terminated and iso-butyl-terminated" chains. As in U.S. Pat. No. 4,814,540, the oligomer produced is free of at least 93% allyl chain ends, from about 500 to about 20,000 g / mol Mn (measured by ¹ H NMR), and is catalytic. Have low productivity (1-12,620 g / mmol metallocene / hour;> 3000 wppm Al in the product).

Similarly, Small and Brookhart, (Macromolecules, 32, 1999, pp. 2322) have predominantly or exclusively 2,1 chain growth, chain growth termination due to beta-hydride elimination, and a significant amount of vinyl end groups. Disclosed is the use of pyridylbisamidoiron catalysts in low temperature polymerizations to produce low molecular weight amorphous propylene materials.
Weng et al. (Macromol Rapid Comm. 2000, 21, pp. 1103-1107) are prepared using dimethylsilyl bis (2-methyl, 4-phenyl-indenyl) zirconium dichloride and methylalumoxane in toluene at about 120 ° C. Disclosed materials containing up to about 81% vinyl ends. The material has an Mn of about 12,300 (determined by ¹ H NMR) and a melting point of about 143 ° C.
Markel et al. (Macromolecules, 33, 2000, pp. 8541-8548) is a comb fraction made of Cp ₂ ZrCl ₂ and (C ₅ Me ₄ SiMe ₂ NC ₁₂ H ₂₃ ) TiCl ₂ activated with methylalumoxane. Branch block polyethylene is disclosed.
Moscardi et al. (Organometallics, 20, 2001, pp. 1918) describe the rac in the batch polymerization of propylene to produce a material whose “allyl end groups are always prevailing over any [propene] and over all other end groups”. Disclosed is the use of -dimethylsilylmethylenebis (3-t-butylindenyl) zirconium dichloride and methylalumoxane. In these reactions, shape control is limited and about 60% of the chain ends are allyl.
Coates et al. (Macromolecules, 38, 2005, pp. 6259) are bis-activated activated with modified methylalumoxane (MMAO; Al / Ti molar ratio = 200) in a batch polymerization conducted at 20 ° C to + 20 ° C for 4 hours. The preparation of low molecular weight syndiotactic polypropylene ([rrrr] = 0.46-0.93) with about 100% allyl end groups using (phenoxyimine) titanium dichloride ((PHI) ₂ TiCl ₂ ) is disclosed. For these polymerizations, propylene was dissolved in toluene to give a 1.65M toluene solution. The catalyst productivity was very low (0.95-1.14 g / mmol Ti / hour).
JP 2005-336092 A2 discloses the production of vinyl-terminated propylene polymers using substances such as H ₂ SO ₄ treated montmorillonite, triethylaluminum, triisopropylaluminum, in which case liquid propylene is fed to the catalyst slurry in toluene Is done. This process produces a substantially isotactic macromonomer that does not have a significant amount of amorphous material.

U.S. Pat.No. 6,897,261 discloses an olefin graft copolymer obtained by copolymerizing an atactic branched macromonomer, wherein the macromonomer comprises (1) propylene and (2) propylene and ethylene, Derived from a monomer selected from the group consisting of alpha-olefins having 20 carbon atoms, cyclic olefins and combinations with at least one selected from styrene, the propylene content of which falls between 0.1 mol% and 100 mol% The macromonomer satisfies the following (a) and (b): (a) Its weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is in the range of 400-200000, (b) The vinyl content is at least 70 mol% of all unsaturated groups in the macromonomer, and the macromonomer satisfies each of the following (i), (ii), and (iii): (I) Temperature dependence of the macromonomer solution viscosity (E ₂ ) Temperature dependence of the linear polymer (which has the same type of monomer, the same chemical composition and the same intrinsic viscosity as the macromonomer polymer) ( The ratio of E ₁ ), E ₂ / E ₁ , satisfies the following relationship: 1.0 <E ₂ / E ₁ <2.5.
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 are semi-batch polymerizations (2.1 kg / cm ² (added to toluene over 30 minutes at 0 ° C.) over a polymerization time of 2.3 to 4 hours at about 0 ° C. to produce an EP copolymer having a Mn of about 4,800 to 23,300. Bis (phenoxyimine) activated with methylalumoxane (MMAO; Al / Ti molar ratio range 150-292) with 30 psi) propylene, followed by a total pressure ethylene gas flow of 2.2 kg / cm ² (32 psi)) Made with titanium dichloride ((PHI) ₂ TiCl ₂ ). In the four reported copolymers, the allyl chain end decreased with increasing ethylene incorporation approximately according to the following formula:
% Allyl chain end (totally unsaturated) = -0.95 (% ethylene mole incorporated) + 100
For example, 65% allyl (compared to total unsaturation) was reported for an EP copolymer containing 29 mole% ethylene. This is the best allyl population obtained. For 64 mol% of incorporated ethylene, only 42% of the unsaturation is allyl. The productivity of these polymerizations ranged from 0.78 × 10 ² g / mmol Ti / hour to 4.62 × 10 ² g / mmol Ti / hour.

Prior to this study, Zhu et al. (Macromolecules, 35, 2002, pp. 10062-10070 and Macromolecules Rap. Commun., 24, 2003, pp. 311-315) were active on B (C ₆ F ₅ ) ₃ and MMAO. Reported only low (about 38%) vinyl-terminated ethylene-propylene copolymers made with a modified tension ring-shaped metallocene catalyst [C ₅ Me ₄ (SiMe ₂ N-tert-butyl) TiMe ₂ .
Janiak and Blank summarize various studies on olefin oligomerization (Macromol. Symp., 236, 2006, pp. 14-22).
US Pat. No. 6,225,432 discloses a branched polypropylene composition having improved melt strength and good processability. Branched polypropylene compositions have a polydispersity of less than 4.0 and a melting point greater than 90 ° C. The weight average branching index of the polypropylene composition is less than 0.95.

  However, a method for producing a branched polyolefin having a large amount of allyl ends on a commercial scale is not yet known. Therefore, allyl-terminated branched polyolefins with allyl ends present in large quantities (greater than 50%) can be produced in a wide range of molecular weights, especially in high yields, with commercial rates (productivity over 5,000 g / mmol / hour). There is a need for new methods of manufacturing. In addition, there is a need for branched polyolefin reactive materials with high amounts of allyl termination that can be functionalized, used in additive applications, or used as a blending component.

The present invention
(i) one or more monomers comprising ethylene and / or propylene are contacted with a catalyst system comprising a metallocene catalyst compound and an activator, preferably at a temperature above 35 ° C. (the metallocene catalyst compound is represented by the following formula: :

Where
M is selected from the group consisting of zirconium or hafnium;
Each X is independently a group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof. (Two Xs may form a condensed ring or part of a ring system);
Each R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group,
Furthermore, provided that any two adjacent R groups may form a fused ring or a multi-centered fused ring system (these rings may be aromatic, partially saturated or saturated), and That any of the adjacent R ⁴ group, R ⁵ group, and R ⁶ group may form a condensed ring or a multi-centered condensed ring (these rings may be aromatic, partially saturated or saturated); As a condition,
T is the formula R ₂ ^a J where J is one or more of C, Si, Ge, N, or P, and each R ^a is independently hydrogen, halogen, C ₁ -C ₂₀ hydrocarbyl group Or a C ₁ -C ₂₀ substituted hydrocarbyl).
At least one R ³ is a substituted or unsubstituted phenyl group when any of R ¹ , R ² , R ⁴ , R ⁵ or R ⁶ is not hydrogen),
(ii) preferably converting at least 50 mol% of the monomers to polyolefins; and
(iii) relates to a polymerization process comprising obtaining a branched polyolefin having an allyl chain end greater than 50%, and a Tm of 60 ° C. or higher, relative to the total unsaturated chain ends.

The present invention also includes one or more alpha olefin derived units comprising ethylene and / or propylene, and
(i) 50% or more of allyl chain ends, based on the total number of unsaturated chain ends, and
(ii) g'vis below 0.90
Relates branched polyolefin having a 7,500 ~60,000 g / mol Mn ⁽¹ H NMR) with.
The present invention also includes one or more alpha olefins containing ethylene and / or propylene, and (i) 50% or more of allyl chain terminals, (ii) g'vis of 0.90 or less, based on the total unsaturated chain terminals, And optionally (iii) a branched polyolefin having a Mn (GPC) greater than 60,000 g / mol with a bromine number which decreases by at least 50% after complete hydrogenation.
Furthermore, the present invention comprises one or more alpha olefin derived units comprising ethylene and / or propylene, and
(i) the ratio of the percentage of saturated chain ends to the percentage of allyl chain ends of 1.2 to 2.0, and
(ii) relates to branched polyolefins having less than 7,500 g / mol Mn ( ¹ H NMR) with 50% or more allyl chain ends, relative to the total moles of unsaturated chain ends.

FIG. 6 is a plot of the relationship between g'vis and log Mw for an allyl-terminated branched polypropylene polymer made with metallocene A / activator III (see Examples, Table 3, Experiments 59-65).

The present inventors have surprisingly discovered a novel method for producing branched polyolefins having a large amount of allyl ends. These novel processes can be carried out under commercial conditions and can produce branched polyolefins at commercial rates. In addition, these processes are typically carried out using non-coordinating anionic activators, preferably bulky activators, as specified below.
Described herein are such methods for producing branched polyolefins, branched olefin products, and compositions comprising such branched polyolefins. As used herein, the term “branch” means a polyolefin having a g′vis of 0.90 or less, or if the polyolefin has a Mn ( ¹ H MNR) of less than 7,500 g / mole, The polyolefin has a percentage ratio of saturated chain ends to allyl chain ends of 1.2 to 2.0. These branched polyolefins with high amounts of allyl chain ends are used as macromonomers for the synthesis of branched poly (macromonomers), block copolymers, and additives such as lubricants, waxes, and adhesives. Or as a compounding agent in these. Advantageously, when used, for example, as an additive to a film composition, the branched nature of these polyolefins improves the desired mechanical properties by allowing optimal thermoforming and molding at lower temperatures. Thus, the energy consumption of the film forming process can be reduced compared to linear polyolefin analogs. More advantageously, the large amount of allyl chain ends of these branched polyolefins provides an easy route to functionalization. Functionalized branched polyolefins can also be useful as additives or compounding agents.

For the purposes of the present invention and the claims, a new numbering scheme for the periodic table family is used in CHEMICAL AND ENGINEERING NEWS, 63 (5), page 27, (1985). Therefore, "Group 4 metal" is an element from Group 4 of the periodic table.
“Catalyst productivity” is a measure of how many kilograms of polymer (P) is produced using a polymerization catalyst containing W moles of catalyst (W), expressed in units of kilograms of polymer per mole of catalyst. obtain.
Conversion is the amount of monomer converted to polymer product, reported as mole%, and calculated based on polymer yield and the amount of monomer fed to 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 kg of catalyst (cat) used (kgP / kgcat).
“Olefin” (also referred to as “alkene”) is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of the present invention and claims, when a polymer or copolymer is referred to as containing olefins (including but not limited to ethylene, propylene, and butene), it is present in such a polymer or copolymer. The olefin is a polymerized form of olefin. For example, if the copolymer is said to have an “ethylene” content of 35% to 55% by weight, the mer units in the copolymer are derived from ethylene in the polymerization reaction, and the derived units are 35% based on the weight of the copolymer. It is understood that it is present at from% to 55% by weight. A “polymer” has two or more identical or different mer units. The term “polymer” as used herein includes oligomers (up to 100 mer units) and larger polymers (units greater than 100 mer). A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units different from each other. A “terpolymer” is a polymer having three different mer units. “Different” as used to refer to a mer unit indicates that the mer units differ from each other by at least one atom or are isomerically different. Thus, the definition of copolymer used herein includes terpolymers and the like.
Mn as used herein is number average molecular weight (measured by ¹ H NMR unless otherwise stated), Mw is weight average molecular weight (measured by gel permeation chromatography, GPC), And Mz is the z-average molecular weight (measured by GPC), wt% is mass%, mol% is mole percent, vol% is volume percent, and mol is mole. Molecular weight distribution (MWD) is defined as Mw divided by Mn (measured by GPC), Mw / Mn. Unless otherwise stated, all molecular weights (eg, Mw, Mn, Mz) have units of g / mol. The room temperature is 23 ° C. unless otherwise specified.
The bromine number is measured according to ASTM D 1159.

Process for producing vinyl-terminated branched polyolefin
(i) ethylene and / or preferably at a temperature above 35 ° C, preferably in the range from about 35 ° C to 150 ° C, from 40 ° C to 140 ° C, from 60 ° C to 140 ° C, or from 80 ° C to 130 ° C. Or propylene (preferably propylene) and optionally one or more C _{4 to} C ₄₀ alpha olefin monomers (preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, And one or more monomers comprising an allylic chain) in contact with a catalyst system capable of producing a branched polyolefin having an allyl chain end (the catalyst system comprises a metallocene catalyst compound and an activator, the metallocene catalyst compound comprising: Represented by the following formula:

(Where
M is selected from the group consisting of zirconium or hafnium (preferably hafnium);
Each X is independently a group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof. (Two Xs may form a condensed ring or part of a ring system) (preferably X is a halide or a hydrocarbyl group having from 1 to 20 carbon atoms, preferably X is Chloride or methyl),
Each R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group,
Furthermore, provided that any two adjacent R groups may form a fused ring or a multi-centered fused ring system (these rings may be aromatic, partially saturated or saturated), and That any of the adjacent R ⁴ group, R ⁵ group, and R ⁶ group may form a condensed ring or a multi-centered condensed ring (these rings may be aromatic, partially saturated or saturated); As a condition,
T is the formula R ₂ ^a J where J is one or more of C, Si, Ge, N, or P (preferably J is Si) and each R ^a is independently hydrogen, A bridging group represented by halogen, C ₁ -C ₂₀ hydrocarbyl or C ₁ -C ₂₀ substituted hydrocarbyl (preferably R ^a is methyl, ethyl, chloride);
At least one R ³ (preferably both) is a substituted or unsubstituted phenyl group when any of R ¹ , R ² , R ⁴ , R ⁵ or R ⁶ is not hydrogen),
(ii) preferably converting at least 50 mol% (more preferably at least 60 mol%, at least 70 mol%, at least 80 mol%) of the monomers into polyolefins; and
(iii) Allyl chain ends greater than 50% (preferably 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more) relative to the total unsaturated chain ends And a polymerization process comprising obtaining a branched polyolefin having a Tm of 60 ° C. or higher (preferably 100 ° C. or higher, preferably 120 ° C. or higher).

The inventive methods described herein are performed at commercial speed. In some embodiments, the productivity is 4500 g / mmol or more, preferably 5000 g / mmol or more, preferably 10,000 g / mmol or more, preferably 50,000 g / mmol or more. In other embodiments, the productivity is at least 80,000 g / mmol, preferably at least 150,000 g / mmol, preferably at least 200,000 g / mmol, preferably at least 250,000 g / mmol, preferably at least 300,000 g / mmol.
In another embodiment, the activity of the catalyst is at least 10,000 kg of polymer per kg of catalyst, preferably more than 50,000 kg of polymer per kg of catalyst, preferably more than 100,000 kg of polymer per kg of catalyst, preferably more than 150,000 kg per kg of catalyst. It is a polymer.
In another embodiment, the conversion of the olefin monomer is at least 50 mol%, preferably 60 mol% or more, preferably 70 mol% or more, preferably 80 mol% or more, based on the mass of monomer entering the reaction zone. .
The inventive methods described herein can be carried out at temperatures and pressures suitable for commercial production of these branched vinyl terminated polymers. Typical temperature and / or pressure is higher than 35 ° C (preferably in the range from about 35 ° C to about 150 ° C, from 40 ° C to 140 ° C, from 60 ° C to 140 ° C, or from 80 ° C to 130 ° C) And a pressure in the range of about 0.35 to 10 MPa (preferably 0.45 to 6 MPa or 0.5 to 4 MPa).
The inventive process described herein has a residence time suitable for the commercial production of these branched vinyl terminated polymers. In a typical polymerization, the residence time of the polymerization process is up to 300 minutes, preferably from about 1 minute to 300 minutes, preferably from 5 minutes to 250 minutes, preferably from about 10 minutes to 120 minutes, or preferably from about 10 minutes to 60 minutes. Range.

Suitable diluents / solvents for 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 (e.g., as found in commercially (Isopar ^TM)); and perhalogenated hydrocarbons such as perfluorinated C ₄ ^- ₁₀ include alkanes It is done. Suitable solvents include ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. Also included are liquid olefins that can act as monomers or comonomers. In preferred embodiments, aliphatic hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic hydrocarbons and alicyclic hydrocarbons such as cyclohexane, cyclohexane Heptane, methylcyclohexane, methylcycloheptane, and mixtures thereof are used as solvents. In another embodiment, the solvent is not aromatic and preferably the aromatic compound is present in the solvent at less than 1% by weight, preferably 0.5% by weight, preferably 0% by weight, based on the weight of the solvent.
In a preferred embodiment, the feed concentration for the polymerization is 60% or less, preferably 40% or less, or preferably 20% or less, preferably 0% by volume of solvent, based on the total volume of the feed stream. is there. It is preferred that the polymerization is carried out in a bulk process.
In certain embodiments, when the butene is a comonomer, the butene source may be a mixed butene stream containing various isomers of butene. It is expected that 1-butene monomer will be preferentially consumed by the polymerization process. The use of such a mixed butene stream will provide economic benefits. This is because these mixed streams are often waste streams from the purification process, such as C ₄ raffinate streams, and are therefore substantially less expensive than pure 1-butene.

  The method of the present invention may be performed in any manner known in the art. Any suspension polymerization method, homogeneous bulk polymerization method, solution polymerization method, slurry polymerization method, or gas phase polymerization method known in the art may be used. Such a process may be carried out batchwise, semi-batchwise or continuously. Homogeneous polymerization methods and slurry polymerization methods are preferred (homogeneous polymerization methods are defined as methods in which at least 90% by weight of the product is soluble in the reaction medium). The bulk homogeneous process is particularly preferred (the bulk process is defined as a process in which the monomer concentration in the total feed to the reactor is 70% by volume or more). Also, no solvent or diluent is present or added in the reaction medium (a small amount used as a carrier or other additive for the catalyst system, or an amount typically found in monomers such as in propylene. Except the amount of propane). The process is preferably a single stage polymerization process. In another embodiment, the method is a slurry method. As used herein, “slurry polymerization method” refers to a polymerization method in which a supported catalyst is used and the monomer is polymerized with supported catalyst particles. At least 95% by weight of the polymer product derived from the supported catalyst is in granular form as solid particles (not dissolved in the diluent). “Continuous” means that there is a continuous addition of reactants to the reactor system and withdrawal of reactants and products from the reactor system. The continuous process can work at steady state, i.e., the effluent composition remains constant over time when the flow rate, temperature / pressure and feed composition remain unchanged. For example, a continuous process for producing a polymer would be a process in which reactants are continuously introduced into one or more reactors and the polymer product is continuously withdrawn.

In a preferred embodiment, the polymerization reaction of hydrogen at a partial pressure of 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 (0.7 to 70 kPa). Present in the vessel. In this system, it has been found that hydrogen can be used to provide increased activity without significantly compromising the ability of the catalyst to produce allyl chain ends. The catalytic activity (calculated as g / mmol catalyst / hour) is preferably at least 20% higher, preferably at least 50% higher, preferably 100% higher than the same reaction without hydrogen.
Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruders, pipes or pumps). The “reaction zone” (also referred to as “polymerization zone”) is defined as the region where the activated catalyst and monomer are contacted and the polymerization reaction takes place. If multiple reactors are used in series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerizations in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In preferred embodiments, the polymerization described herein occurs in a single reaction zone. Also, the polymerizations described herein may occur in multiple reaction zones.
In a preferred embodiment, the polymerization reaction of hydrogen at a partial pressure of 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 (0.7 to 70 kPa). Present in the vessel. In this system, it has been found that hydrogen can be used to provide increased activity without significantly compromising the ability of the catalyst to produce allyl chain ends. The catalytic activity (calculated as g / mmol catalyst / hour) is preferably at least 20% higher, preferably at least 50% higher, preferably 100% higher than the same reaction without hydrogen.
In a preferred embodiment, little or no alumoxane is used in the process to produce the vinyl terminated polymer. Preferably, the alumoxane is present in zero mole percent and the alumoxane is present in a molar ratio of aluminum to transition metal of less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1. .
In another embodiment, when alumoxane was used to produce the vinyl terminated polymer, the alumoxane was treated to remove free alkyl aluminum compounds, particularly trimethylaluminum.
Further, in a preferred embodiment, the activator used herein to produce the vinyl terminated polymer is a bulky activator as defined herein and is separate.
In a preferred embodiment, little or no scavenger is used in the process to produce the vinyl terminated polymer. Preferably, the scavenger (eg trialkylaluminum) is present in zero mole% and 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 to 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.), and 2) atmospheric pressure to 10 MPa (preferably Is carried out at a pressure of 0.35 to 10 MPa, preferably 0.45 to 6 MPa, preferably 0.5 to 4 MPa), and 3) an aliphatic hydrocarbon solvent (for example, 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; preferably aromatics based on the mass of the solvent Less than 1% by weight, preferably 0.5% by weight, preferably 0% by weight), 4) the catalyst system used for the polymerization is less than 0.5 mol% Preferably containing 0 mol% alumoxane and the alumoxane is present in a molar ratio of aluminum to transition metal of less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1. 5) the polymerization occurs in one reaction zone, and 6) the productivity of the catalyst compound is at least 80,000 g / mmol (preferably at least 150,000 g / mmol, preferably at least 200,000 g / mmol, preferably at least 250,000 g / mmol). Mmol), preferably at least 300,000 g / mmol), 7) optionally with the absence of a scavenger (eg trialkylaluminum compound) (eg present at zero mole%, and scavenger less than 100: 1) Preferably present in a molar ratio of scavenger metal to transition metal of less than 50: 1, preferably less than 15: 1, preferably less than 10: 1), and 8) optionally hydrogen from 0.001 to 50 psig (0.007 345 kPa) (preferably 0.01~25 psig (0.07~172 kPa), more preferably present in the polymerization reactor at a partial pressure of 0.1 ~10 psig (0.7 ~70 kPa)). In a preferred embodiment, the catalyst system used for the polymerization does not contain more than one catalyst compound. A “reaction zone” (also referred to as a “polymerization zone”) is a vessel in which polymerization takes place, for example a batch reactor. If multiple reactors are used in series or parallel configuration, each reactor is considered a separate polymerization zone. For multi-stage polymerizations in both batch and continuous reactors, each polymerization stage is considered a separate polymerization zone. In a preferred embodiment, the polymerization occurs in one reaction zone. Room temperature is 23 ° C unless otherwise stated.

Catalyst System In an embodiment herein, the present invention relates to a process for producing vinyl-terminated branched polyolefins at commercial speeds under commercial conditions, the process comprising monomers at 50% or more of allyl chain ends. Contacting in the presence of a catalyst system comprising a metallocene catalyst compound and an activator capable of producing a branched polyolefin having The catalyst system is a mixed catalyst system containing one or more non-metallocene catalyst compounds, one or more metallocene catalyst compounds, or a mixture thereof, and preferably the mixed catalyst system contains two or more metallocene catalyst compounds. It is preferred that the catalyst system is a single catalyst system. Similarly, one, two or more activators may be used in the catalyst system.
In the description herein, the catalyst may be described as a catalyst precursor, a pre-catalyst compound, a 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 polymers. A “catalytic system” is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. An “anionic ligand” is a negatively charged ligand that donates one or more pairs of electrons to a transition metal. A “neutral donor ligand” is a neutral charged ligand that donates one or more pairs of electrons to a metal ion.
For purposes of the present invention and claims, where a catalyst system is described as containing a neutral, stable form of a component, the ionic form of that component is the form that reacts with the monomer to form a polymer. Is well understood by those skilled in the art.
Metallocene catalysts are defined as organometallic compounds having at least one π-bonded cyclopentadienyl moiety (or substituted cyclopentadienyl moiety), and more often two π-linked cyclopentadienyl moieties or substituted moieties . This includes other π-linked moieties such as indenyl or fluorenyl or derivatives thereof.
Particularly useful catalyst system metallocenes, activators, optional co-activators, and optional support components are described below.

(a) The metallocene catalyst compound “hydrocarbyl” is a group formed from hydrogen and carbon. 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” is a compound in which at least one hydrogen is replaced by a heteroatom. Groups made from substituted carbon and hydrogen.
For purposes of the present invention and claims, “alkoxide” includes those where the alkyl group is a C ₁ -C ₄₀ hydrocarbyl. The alkyl group may be linear, branched, or cyclic. The alkyl group may be saturated or unsaturated. In certain embodiments, the alkyl group may include at least one aromatic group.
The metallocene catalyst compound of the catalyst system is represented by the following formula.

Where
M is selected from the group consisting of zirconium or hafnium (preferably hafnium);
Each X is independently a group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof. (Two Xs may form a condensed ring or part of a ring system) (preferably X is a halide or a hydrocarbyl group having from 1 to 20 carbon atoms, preferably X is Chloride or methyl),
Each R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group,
In addition, provided that any two adjacent R groups may form a condensed ring or a multi-centered condensed ring system (these rings may be aromatic, partially saturated or saturated),
Further, any of the adjacent R ⁴ group, R ⁵ group, and R ⁶ group may form a condensed ring or a multi-centered condensed ring (these rings may be aromatic, partially saturated or saturated). On condition that
T is the formula R ₂ ^a J where J is one or more of C, Si, Ge, N, or P (preferably J is Si) and each R ^a is independently hydrogen, A bridging group represented by halogen, C ₁ -C ₂₀ hydrocarbyl or C ₁ -C ₂₀ substituted hydrocarbyl (preferably R ^a is methyl, ethyl, chloride);
At least one R ³ (preferably both) is conditional on being a substituted or unsubstituted phenyl group when any of R ¹ , R ² , R ⁴ , R ⁵ or R ⁶ is not hydrogen.

Particularly preferred R ^a substituents are C ₁ -C ₂₀ hydrocarbyl, such as methyl, ethyl, propyl (including isopropyl, sec-propyl), butyl (including t-butyl and sec-butyl), neopentyl, cyclopentyl, hexyl. , Octyl, nonyl, decyl, phenyl, substituted phenyl, benzyl (including substituted benzyl), cyclohexyl, cyclododecyl, norbornyl, and all isomers thereof.
Examples of useful bridging groups R ₂ ^a T herein 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 CO-CR' ₂ , R ' ₂ CR' ₂ CO- CR ' ₂ CR' ₂ , R ' ₂ CO-CR' ₂ CR ' ₂ , R' ₂ CO-CR '= CR', R ' ₂ CS-CR' ₂ , R ' ₂ CR' ₂ CS-CR ' ₂ CR ' ₂ , R' ₂ CS-CR ' ₂ CR' ₂ , R ' ₂ CS-CR' = CR ', R' ₂ C-Se-CR ' ₂ , R' ₂ CR ' ₂ C-Se-CR' ₂ CR ' ₂ , R' ₂ C-Se-CR ₂ CR ' ₂ , R' ₂ C-Se-CR '= CR', R ' ₂ CN = CR', R ' ₂ C-NR'-CR' ₂ , R ' ₂ C-NR'-CR' ₂ CR ' ₂ , R' ₂ C-NR'-CR '= CR', R ' ₂ CR' ₂ C-NR'-CR ' ₂ CR' ₂ , R ' ₂ CP = CR ', and _{R' 2 C-PR'-CR} ' may be represented by _2, in this case, R' is hydrogen or C ₁ -C ₂₀ containing hydrocarbyl the A substituted hydrocarbyl. Preferably, the bridging group R ₂ ^a T comprises carbon or silica, such as dialkylsilyl, preferably the bridging group is CH ₂ , CH ₂ CH ₂ , C (CH ₃ ) ₂ , SiMe ₂ , SiPh ₂ , Selected from SiMePh and (Ph) ₂ C.

Catalyst compounds that are particularly useful in the present invention include one or more of the following:
rac-dimethylsilylbis (indenyl) hafnium dimethyl,
rac-dimethylsilylbis (2-methylindenyl) zirconium dimethyl,
Dimethyl rac-dimethylsilyl-bis (5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz (f) indene) hafnium dimethyl, and
rac-Dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl.
In another embodiment, “dimethyl” after the transition metal in the list of catalyst compounds above is substituted with dihalide (eg, dichloride or difluoride) or bisphenoxide. In another embodiment, “hafnium” in the list of catalyst compounds above is replaced with zirconium. In another embodiment, “zirconium” in the list of catalyst compounds above is replaced with hafnium.

(b) The terms activator “cocatalyst” and “activator” are used interchangeably herein and convert any one of the above catalyst compounds by converting a neutral catalyst compound to a catalytically active catalyst compound cation. Defined as any compound that can be activated. Non-limiting activators include, for example, ionization activators (which may be neutral or ionic), and conventional types of cocatalysts. Preferred activators are typically ionized anion precursor compounds that pull one reactive σ-bond, metal ligands to make the metal complex cationic, and provide charge-balanced non-coordinating or weakly coordinating anions. Can be mentioned.
It is preferred that little or no alumoxane is used in the process for producing the branched polyolefin. Preferably, the alumoxane is present in zero mole percent and the alumoxane is present in a molar ratio of aluminum to transition metal of less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1: 1. . In another embodiment, when alumoxane was used to produce a branched polyolefin, the alumoxane was treated to remove free alkyl aluminum compounds, particularly trimethylaluminum.
It is preferred that non-alumoxane is used as the activator. Further, in a preferred embodiment, the active agents used herein to produce branched polyolefins are bulky and separate as defined herein.

Ionizing activators Ionizing activators or stoichiometric activators (neutral or ionic), eg tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, trisperfluorophenylboron metalloid precursor or trisperfluoronaphthylboron It is within the scope of the present invention to use metalloid precursors, polyhalogenated heteroborane anions (WO 98/43983), boric acid (US Pat. No. 5,942,459) or combinations thereof. It is also within the scope of the present invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. Many preferred active agents are ionic and 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, and alkenyl groups having 1 to 20 carbon atoms 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) are preferable. More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl, or mixtures thereof. More preferably, the three groups are halogenated, preferably fluorinated aryl groups. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronaphthyl boron.

An ionic stoichiometric activator compound is associated with an active proton, or the remaining ions of the ionized compound, but is not coordinated or some other cation that is slightly loosely coordinated May be included. EP 0 570 982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 B1; EP 0 277 003 A; EP 0 277 004 A; U.S. Pat.No. 5,153,157 No. 5,198,401; No. 5,066,741; No. 5,206,197; No. 5,241,025; No. 5,384,299; No. 5,502,124; All of which are fully incorporated herein by reference.
An ionic catalyst can cause a transition metal compound to react with a neutral Lewis acid such as B (C ₆ F ₆ ) ₃ (which reacts with the hydrolyzable ligand (X) of the transition metal compound after an anion such as ([[ B (C ₆ F ₅ ) ₃ (X)] ⁻ ) (which stabilizes the cationic transition metal species produced by the reaction) can be prepared by reaction. These catalysts can be prepared with, preferably, activator components that are ionic compounds or compositions.
Compounds useful as activator components in the preparation of the ionic catalyst system used in the process of the present invention are cations (preferably Bronsted acids capable of donating protons) and compatible non-coordinating anions ( The anion is relatively large (bulky) and contains an active catalytic species (Group 4 cation) that is produced when the two compounds are combined), said anion being olefinic, diolefinic and acetylene May be sufficiently unstable to be displaced by a neutral unsaturated substrate or other neutral Lewis base such as ether, amine, and the like. Two classes of compatible non-coordinating anions: 1) Anionic coordination complexes containing multiple lipophilic groups covalently coordinated to and masking a centrally charged metal or metalloid core, and 2) multiple Anions containing a number of boron atoms such as carborane, metallacarborane and borane are disclosed in EP 0 277,003 A and EP 0 277,004 A published in 1988.

In a preferred embodiment, the stoichiometric activator comprises cation and anion components and can be represented by the following formula:
(LH) _d ⁺ (A ^d- ) (14)
Where L is a neutral Lewis base, H is hydrogen, (LH) ⁺ is a Bronsted acid, A ^d− is a non-coordinating anion with charge d−, and d is 1, 2 or 3.
Its cationic component, (LH) _d ⁺ is a Bronsted acid, such as a protonated Lewis base, that can protonate alkyl or aryl moieties from bulky ligand metallocene-containing transition metal catalyst precursors to yield cationic transition metal species. May be included.
The activated cation (LH) _d ⁺ may be a Bronsted acid, which can donate a proton to the transition metal catalyst precursor to produce a transition metal cation, and is preferably ammonium, oxonium, phosphonium, silylium, and mixtures thereof, preferably Is methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N, N-dimethylaniline, p-nitro-N, N-dimethylaniline ammonium; phosphonium from triethylphosphine, triphenylphosphine, and diphenylphosphine; ethers such as oxonium from dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; thioether Such as diethyl thioether and sulfonium from tetrahydrothiophene, and mixtures thereof.
Anionic components A ^d- include those having the formula [M ^{k +} Q _n ] ^d- , where k is 1, 2, or 3, n is 2, 3, 4, 5, or 6; n-k = d, M is an element from group 13 of the periodic table of elements, preferably boron or aluminum, and Q is independently hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryl Oxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted hydrocarbyl groups, where Q has up to 20 carbon atoms, provided that Q is a halide with an appearance of 1 or less. . Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluorylaryl. It is a group. Further, suitable A example of ^d-, U.S. Patent No. 5,447,895 (which is included is totally incorporated herein by reference) include diboric-containing compounds disclosed in.

Illustrative, 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 invention include trisubstituted ammonium salts, such as
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, triphenylphosphonium Tetraphenylborate, triethylsilylium tetraphenylborate, benzene (diazonium) tetraphenylborate, trimethylammonium tetrakis (pentafur Rophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (penta Fluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl- (2,4,6-trimethylanily Nium) tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetra (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) 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-tetrafluoro Enyl) borate, N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) 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, triphenylcarbenium Tetrakis (perfluoronaphthyl) borate, Triphenylphosphonium Tetrakis (perfluoronaphthyl) borate, Trie Tyryllium 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 tetrakis (perfluorobiphenyl) 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) ammoni 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- (2,4,6-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 (trifluoro) Methyl) phenyl) borate, and dialkylammonium salts, such as di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, and dicyclohexylammonium tetrakis (pentafluorophenyl) borate, and additional trisubstituted phosphonium salts, such as , Tri (o-tolyl) phosphonium tetrakis (pentafluorophenyl) borate, and tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate.

Most preferably, the ionic stoichiometric activator (LH) _d ⁺ (A ^d- ) 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, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylcarbe Nium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate or triphenylcarbenium tetrakis (perfluorophenyl) borate.
In one embodiment, activation methods using ionized ionic compounds and their non-coordinating anions that are free of active protons but are capable of generating bulky ligand metallocene-catalyzed cations are also contemplated, and EP 0 426 637 A , EP 0 573 403 A, and US Pat. No. 5,387,568, all of which are hereby incorporated by reference.
The term “non-coordinating anion” (NCA) refers to an anion that does not coordinate to the cation, or that is only weakly coordinated to the cation and thereby remains sufficiently unstable to be displaced by a neutral Lewis base. means. A “compatible” non-coordinating anion is one that does not degrade to neutrality when the initially formed complex degrades. Furthermore, the anion will not transfer the anion substituent or fragment to the cation so that it produces a neutral byproduct from the neutral tetracoordinate metallocene compound and the anion. The non-coordinating anions useful for the present invention are compatible and stabilize the metallocene cation in the sense of balancing its ionic charge at +1, yet allow substitution by ethylenically or acetylenically unsaturated monomers during polymerization. It remains unstable enough to do. In addition to these activator compounds or promoters, scavengers such as tri-isobutylaluminum or tri-octylaluminum are used. It is preferred that the activator is a non-coordinating anion activator.

The method of the present invention is also initially a neutral Lewis acid, but a co-catalyst compound or activator compound that forms a zwitterionic complex after reaction with a cationic metal complex and a non-coordinating anion, or a compound of the present invention. Can be used. For example, tris (pentafluorophenyl) boron or aluminum abstracts the hydrocarbyl or hydride ligand to form the cationic metal complex of the present invention and acts to stabilize non-coordinating anions. See EP 0 427 697 A and EP 0 520 732 A for a description of similar Group 4 metallocene compounds. See also EP 0 495 375 A methods and compounds. 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 ion production, activation cocatalyst comprises a cationic oxidant represented by the following formula and a salt of a non-coordinating, compatible anion.
(OX ^{e +} ) _d (A ^d- ) _e (16)
Where OX ^{e +} is a cationic oxidant with a charge of e +, e is 1, 2, or 3, and A ^d− is a non-coordinating anion with a charge d−, and d is 1 , 2 or 3. Examples of cationic oxidizing agents include ferrocenium, hydrocarbyl substituted ferrocenium, Ag ⁺ or Pb ⁺² . A ^d-preferred embodiment is already of these defined anion, especially tetrakis (pentafluorophenyl) borate respect Bronsted acid containing activators.
A typical NCA (ie non-alumoxane activator) activator to catalyst ratio is a 1: 1 molar ratio. Other preferred ranges include from 0.1: 1 to 100: 1, also from 0.5: 1 to 200: 1, also from 1: 1 to 500: 1, and from 1: 1 to 1000: 1. A particularly useful range is from 0.5: 1 to 10: 1, preferably from 1: 1 to 5: 1.

Bulky activators We have surprisingly found that bulky activators are particularly beneficial. Bulky activators can advantageously produce higher Mw, higher Tm, and / or higher amounts of allylic chain ends than the same catalyst containing non-bulky activators under the same polymerization conditions.
As used herein, “bulky activator” refers to an anionic activator represented by the following formula:

Where
Each R ₁ is independently a halide, preferably fluoride,
Each R ₂ is independently a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. (Preferably R ₂ is a fluoride or a perfluorinated phenyl group),
Each R ₃ is a halide, a C ₆ -C ₂₀ substituted 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. Yes (preferably R ₃ is a fluoride or a C ₆ perfluorinated aromatic hydrocarbyl group), 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)
L is a neutral Lewis base;
(LH) ⁺ is a Bronsted acid,
d is 1, 2, or 3;
The anion has a molecular weight greater than 1020 g / mole and at least three of the substituents on the B atom each have a molecular volume greater than 250 cubic cubic and greater than 300 cubic cubic or greater than 500 cubic cubic.
“Molecular volume” is used herein as an approximation of the spatial volume of an activator molecule in solution. Comparison of substituents having different molecular volumes allows substituents having the same molecular volume to be considered “not bulky” compared to substituents having a larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume.
Molecular volume is reported in “Simple“ Envelope Back ”Method for Estimating Liquid and Solid Densities and Branched Volumes” Journal of Chemical Education, Vol. 71, No. 11, November 1994, pages 962-964 May be calculated as follows. Molecular volume (MV) (unit cubic Å) formula MV = 8.3 V _s (wherein, V _s is the scale volume, V _s is which is the sum of the relative volumes of components atoms) is calculated using the , Calculated from the molecular formula of the substituent using the relative volume table below. For fused rings, V _s is reduced by 7.5% per fused ring.

Exemplary bulky substituents of suitable active agents herein and their respective scale and molecular volumes are shown in the table below. A broken bond indicates a bond to boron as in the above general formula.

Useful exemplary bulky activators in the catalyst systems herein include 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, Triethylsilyliumtetrakis (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-dimethylanily Nitro tetrakis (perfluorobiphenyl) borate, N, N-diethylanilinium teto Kiss (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 the mold disclosed in US Pat. No. 7,297,653.
It is within the scope of the present invention for the catalyst compound to be combined with one or more activators or activation methods described above.

(iii) Optional co-activators and scavengers In addition to these activator compounds, scavengers or co-activators may be used. Aluminum alkyl compounds or organoaluminum compounds that can be used as co-activators (or scavengers) include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. It is done.
(iv) Optional Support Material In the embodiments herein, the catalyst system may include an inert simple substance. The carrier material is preferably a porous carrier material such as talc and inorganic oxides. Other carrier materials include zeolites, clays, organoclays, or any other organic or inorganic carrier material, or mixtures thereof.
It is preferred that the support material is an inorganic oxide in a fine form. Inorganic oxide materials suitable for use in the metallocene catalyst systems herein include Group 2, Group 4, Group 13, and Group 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina are magnesia, titania, zirconia and the like. However, other suitable carrier materials such as fine functionalized polyolefins such as fine polyethylene can be used. 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. may 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 an average particle in the range of about 5 to about 500 μm. It is preferable to have a size. The surface area of the support material is in the range of about 50 to about 500 m ² / g, the pore volume is in the range of about 0.5 to about 3.5 cc / g, and the average particle size is in the range of about 10 to about 200 μm. More preferably. The surface area of the support material is in the range of about 100 to about 400 m ² / g, the pore volume is in the range of about 0.8 to about 3.0 cc / g, and the average particle size is in the range of about 5 to about 100 μm. Most preferred. The average pore size of the carrier material useful in the present invention ranges from 10 to 1000 inches, preferably from 50 to about 500 inches, and most preferably from 75 to about 350 inches. In one embodiment, the support material is high surface area amorphous silica (surface area = 300 m ² / gm; 1.65 cm ³ / gm pore volume), an example of which is Davison 952 by Davison Chemical Department of WR Grace and Company. Or it is marketed under the trade name Davison 955. In other embodiments, DAVISON 948 is used.
The carrier material should be dried, i.e. should not contain absorbed water. The support material can be dried by heating or baking at about 100 ° C to about 1000 ° C, preferably at least about 600 ° C. When the support material is silica, it is at least 200 ° C, preferably about 200 ° C to about 850 ° C, most preferably about 600 ° C, for 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 to produce the 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 of making 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. . A slurry of the carrier material in the solvent is prepared by introducing the carrier material into the solvent and heating the mixture to about 0 ° C to about 70 ° C, preferably about 25 ° C to about 60 ° C, preferably room temperature. Contact times typically range from about 0.5 hours to about 24 hours, from about 0.5 hours to about 8 hours, or from about 0.5 hours to about 4 hours.
Suitable nonpolar solvents are those materials in which all of the reactants used herein, i.e., the activator and the metallocene compound, are at least partially soluble and liquid at the reaction temperature. Preferred apolar solvents are alkanes such as isopentane, hexane, n-heptane, octane, nonane, and decane, but various other including cycloalkanes such as cyclohexane, aromatics such as benzene, toluene and ethylbenzene. These materials may also be used.
In embodiments herein, the support material is contacted with a solution of the metallocene compound and the activator so that the reactive groups of the support material are titrated to produce a supported polymerization catalyst. The period of time for contact between the metallocene compound, the active agent, and the support material is the length necessary to titrate the reactive groups of the support material. “Titrate” means to react 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%. The surface reactive group concentration may be determined based on the firing temperature and type of the support material used. The support material firing temperature affects the number of surface reactive groups on the support material that can be utilized to react with the metallocene compound and the activator. The higher the drying temperature, the lower the number of sites. For example, if the support material is silica (which is dehydrated by fluidizing it with nitrogen and heating at about 600 ° C. for about 16 hours prior to its use during the initial catalyst system synthesis step) A surface hydroxyl group concentration of about 0.7 millimoles per milligram (mmol / g) is typically obtained. Thus, the exact molar ratio of activator to carrier surface reactive groups will change. This is preferably determined on a case-by-case basis to ensure that much of the active agent is added to the solution such that it is attached to the carrier material without leaving an excess of active agent in the solution.

The amount of active agent attached to the support material without remaining in excess in solution can be determined in any conventional manner, e.g., any solution in which the active agent is known in the art, e.g., solution in solvent by ¹ H NMR. The active agent is added to the slurry of the carrier in the solvent while stirring the slurry until detected as. For example, for a silica support material heated at about 600 ° C., the amount of activator added to the slurry is from about 0.5: 1 to about 4: 1 molar ratio of B to silica hydroxyl groups (OH), preferably about The amount is from 0.8: 1 to about 3: 1, more preferably from about 0.9: 1 to about 2: 1, most preferably about 1: 1. The amount of boron on silica is ICPES (Inductively Coupled Plasma Emission Spectroscopy) (this is Encyclopedia of Materials Characterization, CR Brundle, CA Evans, Jr. and S. Wilson, edited by Butterworth-Heinemann, Boston, Mass., 1992 , Pp. 633-644, JW Olesik, described in “Inductively Coupled Plasma Light Emission Spectroscopy”). In another embodiment, it is possible to add an amount of active agent that is in excess of the amount attached to the carrier, and then remove the excess active agent, for example, by filtration and washing.

Vinyl End Branched Polyolefin Embodiments herein relate to a branched polyolefin having 50% or more allyl chain ends. The inventors have surprisingly found that the method disclosed herein results in an increased population of long chain branching products, possibly due to vinyl macromonomer reuptake. Although not wishing to be bound by theory, we believe that the branches are probably of the “T” variety and that these branched polyolefins retain a large amount of allyl chain ends.
Branched polyolefins having 50% or more allyl chain ends produced by the method disclosed herein are:
(a) has at least one of the following and branches:
(i) a branching index (g'vis) of less than 0.90 (preferably 0.85 or less, preferably 0.80 or less), or
(ii) The ratio of the percentage of saturated chain ends (preferably isobutyl chain ends) of 1.2 to 2.0 (preferably 1.6 to 1.8) to the percentage of allyl chain ends (the percentage of saturated chain ends is the spectrum of the solvent, tetrachloroethane-d Measured using ¹³ C NMR as described in paragraphs [0095] and [0096] of WO 2009/155471 except that it is referenced to a chemical shift of ₂ ), or
(iii) a ratio of Mn (GPC) / Mn ( ¹ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less), and
(b) At least 50% with respect to the total unsaturated chain ends (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more) And having at least one of the following:
(i) a bromine number which decreases by at least 50% (preferably at least 75%) after complete hydrogenation, or
(ii) Allyl chain end to internal vinylidene ratio greater than 5: 1 (preferably greater than 10: 1), or
(iii) an allyl chain end to vinylidene chain end ratio greater than 10: 1 (preferably greater than 15: 1), or
(iv) Allyl chain end to vinylene chain end ratio greater than 1: 1 (preferably greater than 2: 1, greater than 5: 1 or greater than 10: 1).

With respect to branching, in embodiments where the branched polyolefin has 7,500-60,000 g / mol of Mn (measured by ¹ H NMR), the branched polyolefin is
(i) Branch index (g'vis) less than 0.90 (preferably less than 0.85, less than 0.80, or less than 0.75), and / or
(ii) the ratio of the percentage of saturated chain ends (preferably isobutyl chain ends) of 1.2 to 2.0 (preferably 1.6 to 1.8) to the percentage of allyl chain ends (the percentage of saturated chain ends is the spectrum of the solvent, tetrachloroethane-d Measured using ¹³ C NMR as described in paragraphs [0095] and [0096] of WO 2009/155471, with the exception of being referenced to a chemical shift of ₂ ), and / or
(iii) having a ratio of Mn (GPC) / Mn ( ¹ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less). In case of discrepancy, g'vis should be used (if g'vis cannot be measured, the ratio of the percentage of saturated chain ends to the percentage of allyl chain ends should be used, If the ratio of the percentage of saturated chain ends to the percentage of allyl chain ends is not measurable, the ratio Mn (GPC) / Mn ( ¹ H NMR) should be used).

In embodiments where the branched polyolefin has an Mn (measured by GPC) greater than 60,000 g / mol, the branched polyolefin has a g'vis of less than 0.90 (preferably less than 0.85, preferably less than 0.80) and optionally Have a bromine number that decreases by at least 50% (preferably at least 75%) after complete hydrogenation.
In embodiments where the branched polyolefin has less than 7,500 g / mol (preferably 100-7,500 g / mol) of Mn (measured by ¹ H NMR), one or more alpha olefins (preferably propylene and / or ethylene, And preferably C ₄ -C ₄₀ alpha olefin (preferably C ₄ -C ₂₀ alpha olefin, preferably C ₄ -C ₁₂ alpha olefin, preferably butene, pentene, hexene, heptene, octene, nonene. , Decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof) and
(i) The ratio of the percentage of saturated chain ends (preferably isobutyl chain ends) of 1.2 to 2.0 (preferably 1.6 to 1.8) to the percentage of allyl chain ends (the percentage of saturated chain ends is the spectrum of the solvent, tetrachloroethane-d Measured using ¹³ C NMR as described in paragraphs [0095] and [0096] of WO 2009/155471, with the exception of being referenced to a chemical shift of ₂ ), and / or
(ii) It has a ratio of Mn (GPC) / Mn ( ¹ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less).
In another embodiment, the branched polyolefin having less than 7,500 g / mol (preferably 100-7,500 g / mol) of Mn (measured by ¹ H NMR) is 0.90 or less (preferably 0.85 or less, preferably 0.80 or less ) G'vis.

In one embodiment, the prepared branched polyolefins herein have 7,500-60,000 g / mol of Mn (measured by ¹ H NMR) and one or more alpha olefins (preferably propylene and / or ethylene). And preferably propylene) and optionally C _{4 to} C ₄₀ alpha olefins (preferably C _{4 to} C ₂₀ alpha olefins, preferably C _{4 to} C ₁₂ alpha olefins, preferably butene, pentene, hexene, heptene, octene, Nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), and
(i) 50% or more (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more with respect to the total unsaturated chain ends ) End of the allyl chain,
(ii) 0.9 'or less (preferably 0.85 or less, preferably 0.80 or less) g'vis and / or 1.2 to 2.0 (preferably 1.6 to 1.8) saturated chain end (preferably isobutyl chain end) percentage to allyl chain Ratio of terminal percentages (percentage of saturated chain ends as described in paragraphs [0095] and [0096] of WO 2009/155471, except that the spectrum is based on the chemical shift of the solvent, tetrachloroethane-d ₂ And / or a ratio of Mn (GPC) / Mn ( ¹ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less), and / or ¹³ C NMR
(iii) peak melting point (Tm), if necessary, higher than 60 ° C (preferably higher than 100 ° C, preferably from 60 ° C to 180 ° C, preferably from 80 ° C to 175 ° C),
(iv) optionally greater than 7 J / g (preferably greater than 15 J / g, greater than 30 J / g, greater than 50 J / g, greater than 60 J / g or greater than 80 J / g) ) Heat of fusion (Hf),
(v) Allyl chain end to internal vinylidene ratio, if necessary, greater than 5: 1 (preferably greater than 10: 1)
(vi) optionally greater than 10: 1 (preferably greater than 15: 1) allyl chain end to vinylidene chain end ratio; and
(vii) optionally having an allyl chain end to vinylene chain end ratio greater than 1: 1 (preferably greater than 2: 1, greater than 5: 1 or greater than 10: 1).

In another embodiment, the branched polyolefin produced herein has a Mn (measured by GPC) greater than 60,000 g / mol, and one or more alpha olefins (preferably propylene and / or ethylene, preferably And optionally C _{4 to} C ₄₀ alpha olefins (preferably C _{4 to} C ₂₀ alpha olefins, preferably C _{4 to} C ₁₂ alpha olefins, preferably butene, pentene, hexene, heptene, octene, nonene, decene. , Cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), and
(i) 50% or more (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% with respect to the total unsaturated chain ends Allyl chain end),
(ii) 0.9 'or less (preferably 0.85 or less, preferably 0.80 or less) g'vis,
(iii) optionally a bromine number which decreases by at least 50% (preferably at least 75%) after complete hydrogenation,
(iv) optionally a Tm higher than 60 ° C (preferably higher than 100 ° C, from 60 ° C to 180 ° C, preferably from 80 ° C to 175 ° C), and
(v) greater than 7 J / g, preferably greater than 15 J / g, greater than 30 J / g, greater than 50 J / g, greater than 60 J / g, or greater than 80 J / g, as required ) Hf
Have

In another embodiment, the branched polyolefin produced herein has a Mn (measured by ¹ H NMR) of less than 7,500 g / mol (preferably 100-7,500 g / mol), and one or more Alpha olefins (preferably propylene and / or ethylene, preferably propylene) and optionally C _{4 to} C ₄₀ alpha olefins (preferably C _{4 to} C ₂₀ alpha olefins, preferably C _{4 to} C ₁₂ alpha olefins, preferably Butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), and
(i) 50% or more (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more with respect to the total number of unsaturated chain ends. % Or more) allyl chain end,
(ii) the ratio of the percentage of 1.2 to 2.0 (preferably 1.6 to 1.8) saturated chain ends (preferably isobutyl chain ends) to the percentage of allyl chain ends (the percentage of saturated chain ends is determined by the spectrum ₂ is measured using ¹³ C NMR as described in paragraphs [0095] and [0096] of WO 2009/155471, and / or 0.95 or less (preferably, except referenced to ₂ chemical shifts) 0.90 or less, preferably 0.85 or less, preferably 0.80 or less) Mn (GPC) / Mn ( ¹ H NMR) ratio,
(iii) Tm higher than 60 ° C if necessary (preferably higher than 100 ° C, 60-180 ° C, preferably 80-175 ° C),
(iv) optionally greater than 7 J / g (preferably greater than 15 J / g, greater than 30 J / g, greater than 50 J / g, greater than 60 J / g or greater than 80 J / g) ) Hf,
(v) Allyl chain end to internal vinylidene ratio, if necessary, greater than 5: 1 (preferably greater than 10: 1),
(vi) optionally an allyl chain end to vinylidene chain end ratio greater than 10: 1 (preferably greater than 15: 1), and
(vii) optionally having an allyl chain end to vinylene chain end ratio greater than 1: 1 (preferably greater than 2: 1, greater than 5: 1 or greater than 10: 1).

In certain embodiments, the branched polyolefin has a branching index of 0.90 or less (preferably 0.85 or less, preferably 0.80 or less), g'vis (measured by GPC) for linear polymers of the same composition and microstructure. Have
Preferred branched polyolefins described herein are from 7,500 to 60,000 g / mol, or greater than 60,000 g / mol, or from 100 g / mol to less than 7,500 g / mol (measured by ¹ H NMR) Have Furthermore, the desirable molecular weight range may be a combination of any of the above-described molecular weight upper limits and any molecular weight lower limits. Mn ( ¹ H NMR) is measured according to the NMR method described below in the Examples section. Mn may also be measured using the GPC-DRI method as described below. For the purposes of the claims, Mn is measured by ¹ H NMR unless otherwise indicated.
In another embodiment, the branched polyolefin described herein is 1000 g / mole or more (preferably about 1,000 to about 400,000 g / mole, preferably about 2000 to 300,000 g / mole, preferably about 3,000 to 200,000. g / mol) Mw (determined using the GPC-DRI method as described below) and / or a range of about 1700 to about 150,000 g / mol or preferably about 800 to 100,000 g / mol Mz and / or Mw / Mn in the range of about 1.2 to 20 (also about 1.7 to 10 and also about 1.8 to 5.5).
In a particular embodiment, the branched polyolefin described herein has a ratio of Mn (GPC) / Mn ( ¹ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less). Have. With respect to FIG. 1, FIG. 1 shows a plot of Mn calculated from Mn versus ¹ H NMR data measured by GPC, as shown below. A plot of the best fit line for the experimental data (shown as a solid line) is below the parity plot (dashed line). The slope of the best fit line is 0.73065.

Assuming one unsaturation per polyolefin chain, Mn is calculated from ¹ H NMR data. ¹ H NMR data using a Varian spectrometer at a proton frequency of 250 MHz, 400 MHz, or 500 MHz in a 5 mm probe (400 mHz i proton frequency is used for claims purposes) And collected at room temperature or 120 ° C. (120 ° C. should be used for the purposes of the claims). Data is recorded using a maximum pulse width of 45 ° C, 8 seconds between the pulse and an average 120 transient signal. Spectral signals are integrated and calculated by multiplying 1000 different unsaturated groups with 1000 different numbers of unsaturated types and dividing the result by the total number of carbons. Mn ( ¹ H NMR) is calculated by dividing the total number of unsaturated species by 14,000 and has units of g / mol.
Mn, Mw, Mz, carbon number, and g'vis are high temperature size exclusion chromatographs (from SEC, Waters Corporation or Polymer Laboratories) equipped with DRI by GPC-DRI (gel permeation chromatography-differential refractive index) method. Measured using. Details of the experiment are described in T. Sun, P. Brant, RR Chance, and WW Graessley, Macromolecules, 34, 19, 6812-6820, (2001) and references therein. Three Polymer Laboratories PLgel 10mm mixed-B columns are used. The nominal flow rate is 0.5 cm ³ / min and the nominal injection volume is 300 μL. Various transfer lines, columns and differential refractometer (DRI detector) are contained in an oven maintained at 135 ° C. The solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 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 with an online degasser before entering the SEC. A polymer solution is prepared by placing the dried polymer in a glass container, adding the desired amount of TCB, and then heating the mixture at 160 ° C. with continuous stirring for about 2 hours. All quantities are measured with a weigh scale. The TCB density used to express the polymer concentration in weight / 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 lower concentrations being used for higher molecular weight samples. Prior to experimenting with 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 stabilized for 8-9 hours before injecting the first sample. The concentration at each position in the chromatogram, c, is calculated from the DRI signal, I _DRI , with a baseline drawn using the following formula:

式中、K_DRI はDRI を較正することにより求められる定数であり、かつ(dn/dc) はその系についての屈折率増分である。屈折率、n = 1.500 （135 ℃及びλ = 690 nmでTCB について）。本発明及び特許請求の範囲の目的のために、 (dn/dc) = 0.104 （プロピレンポリマーについて）またそれ以外について0.1 。SEC 方法のこの記載中に使用されるパラメーターの単位は以下のとおりである：濃度がg/cm³ で表され、分子量がg/モルで表され、また固有粘度がdL/gで表される。
LS検出器はWyatt Technology高温ミニ-DAWN である。クロマトグラムの夫々の位置における分子量、M が、静的光散乱についてのZimmモデル(M.B. Huglin著, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971) を使用してLSアウトプットを分析することにより測定される。

Where K _DRI is a constant determined by calibrating DRI, and (dn / dc) is the refractive index increment for the system. Refractive index, n = 1.500 (for TCB at 135 ° C. and λ = 690 nm). For the purposes of the present invention and claims, (dn / dc) = 0.104 (for propylene polymers) and 0.1 otherwise. The unit of parameters used in this description of the SEC method is as follows: concentration is expressed in g / cm ³ , molecular weight is expressed in g / mol, and intrinsic viscosity is expressed in dL / g. .
The LS detector is Wyatt Technology High Temperature Mini-DAWN. The molecular weight, M, at each location in the chromatogram was measured by analyzing the LS output using the Zimm model for static light scattering (MB Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971). The

ここで、ΔR(θ) は散乱角度θにおける測定された過剰Rayleigh 散乱強さであり、ｃはDRI 分析から測定されたポリマー濃度であり、A₂は第二ビリアル係数[本発明の目的のために、A₂ = 0.0006 （プロピレンポリマーについて）、0.0015（ブテンポリマーについて）またそれ以外では0.001]であり、(dn/dc) = 0.104 （プロピレンポリマーについて）、0.098 （ブテンポリマーについて）またそれ以外では0.1 、P(θ) は単分散ランダムコイルについての形状係数であり、かつK_oはその系についての光学定数である。

Where ΔR (θ) is the measured excess Rayleigh scattering intensity at the scattering angle θ, c is the polymer concentration measured from DRI analysis, and A ₂ is the second virial coefficient [for purposes of the present invention. A ₂ = 0.0006 (for propylene polymer), 0.0015 (for butene polymer) and 0.001] otherwise, (dn / dc) = 0.104 (for propylene polymer), 0.098 (for butene polymer) and otherwise 0.1, P (θ) is the shape factor for the monodisperse random coil, and _Ko is the optical constant for the system.

Where N _A is Avogadro's number and (dn / dc) is the refractive index increment for the system. Refractive index, n = 1.500 (for TCB at 145 ° C and λ = 690 nm)
A high temperature Viscotek Corporation viscometer (which has two pressure transducers and has four capillaries arranged in a Wheatstone bridge configuration) is used to measure the specific viscosity. One transducer measures the total pressure drop across the detector, and the other transducer located between the two sides of the bridge measures the differential pressure. The specific viscosity, η _s , for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity [η] at each position in the chromatogram is calculated from the following equation.

Where c is the concentration and was measured from the DRI output.
The branch index (g ' _vis ) is calculated using the output of the SEC-DRI-LS-VIS method as follows: The average intrinsic viscosity, [η] _avg , of the sample is calculated according to the following formula:

Where the sum is for the chromatogram piece i between the integration limits.
The branch index g'vis is defined as follows:

In this case, for the purposes of the present invention and claims, α = 0.695 and k = 0.000579 per linear ethylene polymer, α = 0.705 and k = 0.000262 per linear propylene polymer, and per linear butene polymer. , Α = 0.695 and k = 0.000181. _Mv is the viscosity average molecular weight based on the molecular weight measured by LS analysis. See Macromolecules, 2001, 34, 6812-6820 and Macromolecules, 2005, 38, 7181-7183 for guidance on choosing linear standards with similar molecular weight and comonomer content and measuring the k-factor and α-index. checking ...
In some embodiments, the branched polyolefin has 50% or more (preferably 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more) of allyl chain ends. . Branched polyolefins generally have chain ends (or ends) that are saturated and / or unsaturated chain ends. The unsaturated chain ends of the polymers of the present invention include “allyl chain ends”. The allyl chain end is represented by the following formula.

In the formula, M represents a polymer chain. “Allyl vinyl group”, “allyl chain end”, “vinyl chain end”, “vinyl end”, “allylic vinyl group” and “vinyl end” are used interchangeably in the following description.
“Allyl chain end to vinylidene chain end ratio” is defined as the ratio of the percentage of allyl chain ends to the percentage of vinylidene chain ends. In some embodiments, the allyl chain end to vinylidene chain end ratio is greater than 10: 1 (preferably greater than 15: 1).
“Allyl chain end to vinylene chain end ratio” is defined as the ratio of the percentage of allyl chain ends to the percentage of vinylene chain ends. In some embodiments, the allyl chain end to vinylene chain end ratio is greater than 1: 1 (preferably greater than 2: 1, greater than 5: 1, or greater than 10: 1).
“Allyl chain end to internal vinylidene ratio” is defined as the ratio of the percentage of allyl chain ends to the percentage of internal (or non-terminal) vinylidene groups. In some embodiments, the allyl chain end to internal vinylidene ratio is greater than 5: 1 (preferably greater than 10: 1).
The number of allyl chain ends, vinylidene chain ends, and vinylene chain ends was measured and selected using ¹ H NMR with an NMR spectrometer at least 250 MHz using deuterated tetrachloroethane as a solvent at 120 ° C. In some cases, it is confirmed by ¹³ C NMR. Resconi reports proton and carbon assignments for vinyl-terminated propylene oligomers in J. American Chemical Soc., 114, 1992, pages 1025-1032 (neat perdeuterated tetrachloroethane was used for the proton spectrum, while A 50:50 mixture of normal tetrachloroethane and perdeuterated tetrachloroethane was used for the carbon spectrum; all spectra were recorded on a Bruker spectrometer operating at 100 ° C for protons at 500 MHz and for carbon at 125 MHz) These are useful herein. Allyl chain ends are reported as mole% of the total number of moles of unsaturated groups (ie, total of allyl chain ends, vinylidene chain ends, vinylene chain ends, etc.).

Unsaturated chain ends may be further characterized by using bromine electrotitration, as described in ASTM D 1159. The resulting bromine number is useful as a measure of the unsaturation present in the sample. In embodiments herein, the branched polyolefin has a bromine number that decreases by at least 50% (preferably at least 75%) after complete hydrogenation.
Branched polyolefins also have at least one saturated chain end, preferably at least two saturated chain ends, per branched polyolefin molecule. In some embodiments, the branched polyolefins produced herein have a ratio of 1.2-2.0 (preferably 1.6-1.8) saturated chain ends (preferably isobutyl chain ends) to allyl chain ends. The percentage of saturated chain ends is ¹³ C NMR as described in paragraphs [0095] and [0096] of WO 2009/155471, except that the spectrum is based on the chemical shift of the solvent, tetrachloroethane-d _2. Measured using If the branched polyolefin contains propylene derived units, the saturated chain ends may contain isobutyl chain ends. “Isobutyl chain end” is defined as the end or end of the polymer, as shown in the formula below.

In the formula, M represents a polymer chain. The structure of the branched polyolefin near the end of the saturated chain may vary depending on the type and amount of one or more monomers used and the method of insertion in the polymerization process. In certain preferred embodiments, when the branched polyolefin comprises propylene derived units and C _{4 to} C ₄₀ alpha olefin derived units, the structure of the polymer having 4 carbons at the isobutyl chain end is represented by one of the following formulas: Is done.

Where M represents the remainder of the polymer chain and C _m represents the polymerized monomer, each C _m may be the same or different, where m is from 2 to 8 It is an integer up to.
The percentage of isobutyl chain ends is ¹³ C NMR (described in the Examples section) and Resconi et al., J. Am. Chem. Soc. 114, 1992, 1025-1032 for 100% propylene oligomers. And are reported herein for branched polyolefins.
In some embodiments, the branched polyolefin has a ratio of 1.2-2.0 (preferably 1.6-1.8) saturated chain ends (preferably isobutyl chain ends) to allyl chain ends percentage and saturated chain end percentages. Is measured using ¹³ C NMR as described in paragraphs [0095] and [0096] of WO 2009/155471 except that its spectrum is referenced to the chemical shift of the solvent, tetrachloroethane-d ₂ .
In other embodiments, the branched polyolefins described herein have a Tm above 60 ° C (preferably above 100 ° C, preferably 60-180 ° C, preferably 80-175 ° C).
In other embodiments, the branched polyolefin described herein is greater than 7 J / g (preferably greater than 15 J / g, greater than 30 J / g, greater than 50 J / g, 60 J / g greater than g or greater than 80 J / g).
In other embodiments, the branched polyolefin described herein is 0 ° C or less, preferably -10 ° C or less, more preferably -20 ° C or less, more preferably -30 ° C or less, more preferably -50 ° C. It has the following glass transition temperature (Tg) (measured by differential scanning calorimetry as described below).

  Tm, Hf, and Tg are measured by commercially available equipment such as differential scanning calorimetry (DSC) using TA Instruments model Q100. Typically, 6-10 mg of sample (which has been stored at room temperature for at least 48 hours) is sealed in an aluminum pan and loaded into the apparatus at room temperature. The sample is equilibrated at 25 ° C. and then it is 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. Also, the sample was allowed to equilibrate to 25 ° C. for 5 minutes, then heated to 200 ° C. at a heating rate of 10 ° C./min, followed by equilibration to 200 ° C. for 5 minutes, to −80 ° C. at 10 ° C./min. To be cooled. The endothermic melting transition (if present) is analyzed for the onset of transition and peak temperature. The reported melting temperature is the peak melting temperature from the first heating unless otherwise specified. For samples showing many peaks, the melting point (or melting temperature) is defined as the peak melting temperature associated with the maximum endothermic calorimetric response in that range of temperatures from the DSC melting trace. The area under the DSC curve is used to measure the heat of transition (melting heat during melting or heating, Hf, Hc during crystallization) (Hf value from melting is the heat of crystallization) If different from the obtained Hc value, the value from melting (Tm) should be used), which can be used to calculate the crystallinity (also called% crystallinity). Crystallinity% (X%) is the formula: [area under the curve (unit J / g) / H ° (unit J / g)] * 100 (where H ° is the heat of fusion of the main monomer component homopolymer) Is calculated). These values for H ° are the values for 290 J / g used as the equilibrium heat of fusion (H °) for 100% crystalline polyethylene and the values for 140 J / g for equilibrium melting for 100% crystalline polybutene. Polymer Handbook, Volume 4, Published by John Wiley and Sons, New York, except that it is used as heat (H °) and 207 J / g (H °) is used as the heat of fusion for 100% crystalline polypropylene Should be obtained from 1999.

In another embodiment, any of the branched polyolefins described herein have a viscosity (at 190 ° C.) greater than 50 mPa.seconds, greater than 100 mPa.seconds, or greater than 500 mPa.seconds. In other embodiments, the branched polyolefin has a viscosity of less than 15,000 mPa.sec or less than 10,000 mPa.sec. Viscosity is defined herein as resistance to flow and is measured at elevated temperatures using a Brookfield viscometer according to ASTM D-3236.
In preferred embodiments, any of the branched polyolefins described herein is less than 3% by weight, preferably less than 2% by weight, less than 1% by weight, less than 0.5% by weight, 0.1% by weight, based on the weight of the copolymer. % Functional group (selected from hydroxide, aryl and substituted aryl, halogen, alkoxy, carboxylate, ester, acrylate, oxygen, nitrogen, and carboxyl).
In another embodiment, assuming that any of the branched polyolefins described herein is one unsaturated per chain, as measured by ¹ H NMR, based on the weight of the copolymer composition, at least 50% by weight (preferably at least 75% by weight, preferably at least 90% by weight) of olefins having at least 36 carbon atoms (preferably at least 51 carbon atoms or at least 102 carbon atoms).

In another embodiment, the branched polyolefin is less than 20% (preferably less than 10%, preferably less than 5%, more preferably 2%, based on the weight of the copolymer composition, as measured by gas chromatography. Less than% by weight) dimers and trimers. “Dimer” (and “trimer”) is defined as a copolymer having two (or three) monomer units, which may be the same or different from each other ( “Different” in this case means that it differs by at least one carbon atom). The product is analyzed by a gas chromatograph (Agilent 6890N with automatic injector) using helium as a carrier gas at 38 cm / sec. Column with 60 m length packed with flame ionization detector (FID), injector temperature of 250 ° C, and detector temperature of 250 ° C (J & W Scientific DB-1, 60 mx 0.25 mm IDx 1.0 μm film thickness Is used. The sample is injected into a column in an oven at 70 ° C. and then heated to 275 ° C. for 22 minutes (gradient rate: 10 ° C./min up to 100 ° C., 30 ° C./min up to 275 ° C., hold). An internal standard, usually a monomer, is used to derive the amount of dimer or trimer product obtained. The yield of dimer and trimer products is calculated from the data recorded on the spectrometer. The amount of dimer or trimer product is calculated from the area under the reasonable peak in the GC trace relative to the internal standard.
In another embodiment, less than 25 ppm hafnium or zirconium, preferably 10 ppm, based on the polymer yield from which any of the branched polyolefins described herein were produced and the weight of catalyst used. Less than hafnium or zirconium, preferably less than 5 ppm hafnium or zirconium. ICPES (Inductively Coupled Plasma Emission Spectroscopy) (this is JW Olesik, Encyclopedia of Materials Characterization, CR Brundle, CA Evans, Jr. and S. Wilson, edited, Butterworth-Heinemann, Boston, Mass., 1992, 633-644) (Described in “Inductively Coupled Plasma Light Emission Spectroscopy”) is used to measure the amount of elements in a material.

In yet another embodiment, the branched polyolefin is liquid at 25 ° C.
In some embodiments, the branched polyolefin may be a homopolymer of propylene. Branched polyolefins may also be copolymers, terpolymers, and the like. In certain embodiments herein, the branched polyolefin is from about 0.1 mol% to 99.9 mol% (preferably from about 5 mol% to about 90 mol%, from about 15 mol% to about 85 mol%, about 25 mol%, Mol% to about 80 mol%, about 35 mol% to about 75 mol%, or about 45 mol% to about 95 mol%) propylene. In other embodiments, the branched polyolefin is greater than 5 mol% (preferably greater than 10 mol%, greater than 20 mol%, greater than 35 mol%, greater than 45 mol%, greater than 55 mol%, greater than 70 mol%). % Or more than 85 mol%) propylene.
In some embodiments, it branched polyolefins C ₄ -C ₄₀ monomers, preferably C ₄ -C ₂₀ monomer, or preferably from C ₄ -C ₁₂ monomers. The C _{4 to} C ₄₀ monomer may be linear or cyclic. The cyclic olefin may be a tension ring or a non-tension ring, monocyclic or polycyclic, and may optionally contain heteroatoms and / or one or more functional groups. Exemplary monomers include butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclododecene, 7-oxanorbornene, substituted derivatives thereof, and isomers thereof, Preferred are hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, cyclopentene, norbornene, and their respective homologous pairs and derivatives. It is done.
In some embodiments, branched polyolefin comprises two or more different C ₄ -C ₄₀ monomer, 3 or more different C ₄ -C ₄₀ monomer, or 4 or more different C ₄ -C ₄₀ monomers. In certain embodiments herein, the branched polyolefin is from about 0.1 mol% to 99.9 mol% (preferably from about 5 mol% to about 90 mol%, from about 15 mol% to about 85 mol%, about 25 mol%, Mol% to about 80 mol%, about 35 mol% to about 75 mol%, or about 45 mol% to about 95 mol%) (preferably 2 or more, 3 or more, 4 or more, etc.) C ₄ -C ₄₀ (preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof) monomers. In other embodiments, the branched polyolefin is greater than 5 mol% (preferably greater than 10 mol%, greater than 20 mol%, greater than 35 mol%, greater than 45 mol%, greater than 55 mol%, greater than 70 mol%). %, Or more than 85 mol%) C ₄ -C ₄₀ (preferably butene, pentene, hexene, octene, and decene) monomers.
In some embodiments, the branched polyolefin is homopolypropylene, propylene / ethylene copolymer, propylene / hexene copolymer, propylene / octene copolymer, propylene / decene copolymer, propylene / hexene / octene terpolymer, propylene / hexene / decenter polymer, propylene. / Octene / decenter polymer.

Use of Vinyl-Terminated Polymers The vinyl-terminated branched polymers prepared herein may be functionalized by reacting heteroatom-containing groups with allyl groups of the polymer with or without a catalyst. Examples include catalytic hydrosilylation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydroamination, or maleic with or without an activator such as a free radical generator (eg, peroxide) Can be mentioned.
In certain embodiments, the vinyl-terminated branched polymers produced herein are described in 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, 7433-7434; and US patent application Ser. No. 12 / 487,739 filed Jun. 19, 2009 (published as WO 2009/155472). Functionalized as such.
Functionalized branched polymers can be used for oil addition and many other applications. Preferred uses include additives for lubricants and / or fuels. Preferred heteroatom-containing groups include amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and maleic anhydride.

In particular embodiments herein, the vinyl-terminated branched 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 lubricants. Special embodiments relate to lubricants comprising the vinyl terminated polymers disclosed herein, or functionalized analogs thereof.
In other embodiments, the vinyl-terminated branched polymers disclosed herein may be used as monomers for the preparation of 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, when a vinyl terminated polymer (A) is used as the monomer, it is possible to produce a homopolymer product having the formula (A) _n where n is the degree of polymerization.
In other embodiments, the polymer product produced from a mixture of monomeric vinyl terminated polymers may be a mixed polymer comprising two or more different repeating units. For example, if a vinyl terminated polymer (A) and a different vinyl terminated polymer (B) are copolymerized, the formula (A) _n (B) _m (wherein n is a vinyl terminated polymer present in the mixed polymer product) (A) and m is the number of molar equivalents of the vinyl-terminated polymer (B)).
In yet another embodiment, the polymer product may be produced from a mixture of vinyl end-branched polymers with another alkene. For example, when vinyl-terminated branched polymer (A) and alkene (B) are copolymerized, the formula (A) _n (B) _m (where n is the vinyl-terminated polymer present in the mixed polymer product) It is possible to produce mixed polymer products having the number of molar equivalents and m is the number of molar equivalents of alkene).

In another embodiment, the present invention relates to a functionalized branched polyolefin comprising a heteroatom-containing group and the reaction product of any vinyl-terminated branched polyolefin described herein, wherein preferably The functional group contains one or more heteroatoms selected from the group consisting of P, O, S, N, Br, Cl, F, I, and / or B, and the functionalized branched polyolefin is 0.60 to 1.2, and also have 0.75 to 1.10 functional groups (assuming that preferably Mn did not change more than 15% compared to Mn of vinyl-terminated branched polyolefins prior to functionalization and optional derivatization). The number of functional groups per chain (F / Mn) is WO 2009/155472 (VDRA is VRDA, which is a standardized integral signal strength for vinylidene resonances of about 4.65 to 4.85 ppm and vinylene resonances of about 5.15 to 5.6 ppm. comprising at, pp 26-27, as measured by ¹ H NMR as described in paragraph [00111] - [00114] see).
Preferred heteroatom-containing groups comprise one or more sulfonates, amines, aldehydes, alcohols or acids, preferably heteroatom-containing groups comprise epoxides, succinic acid, maleic acid or maleic anhydride, and heteroatom-containing groups are Including one or more acids, esters, anhydrides, acid esters, oxycarbonyl, carbonyl, formyl, formylcarbonyl, hydroxyl, and acetyl halide.
Functionalization% of branched polyolefin = (F * 100) / (F + VI + VE) Number of vinyl groups / 1000 carbons (VI *) and number of vinylidene groups / 1000 for functionalized branched polyolefins Carbon (VE *) is measured from the ¹ H NMR spectrum of the functionalized polyolefin in the same manner as VI and VE for the unfunctionalized polymer. Preferably, the% functionalization of the branched polyolefin is 75% or more, preferably 80% or more, preferably 90% or more, or more preferably 95% or more.
In another embodiment, the functionalized polyolefin described herein has a Mn and / or Mw and / or Mz that is the same or up to 15% (preferably greater than 10%) than the starting vinyl-terminated polyolefin. “Same” is defined to mean within 5%.
In another embodiment, the vinyl-terminated branched polyolefin described herein is incorporated into any method, blend, product, or composition disclosed in WO 2009/155472, which is hereby incorporated by reference. Can be used for In some embodiments, the composition is a lubricant blend, an adhesive, or a wax. In certain embodiments, the invention relates to the use of the composition as a lubricant blend, adhesive, or wax.

In another embodiment, the present invention relates to:
1 .:
(i) a temperature preferably above 35 ° C. (preferably in the range from about 35 ° C. to 150 ° C., 40 ° C. to 140 ° C., 60 ° C. to 140 ° C., or 80 ° C. to 130 ° C.) and optionally Ethylene and / or propylene (preferably propylene) and optionally one or more C _{4 to} C ₄₀ alpha olefin monomers at a pressure in the range of about 0.35 to 10 MPa (preferably 0.45 to 6 MPa or 0.5 to 4 MPa) (Preferably C _{4 to} C ₂₀ alpha olefin monomer, preferably C _{4 to} C ₁₂ alpha olefin monomer, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, And one or more monomers comprising (and preferably their isomers) a catalyst system capable of producing a branched polyolefin. The system comprises a metallocene catalyst compound and an activator (preferably the activator is a non-alumoxane compound, preferably the alumoxane is present at 0% by weight, and preferably the activator is a non-coordinating anionic activator). The catalyst system includes one or more non-metallocene catalyst compounds, one or more metallocene catalyst compounds, or combinations thereof, preferably the catalyst system includes a single metallocene catalyst), the metallocene catalyst compound is represented by the formula Done:

Where
M is selected from the group consisting of zirconium or hafnium (preferably hafnium);
Each X is independently a group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof. (Two Xs may form part of a condensed ring or ring system) (preferably X is a halide or hydrocarbyl group having from 1 to 20 carbon atoms, preferably X is Chloride or methyl),
Each R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group,
Furthermore, provided that any two adjacent R groups may form a fused ring or a multi-centered fused ring system (these rings may be aromatic, partially saturated or saturated), and Any of the adjacent R ⁴ groups, R ⁵ groups, and R ⁶ groups may form a condensed ring or a multi-centered condensed ring system (these rings may be aromatic, partially saturated or saturated) Subject to

T is the formula R ₂ ^a J where J is one or more of C, Si, Ge, N, or P (preferably J is Si), and each R ^a is independently hydrogen, halogen, C ₁ -C ₂₀ hydrocarbyl group or a C ₁ -C ₂₀ substituted hydrocarbyl (preferably Ra is methyl, ethyl, a is chloride) is a bridging group represented by),
At least one R ³ (preferably both) is a substituted or unsubstituted phenyl group when any of R ¹ , R ² , R ⁴ , R ⁵ or R ⁶ is not hydrogen)
(ii) preferably converting at least 50 mol%, more preferably at least 60 mol%, at least 70 mol%, at least 80 mol% of the monomer into a polyolefin, and
(iii) Allyl chain ends greater than 50% (preferably 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more) with respect to the total unsaturated chain ends And a branched polyolefin having a Tm of 60 ° C. or higher (preferably 100 ° C. or higher, preferably 120 ° C. or higher).
2. The process of paragraph 1 or 12, wherein butene comonomer is present and the mixed butene stream is the source of butene comonomer.
3. The method of paragraphs 1, 2, or 12, wherein the activator is a bulky activator represented by the formula:

(Where
Each R ₁ is independently a halide, preferably fluoride,
Each R ₂ is independently a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. (Preferably R ₂ is a fluoride or a perfluorinated phenyl group),
Each R ₃ is a halide, a C ₆ -C ₂₀ substituted 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. Yes (preferably R ₃ is a fluoride or a C ₆ perfluorinated aromatic hydrocarbyl group), 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)
L is a neutral Lewis base;
(LH) ⁺ is a Bronsted acid,
d is 1, 2, or 3;
The anion has a molecular weight greater than 1020 g / mol and at least three of the substituents of the B atom each have a molecular volume greater than 250 cubic cubic and greater than 300 cubic cubic or greater than 500 cubic cubic)

4. 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 (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 tetrakis (perfluoro Biphenyl) 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 (perfluoro Biphenyl) borate, triethylsilylium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, and [4-t-butyl-PhNMe ₂ H] [(mC ₆ F ₅ -C ₆ F ₄ ) ₄ The method of paragraph 3, which is at least one of B].
5. The method of paragraphs 1, 2, 3, 4, or 12 wherein the method is carried out in a single reaction zone (preferably solution polymerization).
6. Productivity is 4500 g / mmol or more (preferably 5000 g / mmol or more, preferably 10,000 g / mmol or more, preferably 50,000 g / mmol or more), and productivity is at least 80,000 g / mmol, preferably Process according to paragraphs 1, 2, 3, 4, 5, or 12, which is at least 150,000 g / mmol, preferably at least 200,000 g / mmol, preferably at least 250,000 g / mmol, preferably at least 300,000 g / mmol.
7. Paragraphs 1, 2, wherein the polymerization residence time is up to 300 minutes (preferably in the range from about 1 to 300 minutes, preferably from about 5 to 250 minutes, or preferably from about 10 to 120 minutes). 3, 4, 5, 6, or 12 methods.

8. having 7,500-60,000 g / mol of Mn (measured by ¹ H NMR), one or more alpha-olefins (preferably propylene and / or ethylene, preferably propylene) and optionally one or more C ₄ -C ₄₀ alpha-olefin monomer (preferably C ₄ -C ₂₀ alpha-olefin monomers, preferably C ₄ -C ₁₂ alpha-olefin monomer, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, Cyclooctene, cyclooctadiene, and isomers thereof), and
(i) 50% or more (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more with respect to the total number of unsaturated chain ends. % Or more) allyl chain end,

(ii) Percentage of 0.9 'or less (preferably 0.85 or less, preferably 0.80 or less) g'vis and / or 1.2 to 2.0 (preferably 1.6 to 1.8) saturated chain ends (preferably isobutyl chain ends) vs. allyl chain ends And / or a ratio of Mn (GPC) / Mn ( ¹ H NMR) of 0.95 or less (preferably 0.90 or less, preferably 0.85 or less, preferably 0.80 or less),
(iii) Tm above 60 ° C if necessary (preferably higher than 100 ° C, preferably 60-180 ° C, preferably 80-175 ° C),
(iv) optionally greater than 7 J / g (preferably greater than 15 J / g, greater than 30 J / g, greater than 50 J / g, greater than 60 J / g or greater than 80 J / g) ) Hf,
(v) Allyl chain end to internal vinylidene ratio, if necessary, greater than 5: 1 (preferably greater than 10: 1),
(vi) optionally an allyl chain end to vinylidene chain end ratio greater than 10: 1 (preferably greater than 15: 1), and
(vii) Paragraphs 1-7 or 12 having an allyl chain end to vinylene chain end ratio, optionally greater than 1: 1 (preferably greater than 2: 1, greater than 5: 1 or greater than 10: 1). Branched polyolefin produced by the process of
9. Mn (measured by GPC) greater than 60,000 g / mol, one or more alpha olefins (preferably propylene and / or ethylene, preferably propylene) and optionally one or more C ₄ -C ₄₀ Alpha olefin monomers (preferably C _{4 to} C ₂₀ alpha olefin monomers, preferably C _{4 to} C ₁₂ alpha olefin monomers, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclo Octadiene and isomers thereof), and
(i) 50% or more with respect to the total number of unsaturated chain ends (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95 %) Of allyl chain ends,
(ii) 0.9 'or less (preferably 0.85 or less, preferably 0.80 or less) g'vis,
(iii) optionally a bromine number which decreases by at least 50% (preferably at least 75%) after complete hydrogenation,
(iv) optionally a Tm higher than 60 ° C (preferably higher than 100 ° C, preferably from 60 ° C to 180 ° C, preferably from 80 ° C to 175 ° C), and
(v) greater than 7 J / g, preferably greater than 15 J / g, greater than 30 J / g, greater than 50 J / g, greater than 60 J / g, or greater than 80 J / g, as required ) Hf
A branched polyolefin produced by the process of paragraphs 1-7 or 12 having:

10. Less than 7,500 g / mol, preferably 100-7,500 g / mol Mn (measured by ¹ H NMR), one or more alpha olefins (preferably propylene and / or ethylene, preferably propylene) and Optionally one or more C _{4 to} C ₄₀ alpha olefin monomers (preferably C _{4 to} C ₂₀ alpha olefin monomers, preferably C _{4 to} C ₁₂ alpha olefin monomers, preferably butene, pentene, hexene, heptene, octene, Nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and isomers thereof), and
(i) 50% or more (preferably 60% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more with respect to the total number of unsaturated chain ends. % Or more) allyl chain end,
(ii) The ratio of the percentage of 1.2-2.0 (preferably 1.6-1.8) saturated chain ends (preferably isobutyl chain ends) to the percentage of allyl chain ends, and / or 0.95 or less (preferably 0.90 or less, preferably 0.85 or less). , Preferably 0.80 or less) Mn (GPC) / Mn ( ¹ H NMR) ratio,
(iii) Tm above 60 ° C if necessary (preferably higher than 100 ° C, preferably 60-180 ° C, preferably 80-175 ° C),
(iv) optionally greater than 7 J / g (preferably greater than 15 J / g, greater than 30 J / g, greater than 50 J / g, greater than 60 J / g or greater than 80 J / g) ) Hf,
(v) Allyl chain end to internal vinylidene ratio, if necessary, greater than 5: 1 (preferably greater than 10: 1),
(vi) optionally an allyl chain end to vinylidene chain end ratio greater than 10: 1 (preferably greater than 15: 1), and
(vii) Paragraphs 1-7 or 12 having an allyl chain end to vinylene chain end ratio, optionally greater than 1: 1 (preferably greater than 2: 1, greater than 5: 1 or greater than 10: 1). Branched polyolefin produced by the process of

11. The functionalized branched polyolefin of paragraphs 8-10, wherein the functional group is selected from amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and maleic anhydride.
12.
(i) a temperature above 35 ° C. (preferably in the range from about 35 ° C. to 150 ° C., 40 ° C. to 140 ° C., 60 ° C. to 140 ° C., or 80 ° C. to 130 ° C.) and, if necessary, about Ethylene and / or propylene (preferably propylene) and optionally one or more C _{4 to} C ₄₀ alpha olefin monomers (preferably at a pressure in the range of 0.35 to 10 MPa (preferably 0.45 to 6 MPa or 0.5 to 4 MPa) Is a C _{4 to} C ₂₀ alpha olefin monomer, preferably a C _{4 to} C ₁₂ alpha olefin monomer, preferably butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and these The one or more monomers containing the isomers of (Preferably the activator is a non-alumoxane compound, preferably the alumoxane is present at 0% by weight, preferably the activator is a non-coordinating anionic activator) The system includes one or more non-metallocene catalyst compounds, one or more metallocene catalyst compounds, or combinations thereof, preferably the catalyst system includes a single metallocene catalyst), the metallocene catalyst compound is represented by the formula :

Where
M is selected from the group consisting of zirconium or hafnium (preferably hafnium);
Each X is independently a group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof. (Two Xs may form part of a condensed ring or ring system) (preferably X is a halide or hydrocarbyl group having from 1 to 20 carbon atoms, preferably X is Chloride or methyl),
Each R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group,
Furthermore, provided that any two adjacent R groups may form a fused ring or a multi-centered fused ring system (these rings may be aromatic, partially saturated or saturated), and Any of the adjacent R ⁴ groups, R ⁵ groups, and R ⁶ groups may form a condensed ring or a multi-centered condensed ring system (these rings may be aromatic, partially saturated or saturated) Subject to
T is the formula R ₂ ^a J where J is one or more of C, Si, Ge, N, or P (preferably J is Si), and each R ^a is independently hydrogen, A bridging group represented by halogen, C ₁ -C ₂₀ hydrocarbyl or C ₁ -C ₂₀ substituted hydrocarbyl (preferably R ^a is methyl, ethyl, chloride);
At least one R ³ (preferably both) is a substituted or unsubstituted phenyl group when any of R ¹ , R ² , R ⁴ , R ⁵ or R ⁶ is not hydrogen)
(ii) converting at least 50 mol% (preferably at least 60 mol%, at least 70 mol%, at least 80 mol%) of the monomer into a polyolefin; and
(iii) More than 50% of all unsaturated chain ends (preferably 60% or more, preferably 70% or more, preferably 80% or more, preferably 90% or more, preferably 95% or more) And a branched polyolefin having a Tm of 60 ° C. or higher (preferably 100 ° C. or higher, preferably 120 ° C. or higher).

Product characterization The product was characterized by ¹ H NMR, GPC-3D, and DSC as indicated above.
Metallocenes used in the examples The following metallocenes were used in the following examples.

Metallocenes A and C were obtained from Albemarle (Baton Rouge, LA) and used without further purification. Metallocene B was synthesized as shown below.
According to the typical dry box procedure for the synthesis of metallocene B synthetic air sensitive compounds, dry glassware (90 ° C., 4 hours) and anhydrous solvents purchased from Sigma Aldrich (St. Louis, MO) (these are 3A sieves) Including further drying). All reagents were purchased from Sigma-Aldrich (Milwaukee, WI) and used without further purification unless otherwise stated.
The metallocene B dichloride precursor (B-Cl ₂ ) was obtained from Albemarle and converted to metallocene B according to the following procedure: 3.02 g of B-Cl ₂ in a purged Vacuum Atmospheres ^™ dry box under inert atmosphere Dissolved in 150 mL of dry toluene in a 250 mL 1 neck round bottom flask. To this, 4.0 mL (5 equivalents) of 3.0M methylmagnesium bromide was added dropwise. The solution was heated in an oil bath at 90 ° C. overnight. The mixture was then cooled to room temperature, at which time 10.0 mL of trimethylsilyl chloride was added dropwise. After stirring for 10 minutes, 10.0 mL of dry 1,4-dioxane was added and the mixture was stirred for an additional 10 minutes. The mixture was filtered through an oven-dried fine glass filter to remove the magnesium salt. The flask was rinsed with about 20 mL of n-pentane and combined with the filtrate by passing it through a frit. The solvent was removed in vacuo to give 2.23 g of metallocene B as an off-white powder (74% yield).
Activators used in the examples The following activators were used in the following examples. Activators I and III were purchased from Albemarle. Activator II was purchased from Single Site Catalyst.

Polymerization Conditions for Example 1-2 All of the examples were prepared in a 0.5 liter autoclave reactor operated in a continuous stirred tank solution process. The autoclave was equipped with a stirrer, water cooling / steam heating element and temperature controller, and pressure controller. The solvent, monomer, eg, propylene was purified by first passing through a three column purification system. The purification column was periodically regenerated whenever there was evidence of low activity of polymerization.
The amount of solvent supplied to the reactor was measured with a mass flow meter. A plasma feed pump controlled the solvent flow rate and increased the solvent pressure to the reactor. The compressed liquefied propylene feed rate was measured with a mass flow meter and the flow rate was controlled with a pulse feed pump. Solvent and monomer were initially fed to the manifold. The solvent and monomer mixture was then cooled to about −15 ° C. by passing through a condenser and then fed to the reactor through a single tube. The collected sample was first air dried in a hood to evaporate most of the solvent and then dried in a vacuum oven at a temperature of about 90 ° C. for about 12 hours. The vacuum oven dried sample was weighed to obtain the yield. Monomer conversion was calculated based on the polymer yield for the amount of monomer fed to the reactor. All reactions were performed at a pressure of about 2.4 MPa / g.
The catalysts used in the following examples are rac-dimethylsilylbisindenylhafnium dimethyl (catalyst A), rac-dimethylsilylbis (2-methylindenyl) zirconium dimethyl (catalyst B), and rac-dimethylsilylbis (2 -Methyl-4-phenylindenyl) zirconium dimethyl (catalyst C). The activators used were N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (activator I), trityltetrakis (pentafluorophenyl) borate (activator II), and N, N-dimethylanilinium tetrakis (hepta Fluoro-2-naphthyl) borate (active agent III). All metallocene catalysts were preactivated with activator at a molar ratio of about 1: 1 in 900 ml of toluene. All catalyst solutions were kept in an inert atmosphere and fed to the reactor by a metering pump. Tri-n-octylaluminum (TNOAL) solution (available from Sigma Aldrich, Milwaukee, Wis.) Was further diluted in isohexane and used as a scavenger.

The propylene polymerization polymerization conditions, feedstock conversion (%), and catalyst productivity are listed in Table 1 below. In all experiments, the inlet propylene feed concentration was 3.5-4 M. Two standard cubic centimeters of H ₂ were used in the feed of experiment # 42. Tri (n-octyl) aluminum (TNOAL) was used throughout as a scavenger. The molar ratio of TNOAL to metallocene was about 20. The residence time was constant at 5 minutes.

List of abbreviations: ¹ : Met. = Metallocene, ² : Act. = Activator; T _p = polymerization reaction temperature; *> It is understood that the propylene conversion calculated to be 100% is 100%.
Propylene conversion was high: 53-100%. The productivity of metallocene C was observed to be 3-6 times higher than that of metallocene A. The productivity of metallocene B was comparable to metallocene C in most cases.
Characterization of polymer products
Differential scanning calorimetry (DSC)
DSC was used to analyze the polymer from Experiment 1-65. Data from several analyzes of the polymer product are shown in Table 2 below.

List of abbreviations: ¹ : Met. = Metallocene, ² : Act. = Activator; T _p is the polymerization reaction temperature; *> 100% propylene conversion calculated to be 100%.
Metallocene C provides excellent melting point capability. An increase in the polymerization temperature causes a decrease in the melting point. It is believed that the melting point reduction results from a higher population of steric and positional defects in the product. Of the active agents, it is clear that Activator III is most effective in raising the melting point.
Gel permeation chromatography (GPC-3D)
The GPC 3D results for some of the polymers are summarized in Table 3.

Mwの増大によるg’vis の低下が殆どのGPC クロマトグラムで観察され、これが長鎖分枝の証明として採用された。図２中で、g’f(log Mw)をメタロセンA/活性剤III 生成物の4種について比較した。全ての４種が実質的な長鎖分枝についての標示を示した。その他の生成物、例えば、メタロセンB/活性剤Ｉ及びメタロセンB/活性剤IIを使用して得られたものは極めて小さいLCB と合致するg’f(log MW) プロットを有する。全てのこれらの生成物を長鎖分枝を誘導し得る比較的高いプロピレン転化率条件 (60〜100%) 下でつくった。
¹ HNMR 結果
実験1-65のポリマー生成物の幾つかの分析からのデータを下記の表４に示す。 It was observed that the molecular weight decreased with increasing polymerization temperature. A significant increase in Mw for all three metallocenes was observed when Activator III was used. Polymers made with activators I and II tended to fall within the same Mw range for each metallocene within the temperature range tested.
When DSC and GPC data are combined, the following metallocene / activator trends (1) and (2) were observed when the comparison was made at the same polymerization temperature:

A decrease in g'vis due to an increase in Mw was observed in most GPC chromatograms, which was taken as proof of long chain branching. In FIG. 2, g'f (log Mw) was compared for four metallocene A / activator III products. All four showed indications for substantial long chain branching. Other products, such as those obtained using metallocene B / activator I and metallocene B / activator II, have g'f (log MW) plots that match very small LCBs. All these products were made under relatively high propylene conversion conditions (60-100%) that could induce long chain branching.
¹ HNMR Results Data from several analyzes of the polymer product of Experiment 1-65 are shown in Table 4 below.

¹ H NMR spectra were recorded for most samples. A summary of the concentration of olefinic unsaturation is shown in Table 4. Assuming one unsaturation per chain, the number average molecular weight of each sample was calculated from ¹ H NMR data and in Table 4 these values were compared to the number average molecular weight derived from GPC. Given the signal-to-noise limits, the Mn calculated from ¹ H NMR is considered quite reliable up to about 50,000 g / mol. A parity plot of Mn ( ¹ H NMR) versus Mn (GPC-DRI) is shown in FIG. In most cases, the Mn derived from the two methods is similar, with some notable exceptions. Deviations from parity are thought to be due to contributions from long chain branches.

The percentage vinyl ranking as a function of the metallocene-activator used for a given polymerization temperature is summarized in (3) below.
% Vinyl: A / III> C / III> B / III> C / II> C / I> A / I ≧ B / II ~ A / II> B / I (3)
It was also observed that% vinyl often increased substantially and generally as the polymerization temperature was increased for each metallocene / activator pair tested.
All documents described herein, including any priority documents, related applications and / or test operations, are included herein by reference to the extent they are not inconsistent with this specification, Priority documents not listed in the filed application or application documents are not included in this description for reference. While the invention has been illustrated and described, as will be apparent from the foregoing general description and specific embodiments, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, the present invention is not intended to be limited thereby. Similarly, the term “comprising” is considered synonymous with the term “including” for the purposes of Australian law. Similarly, “including” encompasses the terms “consisting essentially of”, “consisting of”, and “consisting of” and therefore, wherever “including” is used, “Is”, “is”, or “consists of” may be substituted.

Claims (34)

(i) contacting one or more monomers comprising ethylene and / or propylene with a catalyst system comprising a metallocene catalyst compound and an activator, wherein the metallocene catalyst compound has the formula:

[Where:
M is selected from the group consisting of zirconium or hafnium;
Each X is independently a group consisting of hydrocarbyl groups having 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes, amines, phosphines, ethers, and combinations thereof. (Two Xs may form a condensed ring or part of a ring system);
Each R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ is independently hydrogen or a substituted or unsubstituted hydrocarbyl group, heteroatom or heteroatom-containing group,
In addition, provided that any two adjacent R groups may form a condensed ring or a multi-centered condensed ring system (these rings may be aromatic, partially saturated or saturated),
Further, any of the adjacent R ⁴ groups, R ⁵ groups, and R ⁶ groups may form a condensed ring or a multi-centered condensed ring system (these rings may be aromatic, partially saturated or saturated). On condition that it is good,
T is the formula R ₂ ^a J where J is one or more of C, Si, Ge, N, or P, and each R ^a is independently hydrogen, halogen, C ₁ -C ₂₀ hydrocarbyl group Or a C ₁ -C ₂₀ substituted hydrocarbyl).
At least one R ³ is a substituted or unsubstituted phenyl group when any of R ¹ , R ² , R ⁴ , R ⁵ or R ⁶ is not hydrogen]
A process represented by; and
(ii) obtaining a branched polyolefin having an allyl chain end greater than 50% and a Tm of 60 ° C. or higher, relative to the total unsaturated chain ends;
A polymerization method comprising:   The process of claim 1, wherein step (i) occurs at a temperature greater than 35 ° C and at least 50 mol% of the monomers are converted to polyolefins.   The process according to claim 1 or 2, wherein the monomer is propylene. Including contact with C ₄ -C ₄₀ alpha-olefin comonomer of contact or further a kind of the catalyst system according to claim 1, 2, or 3 A method according. C ₄ -C ₄₀ alpha-olefin comonomer is butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, and selected from these isomers, The method of claim 4.   The process according to any one of claims 1 to 5, wherein the catalyst system is a single catalyst system.   The method according to any of claims 1 to 6, wherein the activator is a non-alumoxane activator or a non-coordinating anion activator. Activator is formula:

Represented by
Where
Each R ₁ is independently a halide,
Each R ₂ is independently a halide, a C ₆ -C ₂₀ substituted aromatic hydrocarbyl group or a formula —O—Si—R _{a where} R _a is a C ₁ -C ₂₀ hydrocarbyl or hydrocarbyl silyl group. A siloxy group of
Each R ₃ is a halide, a C ₆ -C ₂₀ substituted 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. R ₂ and R ₃ can form one or more saturated or unsaturated, substituted or unsubstituted rings,
L is a neutral Lewis base;
(LH) ⁺ is a Bronsted acid,
2. d is 1, 2 or 3, and the anion has a molecular weight greater than 1020 g / mol, and at least three of the substituents of the B atom each have a molecular volume greater than 250 cubic cubic meters. 7. The method according to any one of 6 to 6. Activating agents 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, triethylsilyl tetrakis (perfluoronaphthyl) borate, benzene (diazonium) tetrakis (perfluoronaphthyl) borate, trimethylammonium tetrakis (perfluorobiphenyl) borate, triethylammonium tetrakis (perfluorobiphenyl) borate, tri Propylammonium tetrakis (perfluorobiphenyl) 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- Methyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate, tropylium tetrakis (perfluorobiphenyl) borate, triphenylcarbenium tetrakis (perfluorobiphenyl) borate, triphenylphosphonium tetrakis (perfluorobiphenyl) borate, triethyl One or more of silylium tetrakis (perfluorobiphenyl) borate, benzene (diazonium) tetrakis (perfluorobiphenyl) borate, [4-t-butyl-PhNMe ₂ H] [(mC ₆ F ₅ -C ₆ F ₄ ) ₄ B] 6. The method according to any one of claims 1 to 5, wherein:   10. A method according to any one of claims 1 to 9, wherein the method occurs in a single reaction zone.   11. A process according to any of claims 1 to 10, wherein the alumoxane is present at 0 mol%.   The method according to claim 1, wherein the polymerization is a solution polymerization.   The method according to any one of claims 1 to 12, wherein the productivity is 4500 g / mmol or more.   14. A process according to any preceding claim, wherein the contacting occurs at a temperature in the range of about 35 ° C to 150 ° C.   15. A method according to any of claims 1 to 14, wherein the residence time is up to 300 minutes.   Metallocene is (rac-dimethylsilylbis (indenyl) hafnium dimethyl, (rac-dimethylsilylbis (2-methylindenyl) zirconium dimethyl, (rac-dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dimethyl), And dimethyl rac-dimethylsilyl-bis (5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz (f) indene) hafnium dimethyl, The method according to any one of 1 to 15.   The method according to claim 1, which is a continuous method. Having one or more alpha olefin-derived units having Mn ( ¹ H NMR) of 7,500-60,000 g / mol, including ethylene and / or propylene, and
(i) 50% or more of allyl chain ends, based on the total number of unsaturated chain ends, and
(ii) g'vis below 0.90
Branched polyolefin having   The branched polyolefin of claim 18, wherein the ratio of the percentage of saturated chain ends to the percentage of allyl chain ends is from 1.2 to 2.0. Having one or more alpha olefin-derived units having an Mn ( ¹ H NMR) of less than 7,500 g / mol, including ethylene and / or propylene, and
(i) the ratio of the percentage of saturated chain ends to the percentage of allyl chain ends of 1.2 to 2.0, and
(ii) A branched polyolefin having 50% or more of allyl chain ends relative to the total moles of unsaturated chain ends.   21. The branched polyolefin of claim 20, having a Mn greater than 100 g / mol. A ratio of 0.95 or less of ^{Mn (GPC) / Mn (1} H NMR), according to claim 18, 19, 20, or 21 branched polyolefin according.   23. A branched polyolefin according to claim 18, 19, 20, 21 or 22 having an allyl chain end to internal vinylidene ratio greater than 5: 1.   24. The branched polyolefin of claim 18, 19, 20, 21, 22, or 23, having an allyl chain end to vinylidene chain end ratio greater than 10: 1.   25. The branched polyolefin of claim 18, 19, 20, 21, 22, 23, or 24, having an allyl chain end to vinylene chain end ratio greater than 1: 1. Having one or more alpha olefin derived units having Mn (GPC) greater than 60,000 g / mol, including ethylene and / or propylene, and
(i) 50% or more of allyl chain ends with respect to the total unsaturated chain ends,
(ii) g'vis of 0.90 or less, and
(iii) Branched polyolefin, optionally having a bromine number that decreases by at least 50% after complete hydrogenation. Having Mn of 7,500-60,000 g / mol, containing propylene-derived units, and
(i) g'vis below 0.90, and
(ii) A functionalized branched polyolefin having a saturated chain end to functional group ratio of 1.2 to 2.0.   28. A branched polyolefin according to any of claims 18 to 27 comprising propylene derived units and ethylene derived units. Furthermore C ₄ -C ₄₀ contains alpha-olefin-derived units, branched polyolefins according to any of claims 18 28.   30. A branched polyolefin according to any of claims 18 to 29, having a Tm higher than 60C.   31. A branched polyolefin according to any of claims 18 to 30 having a Hf greater than 7 J / g.   32. The functionalized polyolefin according to any one of claims 27 to 31, wherein the functional group is selected from amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and maleic anhydride.   33. The functionalized polyolefin according to claim 32, wherein the functional group is maleic acid or maleic anhydride.   A lubricant comprising the functionalized polyolefin according to any of claims 27 to 33.

Images