dielectric fluid composition

专利摘要:
DIELECTRIC FLUID COMPOSITION. In general, the present invention relates to a dielectric composition which is a poly-alpha-olefin or a poly(co-ethylene/alpha-olefin) having a weight average molecular weight greater than 200 and less than 10,000 Dalton. The dielectric composition uses a metal-binder complex as a precatalyst and exhibits a hyperbranched structure that allows for low viscosity, and therefore good flow characteristics combined with high flash point due to the ability to increase molecular weight via branching rather than growth of main chain. Other desirable properties include decreased pour point due to breakage of crystallization, and desirable thermooxidative stability.
公开号:BR112014015971B1
申请号:R112014015971-8
申请日:2012-11-28
公开日:2021-05-18
发明作者:Suh Joon Han；Jerzy Klosin；Zenon Lysenko
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

[001] The present invention relates to a process for polymerizing α-olefin or for copolymerizing an α-olefin with ethylene. More particularly, the present invention relates to a process for preparing dielectric fluids, particularly transformer fluids, which are hyperbranched oils.
[002] The main function of transformers is to increase or decrease the alternating voltage in a substation according to requirements in order to transmit electricity with low loss over long distances via transmission and distribution lines. During this process, the transformer heats up, and this heat must be dissipated by means of a liquid refrigerant.
[003] The thermal control of transformers is very critical for the safety of the reactor operation. Although conventional transformers operate efficiently at relatively high temperatures, excessive heat is detrimental to transformer life. This is because transformers contain electrical insulation which is used to prevent live conductors or components from sparking or contacting other components, conductor or internal circuitry. The higher the temperature experienced by the insulation, the shorter the life of the insulation. When insulation fails, an internal defect or short circuit may occur. To prevent excessive temperature rise and premature transformer failure, transformers are typically charged with a liquid refrigerant to dissipate relatively large amounts of heat generated during normal transformer operation. The refrigerant also functions as a dielectric medium to electrically insulate transformer components. The dielectric liquid must be capable of cooling and insulating to increase transformer durability (eg, 20 years or more). Since dielectric fluids cool the transformer by convection, the viscosity of a fluid at various temperatures is one of the key factors in determining its efficiency.
[004] In recent years, mineral oils have been used for this purpose, because they are good electrical insulators and also have a high thermal conductivity. However, they are also significantly flammable, which raises a safety issue for indoor, factory and underground operations.
[005] In view of these needs, it is desirable in the art to provide dielectric fluids that are capable of desirable flow behaviors at normal operating temperatures, which may include a wide range of temperatures; a high flash point (flammation), preferably above 200°C; and desirable thermal oxidation stability, in order for the dielectric fluid to maintain its effectiveness for a considerable period of time, despite its function to dissipate continuously or often large amounts of heat. Furthermore, it is desirable that the fluid be relatively economical and can be prepared conveniently or efficiently.
[006] In one aspect, the present invention is a dielectric fluid composition comprising a poly-α-olefin or a poly(co-ethylene/α-olefin) having a weight average molecular weight greater than 200 and less than 10,000 Dalton (Da ) prepared from a process including a step of contacting together (1) a monomer selected from (a) an α-olefin; or (b) a combination of an α-olefin and ethylene; and (2) a catalytic amount of a catalyst, wherein the catalyst includes a mixture or reaction product of ingredients (2a) and (2b) that is prepared prior to the contacting step, wherein ingredient (2a) is at least a metal-ligand complex of formula (I):
in which M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; n is an integer from 0 to 3, where when n is 0, X is absent; each X is independently a monodentate ligand that is neutral, monoanionic, or dianionic, or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; X and n are chosen such that the metal-binder complex of formula (I) is overall neutral; each Z is independently O, S, N-hydrocarbyl C1-C40, or P-hydrocarbyl C1-C40; L is C1-C40 hydrocarbylene or C1-C40 heterohydrocarbylene, wherein the C1C40 hydrocarbylene has a moiety comprising a linker backbone of 2 carbon atoms connecting the Z atoms in formula (I) and the C1-C40 heterohydrocarbylene has a moiety comprising a main chain linker of 2 carbon atoms connecting the Z atoms in formula (I), each atom of the 2 atom linker of the C1-C40 heterohydrocarbylene being independently a carbon atom or a heteroatom, each of which heteroatom is independently O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN), with each RC independently being hydrocarbyl C1- unsubstituted C18 or the two RC join to form a C2-C19 alkylene, each RP is unsubstituted C1-C18 hydrocarbyl; and each RN is unsubstituted C1-C18 hydrocarbyl, a hydrogen atom, or absent; each R1a, R2a, R1b and R2b is independently a hydrogen, C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, N(RN)2, NO2, ORC, SRC, Si(RC)3, Ge(RC)3, CN , CF3, F3CO, halogen atom; and each of the others of R1a, R2a, R1b and R2b is independently hydrogen, C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, N(RN)2, NO2, ORC, SRC, Si(RC)3, CN, CF3 , F3CO, or halogen atom; each of R3a, R4a, R3b, R4b, R7c, R8c, R6d, R7d, and R8d is independently a hydrogen atom, C1-C40 hydrocarbyl, C1-C40 heterohydrocarbyl, SC CPNN CC i(R)3, Ge( R)3, P(R)2, N(R)2, N(R)2, OR, SR, NO2, CN, CF3, RCC CCCCS(O)-, RS(O)2-, (R)2C =N-, RC(O)O-, R OC(O)-, RC(O)N(R)-, (RC)2N C(O)- or halogen atom; each of R5c and R5d is independently a C6-C40 aryl or C1-C40 heteroaryl group; each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and heterohydrocarbylene groups is independently unsubstituted or substituted with one or more RS substituents; and each RS is independently a halogen atom, polyfluor substitution, perfluor substitution, unsubstituted C1-C18 alkyl, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS -, RS(O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)-, RC(O)N(R) -, or R2NC(O)-, or two of the RS come together to form an unsubstituted C1-C18 alkylene group, each R being independently an unsubstituted C1-C18 alkyl group; and wherein the ingredient (2b) is at least one activation cocatalyst, such that the ratio of the total number of moles of the at least one metal-binder complex (2a) to the total number of moles of the at least one activation cocatalyst (2b) is from 1:10,000 to 100:1, under conditions such that a product selected from a poly-α-olefin and a poly(co-ethylene/α-olefin) is formed, the product having weight distribution component molecular weight and a main chain weight average molecular weight (Mw) that is greater than 200 Da and less than 10,000 Da, the product including at least two isomers in each distribution component above 300 Da.
[007] The invention offers new compositions of dielectric fluids comprising poly-α-olefin or poly(co-ethylene-α-olefin) using as catalyst one or more of a group of compounds having a two-atom bridge between oxygen atoms of bis-ether. These catalysts were found to provide a unique ability to produce low molecular weight polymers with unique isomeric distribution where there are at least two isomers for each distribution component above 300 Da and at least three isomers for each distribution component above 400 Dalton . The term "distribution component" means a single given molecular species, including all of its isomers. Examples of such may include dimers, trimers, tetramers, etc. These low molecular weight polymers include both poly-α-olefins and poly(co-ethylene-α-olefins), generally having molecular weights greater than 200 Da and less than 10,000 Da, preferably less than 5,000 Da. Processing can be carried out over a wide temperature range, from 40°C to 300°C. Because of their relatively low molecular weights, these products exhibit controlled viscosity and are generally liquid, which increases their number of potential applications. Most importantly, the products exhibit unique structural and property relationships that make them particularly useful as dielectric fluids.
[008] Importantly, these compositions are structurally hyperbranched polyolefin liquids, the viscosity of which actually decreases when the main chain chain length decreases. Simultaneously. The burning point increases as the molecular weight of the dielectric fluid composition increases. This combination allows the possibility of increasing the molecular weight by increasing the number of branches while simultaneously controlling the hydrodynamic volume and therefore the viscosity, minimizing the size of the main carbon chain. The result is a higher flash point, well above the expected range for linear hydrocarbon liquids such as mineral oils, and a considerably lower pour point due to the interruption of crystallization caused by the hindered chain arrangement due to the hyperbranched structure. These highly desirable qualities allow the use of the dielectric fluid compositions of the invention in applications including, but not limited to, transformer oils, insulating fluids for transmission and distribution cables, switch fluids, dielectric fluids for telecommunication cables, insulating fluids for bushings, dielectric fluids for electronic devices such as printed circuits, and dielectric fluids for electrical appliances such as motors and generators. For convenience, all of the applications mentioned above are here considered to fall within the limits of the generalized phrase "dielectric fluid composition".
[009] Here, the preparation of low molecular weight poly-α-olefins or poly(co-ethylene-α-olefins) (ie ethylene/α-olefin copolymers) generally occurs by contact between the selected catalyst or catalysts and the other starting ingredients, with a first step comprising contacting the lethal-ligand complex with an appropriate activating cocatalyst to form a catalyst, followed by contacting the catalyst or catalysts with the selected monomeric materials under appropriate reaction conditions to form the desired end product.
[010] In general, catalysts useful in the present invention belong to the group defined by co-pending US publication No. 2011/0282018 A1, filed May 11, 2011, attorney document No. 69428. However, catalysts used herein form a subset thereof that exhibit surprising capabilities not shared by other members of that group, notably to form the dielectric fluid compositions of the present invention.
[011] In some embodiments, each of the chemical groups (eg, X, L, R1a, etc.) of the metal-binder complex of formula (I) is unsubstituted, that is, it can be defined without the use of an RS substituent. In other embodiments, at least one of the chemical groups in the metal-ligand complex independently contains one or more RS substituents. Preferably, there is no more than a total of 20 RS, more preferably no more than 10 RS, and even more preferably no more than 5 RS. Where the compound of the invention contains two or more RS substituents, each RS independently binds to the same substituted chemical group or to a different unsubstituted chemical group. When two or more RS bind to the same chemical group, they independently bind to the same or different carbon atom or heteroatom in the same chemical group, up to and including per-substitution of the chemical group.
[012] The term "per-substitution" means each hydrogen atom (H) bonded to a carbon atom or heteroatom of a functional group or of a corresponding unsubstituted compound that is substituted by a substituent (eg RS). The term "polysubstitution" means at least two, but not all, hydrogen atoms bonded to carbon atoms or heteroatoms of a functional group or a corresponding unsubstituted compound that are replaced by substituents (eg, RS). In some embodiments, at least one RS is a polyfluorine replacement or a perfluorine replacement.
[013] As used herein, "polyfluorine substitution" and "perfluorine substitution" each count as an RS substituent. In some embodiments, each RS is independently selected from a group consisting of a halogen atom and any one of polyfluorine substitution, perfluorine substitution, unsubstituted C1-C18 alkyl, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS-, RS(O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O) -, RC(O)N(R)-, and R2NC(O)-, each R is independently an unsubstituted C1-C18 alkyl group. In some embodiments each RS is independently selected from a group consisting of a halogen atom, unsubstituted C1-C18 alkyl, and any of polyfluor substitution, perfluor substitution, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si -, R3Ge-, RO-, RS-, RS(O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)- , RC(O)N(R)-, and R2NC(O)-. In some embodiments each RS is independently selected from a group consisting of a C1-C18 alkyl group and any of polyfluor substitution, perfluor substitution, unsubstituted C1-C18 alkyl, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS-, RS(O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O) -, RC(O)N(R)-, and R2NC(O)-. In some embodiments two R2 join to form an unsubstituted C1-C18 alkylene. Even more preferably, the RS substituents are independently unsubstituted C1-C18 alkyl, F, unsubstituted C1-C18 alkylene, or a combination thereof; and even more preferably unsubstituted C1-C8 alkyl or unsubstituted C1-C8 alkylene. The C1C8 alkyl and C1-C8 alkylene substituents are especially useful for forming substituted chemical groups that are bicyclic or tricyclic analogs of corresponding unsubstituted monocyclic or bicyclic chemical groups.
[014] The term "hydrocarbylene" means a bivalent hydrocarbon radical having at least one carbon atom, such that each bivalent hydrocarbon radical is independently aromatic or non-aromatic, saturated or unsaturated, normal or branched chain, cyclic or acyclic , substituted or unsubstituted, or a combination of at least two of them. The two free valences of the bivalent hydrocarbon radical can be on a single carbon atom or, preferably, on different carbon atoms. The term "alkylene" is a hydrocarbylene in which the bivalent hydrocarbon radical is non-aromatic, saturated, straight-chain or branched, and unsubstituted or substituted. The term "hydrocarbyl" is as defined above for hydrocarbylene, except that hydrocarbylene is a divalent radical and hydrocarbyl is a monovalent radical and thus has a hydrogen in place of the second radical. The term "alkyl" is a hydrocarbyl in which the hydrocarbon radical is non-aromatic, saturated, straight-chain or branched, acyclic, and unsubstituted or substituted. Preferably, the substituted alkyl substituent is aryl. The term "heterohydrocarbylene" means a bivalent heterohydrocarbon radical having at least one carbon atom and from 1 to 6 heteroatoms, each bivalent heterohydrocarbon radical being independently aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched, cyclic or acyclic, unsubstituted or substituted, or a combination of at least two of these. The two free valences of the bivalent heterohydrocarbon radical may be on a single atom, or preferably on different atoms, each atom having a free valence being carbon or heteroatom. The term "heterohydrocarbyl" is as defined above for heterohydrocarbylene, except that heterohydrocarbyl is bivalent and heterohydrocarbyl is monovalent.
[015] In some embodiments, the present invention considers such molecules or unsubstituted chemical groups having a lower limit of at least 1 carbon atom. However, the invention includes embodiments having higher lower limits (for example, at least one of 2, 3, 4, 5, 6, 7, and 8 carbon atoms). In particular, embodiments including higher lower limits may be particularly preferred as would be well known for a minimal aspect of the chemical group or molecule (e.g., at least 3 carbons for cycloalkyl or α-olefin).
[016] Preferably, each hydrocarbyl is independently unsubstituted or substituted alkyl, cycloalkyl (having at least 3 carbon atoms), C3-C20 cycloalkyl-C1-C20 alkylene, aryl (having at least 6 carbon atoms, or aryl C 6 -C 20 -C 1 -C 20 alkylene Preferably, each of the aforementioned hydrocarbyl groups independently has a maximum of 40, more preferably 20, and most preferably 12 carbon atoms.
[017] Preferably, each alkyl independently has a maximum of 40, more preferably 20, even more preferably 12, and most preferably 8 carbon atoms. Some non-limiting examples of unsubstituted C1-C40 alkyl include unsubstituted C1-C20 alkyl, unsubstituted C1-C10 alkyl, unsubstituted C1-C5 alkyl, methyl, ethyl, 1-propyl, 2-methyl-propyl, 1.1 -dimethyl-ethyl, and 1 heptyl. Non-limiting examples of substituted C1-C40 alkyl include substituted C1-C20 alkyl, substituted C1-C10 alkyl, trifluoromethyl and C45 alkyl. The C45 alkyl group can be, for example, C27-C40 alkyl substituted by an RS, which is respectively C1-C5 alkyl. Preferably, each C1-C5 alkyl is independently methyl, trifluoromethyl, ethyl, 1-propyl, 2-methyl-ethyl, or 1,1-dimethyl-ethyl.
[018] Preferably, each aryl independently has from 6 to 40 carbon atoms. The term "C6-C40 aryl" means an unsubstituted or substituted (by at least one RS) aromatic mono, bi or tricyclic radical from 6 to 40, preferably from 6 to 14 ring carbon atoms, and the mono, bi radical. or tricyclic comprises, respectively, 1, 2 or 3 rings, wherein 1 ring is aromatic, at least one of the 2 or 3 rings is aromatic, and the 2 or 3 rings are independently fused or unfused. Analogously, other aryl groups are defined (eg, C6-C10 aryl). Preferably, the C6-C40 aryl group has a maximum of 20 carbon atoms (i.e., C6-C20 aryl), more preferably 10 carbon atoms, and most preferably 6 carbon atoms. Non-limiting examples of unsubstituted C6-C40 aryl include unsubstituted C6-C20 aryl, unsubstituted C6-C18 aryl, phenyl, (C3-C6 cycloalkyl)-phenyl, fluorenyl, tetrahydro-fluorenyl, indacenyl, hexahydro-indacenyl, indenyl, dihydro-indenyl, naphthyl, tetrahydronaphthyl, and phenanthrene. Examples of substituted C6-C40 aryl include substituted C6-C20 aryl, substituted C6-C18 aryl, 2-(C1-C5 alkyl)-phenyl, 2,4-bis(C1-C5 alkyl)-phenyl, 2,4-bis (C20 alkyl)-phenyl, poly-fluoro-phenyl, penta-fluoro-phenyl, and fluoren-9-one-1-yl.
[019] Preferably, each cycloalkyl independently has from 3 to 40 carbon atoms. The term "C3-C40 cycloalkyl" means a saturated cyclic hydrocarbon radical of 3 to 40 carbon atoms that is unsubstituted or substituted by at least one RS. Other cycloalkyl groups (eg C3-C12 cycloalkyl) are defined in an analogous way. Preferably, C3-C40 cycloalkyl has a maximum of 20 carbon atoms (i.e., C3-C20 cycloalkyl), and more preferably 6 carbon atoms. Non-limiting examples of unsubstituted C3-C40 cycloalkyl include unsubstituted C3-C20 cycloalkyl, unsubstituted C3-C10 cycloalkyl, cyclopropyl, and cyclodecyl. Examples of substituted C3-C40 cycloalkyl include substituted C3-C20 cycloalkyl, substituted C3-C10 cycloalkyl, cyclopentan-2-yl, and 1-fluoro-cyclohexyl.
[020] Preferably, each hydrocarbylene independently has from 1 to 40 carbon atoms. Examples of C1-C40 hydrocarbylene include unsubstituted or substituted C6-C40 arylene, C3-C40 cycloalkylene, and C1-C40 alkylene (e.g., C1-C20 alkylene). In some embodiments, the two free valences are on the same carbon (eg, -CH2-) or on adjacent carbon atoms (ie, diradicals-1,2), or are spaced apart by a two, etc., intermediate carbon atoms (eg, 1,3-diradicals, 1,4-diradicals, etc.) respectively. Preferred is a 1,2 diradical, a 1,3 diradical, a 1,4 diradical, or an α, w diradical, and more preferably a 1,2 diradical. The α, w diradical is a bivalent radical that has a maximum main carbon chain spacing between the carbons of the radicals. More preferably it is a 1,2-diradical version of C6-C18 arylene, C3-C20 cycloalkylene, or C2-C20 alkylene; a 1,3-diradical version of C6-C18 arylene, C4-C20 cycloalkylene, or C3-C20 alkylene; or a 1,4-diradical version of C6-C18 arylene, C6-C20 cycloalkylene, or C4-C20 alkylene.
[021] Preferably, each alkylene independently has from 1 to 40 carbon atoms. The term "C 1 -C 40 alkylene" means a straight or branched chain saturated bivalent radical (i.e., the free valences are not on the ring atoms) of 1 to 40 carbon atoms that is unsubstituted or substituted by at least one RS . In an analogous way other alkylene groups are defined (for example, C1-C12 alkylene). Examples of unsubstituted C1-C40 alkylene include unsubstituted C1-C20 alkylene, including unsubstituted 1,2-C2-C10 alkylene, 1,3-C3-C10 alkylene, 1,4-C4-C10 alkylene, -CH2-, -CH2CH2-, -(CH2)3-, -CH2CHCH3, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, and -(CH2)4C(H)(CH3)-. Examples of substituted C1-C40 alkylene include substituted C1-C20 alkylene, -CF2-, -C(O)-, and -(CH2)14C(CH3)2(CH2)5- (i.e., 6,6-dimethyl- 1,20-eicosylene). Since it was mentioned above that two RS can join to form a C1-C18 alkylene, examples of substituted C1-C40 alkylene also include 1,2-bis(methylene)cyclopentene, 1,2-bis(methylene)cyclohexane , 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.
[022] Preferably, each cycloalkylene independently has from 3 to 40 carbon atoms. The term "C3-C40 cycloalkylene" means a bivalent cyclic radical (i.e., the free valences are on the ring atoms) that is unsubstituted or substituted by at least one RS. Examples of unsubstituted C3-C40 cycloalkylene include 1,3-cyclopropylene, 1,1-cyclopropylene, and 1,2-cyclohexylene. Examples of substituted C3-C40 cycloalkylene include 2-oxo-1,3-cyclopropylene and 1,2-dimethyl-1,2-cyclohexylene.
[023] Preferably, each heterohydrocarbyl independently has from 1 to 40 carbon atoms. The term "C1-C40 heterohydrocarbyl" means a heterohydrocarbon radical and the term "C1-C40 heterohydrocarbylene" means a bivalent heterohydrocarbon radical, and each heterohydrocarbon independently has at least one heteroatom B(RC)O, S, S( O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), and N(RN), where each RC is independently unsubstituted C1-C18 hydrocarbyl, each RP is unsubstituted C1-C18 hydrocarbyl, and each RN is unsubstituted or absent C1-C18 hydrocarbyl (e.g., absent when N comprises -N= or N substituted on three carbons). The radicals of the bivalent radical can be of the same or different types of atoms (for example, both on saturated acyclic atoms or one on an acyclic atom and one on an aromatic atom). In an analogous way other heterohydrocarbyl groups (for example C1-C12 heterohydrocarbyl) and heterohydrocarbyl are defined. Preferably, the heteroatoms are: O, S, S(O), Si(RC)2, P(RP), or N(RN). The heterohydrocarbon radical and each of the two heterohydrocarbon radicals is independently on a carbon atom or heteroatom thereof, although preferably each is on a carbon atom when attached to a heteroatom in formula (I) or to a heteroatom of another heterohydrocarbyl or heterohydrocarbylene. Each C1-C40 heterohydrocarbyl and each C1-C40 heterohydrocarbylene is independently unsubstituted or substituted (by at least one RS), aromatic or non-aromatic, saturated or unsaturated, straight-chain or branched-chain, cyclic (including mono and polycyclic , fused and unfused polycyclic) or acyclic, or a combination of two or more thereof; and each is respectively the same or different from the other.
[024] Preferably, each heteroaryl independently has from 1 to 40 carbon atoms. The term "C1-C40 heteroaryl" means an unsubstituted or substituted (by at least one RS) mono, bi or tricyclic heteroaromatic hydrocarbon radical of 1 to 40 total carbon atoms and 1 to 4 heteroatoms; from 1 to 44 total ring atoms, preferably from 5 to 10 total ring atoms, and the mono, bi or tricyclic radical respectively comprises 1, 2 or 3 rings, 1 ring being heteroaromatic; at least one of the 2 or 3 rings is heteroaromatic, and the 2 or 3 rings are independently fused or unfused. Similarly, other heteroaryl groups are defined (eg, C1-C12 heteroaryl). The monocyclic heteroaromatic hydrocarbon radical has a 5- or 6-membered ring. The 5-membered ring has from 1 to 4 carbon atoms and from 4 to 1 heteroatoms, respectively, each heteroatom being O, S, N, or P, and preferably O, S, or N. Examples of heteroaromatic hydrocarbon radicals of 5-membered ring include pyrrol-1-yl, pyrrol-2-yl, furan-3-yl, thiophen-2-yl, pyrazol-1-yl, isoxazol-2-yl, isothiazol-5-yl, imidazol-2 -yl, oxazol-4-yl, thiazol-2-yl, 1,2,4-triazol-1-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl , tetrazol-1-yl, tetrazol-2-yl, and tetrazol-5-yl. The 6-membered ring has 4 or 5 carbon atoms and 2 or 1 heteroatoms, the heteroatoms being N or P, preferably N. Examples of 6-membered heteroaromatic hydrocarbon radicals include pyridin-2-yl, pyrimidin-2-yl, and pyrazin-2-yl. Preferably, the bicyclic heteroaromatic hydrocarbon radical is a 5,6-ring or fused-6.6-ring system. Examples of the 5,6-ring system bicyclic heteroaromatic hydrocarbon radical include indole-1-yl, and benzimidazol-1-yl. Examples of a bicyclic heteroaromatic hydrocarbon radical is a -6,6 ring system include quinolin-2-yl, and isoquinolin-2-yl. The tricyclic heteroaromatic hydrocarbon radical is a -5,6,5, -5,6.6, -6,5,6 or -6,6.6 fused ring system. An example of a fused 5,6.5 ring system is dihydropyrrole[3,2-f]indol-1-yl. An example of a 6,5,6 fused ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6 ring system is acridin-9-yl. The 5-membered rings and 6-membered rings of the -5,6, -6.6, -5,6,5, -5,6.6, -6,5,6, and -6.6 ring systems ,6 can be independently described as above for 5-membered and 6-membered rings, respectively, except where ring fusions occur.
[025] The aforementioned heteroalkyl and heteroalkylene groups are saturated monovalent or bivalent straight or branched chain radicals containing at least one carbon atom and at least one heteroatom (up to 4 heteroatoms) Si(RC)2, Ge(RC)2, P (RP), N(RN), N, O, S, S(O), and S(O)2 defined above, each of the heteroalkyl and heteroalkylene groups being independently unsubstituted or substituted by at least one LOL.
[026] Unless otherwise indicated herein, the term "heteroatom" means O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N( RN), where independently, each RC is unsubstituted C1-C18 hydrocarbyl, or two RCs join to form a C2-C19 alkylene (for example, two RCs together with the silicon atom to which they are attached form a 3 to 3 to silacycloalkyl 20 members), each RP is unsubstituted C1-C18 hydrocarbyl, and each RN is unsubstituted C1-C18 hydrocarbyl, a hydrogen atom, or absent (absent when N comprises -N= in an N-containing heteroaryl).
[027] Preferably, there is no O-O, S-S, O-S bond other than the O-S bond in a bivalent radical functional group S(O) or S(O)2 in the metal-linker complex of formula (I). More preferably, there is no OO, NN, PP, NP, SS, or OS bond other than the OS bond in a bivalent S(O) or S(O)2 radical functional group in the metal-ligand complex of formula (I ).
[028] The term "saturated" means devoid of carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. Where a saturated chemical group is replaced by one or more RS substituents, optionally, one or more double and/or triple bonds may or may not be present in RS substituents. The term "unsaturated" means to contain one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds, not including any such double bonds that may be present in RS substituents, if any, or in (hetero)aromatic rings, if any.
[029] In the metal-ligand complex of formula (I) certain variables and chemical groups n, M, X, Z, L, R1a, R2a, R3a, R4a, R1b, R2b, R3b, R4b, R5c, R6c, R7c , R8c, R5d, R6d, R7d, and R8d, where formulas allow, are preferred. Examples of such preferred groups follow.
[030] Preferably, M is zirconium or hafnium, and more preferably M is zirconium. The formal oxidation state of M can vary as +2 or +4. Any combination of a preferred M and a preferred formal oxidation state can be employed.
[031] In various embodiments n can be 0, 1, 2, or 3.
[032] Certain X groups are preferred. In some embodiments each X is, independently, the monodentate linker. Preferably, when there are two or more monodentate X linkers, each X will be the same. In some embodiments, the monodentate binder is the monoanionic binder. The monoanionic ligand has a resulting formal oxidation state of -1. Preferably, each monoanionic ligand is independently hydride, hydrocarbyl carbanion, heterohydrocarbyl carbanion, halide, nitrate, carbonate, phosphate, sulfate, HC(O)O-, hydrocarbyl-C(O)O-, HC(O)N(H )-, hydrocarbyl-C(O)N(H)-, hydrocarbyl-C(O)N- -KL-KL-K-K-MKL - (hydrocarbyl C1-C20) , RRB, RRN, RO, RS, or RRRSi, where each RK, RL, and RM is hydrogen, hydrocarbyl, or heterohydrocarbyl, or RK and RL join to form a C4-C40 heterohydrocarbylene or hydrocarbylene, and RM is as defined above.
[033] In some embodiments, at least one monodentate ligand of X is, independently, the neutral ligand. Preferably, the neutral linker is a Lewis base group X KL KLKLX KL which is RNRR, ROR, RSR, or RPRR, each RX independently being hydrogen, hydrocarbyl, (hydrocarbyl C1-C10)3Si, (hydrocarbyl C1 -C10)3Si-C1-C10 hydrocarbyl, or heterohydrocarbyl and each RK and RL is independently as defined above.
[034] In some embodiments, each X is a monodentate ligand that is independently a halogen atom, C1-C20 hydrocarbyl, (C1-C20 hydrocarbyl)-C(O)O- unsubstituted, or RKRLN- where each one of RK and RL is independently C1-C20 hydrocarbyl. In some embodiments each monodentate X linker is a chlorine atom, C1-C10 hydrocarbyl (eg, C1-C6 alkyl or benzyl), (C1-C10 hydrocarbyl-C(O)O- unsubstituted, or RKRLN- in which each of RK and RL is independently an unsubstituted C1-C10 hydrocarbyl.
[035] In some embodiments there are at least two X's and the two X come together to form the bidentate ligand. In some embodiments, the bidentate binder is a neutral bidentate binder. Preferably, the neutral bidentate linker is a diene of the formula (RD)2C=C(RD)-C(RD)=C(RD)2, in which each RD is independently H, unsubstituted C1-C6 alkyl, phenyl, or naphthyl. In some embodiments, the bidentate ligand is a mono-ligand (Lewis base) monoanionic. The monoanionic mono-linker (Lewis base) is preferably a 1,3-dionate of formula (D): RE-C(O-)=CH-C(=O)-RE(D) in which each RD is independently H, unsubstituted C1-C6 alkyl, phenyl, or naphthyl. In some embodiments, the bidentate ligand is a dianionic ligand. The dianionic ligand has a resulting formal oxidation state of -2. Preferably, each dianionic ligand is independently carbonate, oxalate (i.e., -O2CC(O)-), C2-C40 hydrocarbylene dicarbanion, heterohydrocarbylene dicarbanion, phosphate, or sulfate.
[036] As mentioned previously, one selects the number and charge (neutral, monoanionic, dianionic) of X depending on the formal oxidation state of M such that the metal-ligand complex of formula (I) is globally neutral.
[037] In some embodiments, each X is the same, with each X being methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethyl-propyl, trimethyl-silyl-methyl, phenyl, benzyl, or chlorine. In some embodiments n is 2 and each X is the same.
[038] In some embodiments at least two X's are different. In some embodiments n is 2 and each X is one other than methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2,2-dimethyl-propyl, trimethyl-silyl-methyl, phenyl, benzyl, and chlorine.
[039] The integer n indicates the number of X. Preferably, n is 2 or 3 and at least two X are independently monoanionic monodentate ligands and a third X, if present, is a neutral monodentate ligand. In some embodiments, n is 2 and two X come together to form a bidentate binder. In some embodiments, the bidentate linker is 2,2-dimethyl-2-silapropane-1,3-diyl or 1,3-butadiene.
[040] In some embodiments, L is a hydrocarbylene of two carbon atoms. In some embodiments, L comprises the linker backbone of 2 carbon atoms (for example, L is -CH2CH2-, -CH=CH- or -CH(CH3)CH(CH3)-). In some embodiments L is unsubstituted alkylene, and more preferably L is unsubstituted alkylene acyclic, and even more preferably unsubstituted alkylene acyclic is -CH2CH2-, -CH=CH-, cis-CH(CH3)CH(CH3 ) -, trans-CH(CH3)CH(CH3)-.
[041] In some embodiments, L is unsubstituted 1,2-cycloalkylene, and more preferably L is cis-1,2-cyclopentanediyl or cis-1,2-cyclohexanediyl. In some embodiments L is substituted cycloalkylene.
[042] In some embodiments, L is unsubstituted or substituted two-atom heterohydrocarbylene. In some embodiments, L comprises the 2-atom linker backbone (for example, L is -CH2CH(OCH3)- or -CH2Si(CH3)2-).
[043] Certain groups R1a, R2a, R1b, and R2b are preferred. In certain embodiments, one of R1a, R2a, R1b, and R2b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom; and each of the others of R1a, R2a, R1b, and R2b is a hydrogen atom. In some such embodiments each of R2a, R1b, and R2b is a hydrogen atom. In other such embodiments, each of R1a, R1b, and R2b is a hydrogen atom.
[044] In some embodiments, two of R1a, R2a, R1b, and R2b are independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom; and each of the others of R1a, R2a, R1b, and R2b is a hydrogen atom. In some such embodiments each of R1b and R2b is hydrogen. In other such some embodiments each of R2a and R2b is a hydrogen atom. In still other such some embodiments each of R1a and R1b is a hydrogen atom.
[045] In some embodiments three of R1a, R2a, R1b, and R2b are independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom, and the other of R1a, R2a, R1b, and R2b is a hydrogen atom. In some such embodiments, R1b is the hydrogen atom. In some such other embodiments, R2b is the hydrogen atom.
[046] In some embodiments, each of R1a, R2a, R1b, and R2b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom.
[047] In some embodiments one of R1a and R1b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom, and the other of R1a and R1b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments, one of R1a and R1b is independently hydrogen, hydrocarbyl, or halogen atom, and the other of R1a and R1b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments, each of R1a and R1b is independently hydrogen, hydrocarbyl, or a halogen atom. In some embodiments, at least one of R1a and R1b is hydrocarbyl. In some embodiments, each of R1a and R1b is halogen.
[048] In some embodiments one of R2a and R2b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom, and the other of R2a and R2b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments, one of R2a and R2b is independently hydrogen, hydrocarbyl, or halogen atom, and the other of R2a and R2b is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments, each of R2a and R2b is independently hydrogen, hydrocarbyl, or a halogen atom. In some embodiments, at least one of R2a and R2b is hydrocarbyl. In some embodiments, at least one of R2a and R2b is a halogen atom.
[049] Certain combinations of R1a, R2a, R1b, and R2b are preferred. In certain embodiments, R1a is a hydrogen atom; R1b is hydrocarbyl, heterohydrocarbyl, or halogen atom; R2b is independently hydrocarbyl, heterohydrocarbyl, or halogen atom; and R2b is independently hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments, R1b is independently hydrocarbyl or a halogen atom.
[050] In some embodiments each of R1a and R1b is independently a hydrogen atom, and at least one, and preferably each of R2a and R2b is independently hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments, at least one and preferably each of R2a and R2b is independently hydrocarbyl, or a halogen atom.
[051] In some embodiments, at least three of R1a, R2a, R1b, and R2b are independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom, and the remainder of R1a, R2a, R1b, and R2b is an atom of hydrogen, hydrocarbyl, heterohydrocarbyl, or a halogen atom. In some embodiments, at least three and in other embodiments each of R1a, R2a, R1b, and R2b is independently a hydrocarbyl or a halogen atom.
[052] Certain combinations of R2a, R2b, R3a, and R3b are preferred. In certain embodiments, R2a is a hydrogen atom; R2b is hydrocarbyl, heterohydrocarbyl, or halogen atom; R3a is independently hydrogen, hydrocarbyl, heterohydrocarbyl, or halogen atom; and R3b is independently a hydrogen atom, hydrocarbyl, heterohydrocarbyl, or halogen atom. In some embodiments, R2b is independently hydrocarbyl or a halogen atom.
[053] Certain combinations of R1a, R1b, R2a, R2b, R3a and R3b are more preferred. In some embodiments, each of R2a and R2b is a hydrogen atom and each of R1a, R1b, R3a and R3b is independently hydrocarbyl, heterohydrocarbyl, or halogen atom; and more preferably, each of R2a and R2b is a hydrogen atom and each of R1a and R1b is independently C1-C6 hydrocarbyl, C1C5 heterohydrocarbyl, fluorine atom, or chlorine atom, and each of R3a and R3b is independently C1-C12 hydrocarbyl, C1-C11 heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom. In some embodiments, each of R1a and R1b is independently hydrogen atom, each of R2a and R2b is independently C1-C8 hydrocarbyl, C1-C7 heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom ; and each of R3a and R3b is, independently, C1C12 hydrocarbyl, C1-C11 heterohydrocarbyl, fluorine atom, chlorine atom, or bromine atom.
[054] Preferably, each hydrocarbyl, when used to define R1a, R1b, R2a, R2b, R3a or R3b, is independently alkyl or cycloalkyl. Preferably, the alkyl group is C1-C12 alkyl, more preferably C1-C8 alkyl, even more preferably C1-C6 alkyl, and even more preferably C1-C4 alkyl. Preferably, the cycloalkyl group is C3-C6 cycloalkyl, and more preferably C3-C4 cycloalkyl. Preferably the C3-C4 cycloalkyl is cyclopropyl. Preferably, the C1-C4 alkyl is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-propyl, or 1,1-dimethyl-ethyl, and more preferably methyl, ethyl, 2-propyl, or 1,1-dimethyl-ethyl. In some embodiments, the C1-C4 alkyl is ethyl, 2-propyl, or 1,1-dimethyl-ethyl. Preferably, each halogen atom, when used to define R1a, R1b, R2a, R2b, R3a or R3b, is independently a fluorine atom or a chlorine atom.
[055] In some embodiments, each of R1a, R1b, R3a and R3b is independently methyl, ethyl, 2-propyl, 1,1-dimethyl-ethyl, mono-, di- or trifluoro-methyl, methoxy, ethoxy, 1-methyl-ethoxy, mono-, di- or trifluoro-methoxy, halogen atom, cyano, nitro, dimethylamino, aziridin-1-yl, or cyclopropyl. In some embodiments at least one, and in some embodiments, each of R2a and R2b is a hydrogen atom and each of R1a, R1b, R3a and R3b is independently methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 1,1-dimethyl-ethyl, cyano, dimethylamino, methoxy, trifluoro-methyl, bromine atom, fluorine atom, or chlorine atom.
[056] In some embodiments of the metal-ligand complex of formula (I), each of R1a and R1b is a hydrogen atom and at least one, and in some embodiments, each of R2a, R2b, R3a and R3b, is independently methyl, ethyl, 2-propyl, 1,1-dimethyl-ethyl, mono-, di- or trifluoro-methyl, methoxy, ethoxy, 1-methyl-ethoxy, mono-, di- or tri- fluoro-methoxy, halogen atom, cyano, nitro, dimethylamino, aziridin-1-yl, or cyclopropyl. In some embodiments, at least one, and in some embodiments, each of R1a and R1b is a hydrogen atom and each of R2a, R2b, R3a and R3b is independently methyl, ethyl, 1-propyl, 2-propyl , 1-butyl, 1,1-dimethyl-ethyl, cyano, dimethylamino, methoxy, trifluoro-methyl, bromine atom, fluorine atom, or chlorine atom.
[057] In some embodiments of the metal-binder complex of formula (I), one of R1a and R1b is methyl, and the other of R1a and R1b is as in any of the preferred embodiments described herein. More preferably, in some such embodiments each of R2a and R2b is a hydrogen atom and each of R3a and R3b is, independently, as in any of the preferred embodiments described herein.
[058] In some embodiments of the metal-binder complex of formula (I), at least one, and more preferably each of R1a and R1b is independently methyl, ethyl, 2-propyl, 1,1-dimethyl-ethyl , mono-, di- or trifluoro-methyl, methoxy, ethoxy, 1-methyl-ethoxy, mono-, di- or trifluoro-methoxy, halogen atom, cyano, nitro, dimethylamino, aziridin-1-yl , or cyclopropyl. More preferably, in such embodiments, at least one, and more preferably each of R2a and R2b is a hydrogen atom and each of R3a and R3b is, independently, as in any of the preferred embodiments described herein. In some such embodiments preferably at least one, and more preferably each of R1a and R1b is a halogen atom or C1-C6 alkyl, and even more preferably C1-C4 alkyl, fluorine or chlorine atom. In some embodiments at least one, and more preferably each of R1a and R1b is a fluorine atom. In some embodiments at least one, and more preferably each of R1a and R1b is a chlorine atom. In some embodiments at least one, and more preferably each of R1a and R1b is C1-C4 alkyl, and more preferably methyl. In general, any combination of R1a and R1b, R2a and R2b, and R3a and R3b can be made within the selections provided, permitted, or exemplified.
[059] In some embodiments of the methyl-linker complex of formula (I) or the linker of formula (Q) at least one of R1a, R1b, R3a, R3b, R7c and R7d is not methyl. In some embodiments of the methyl-linker complex of formula (I) at least one of R7c, R7d, R3a, and R3b is not methyl.
[060] Certain R4a and R4b are preferred. In some embodiments, each of R4a and R4b is a hydrogen atom. In some embodiments at least one and in some embodiments each of R4a and R4b is independently as defined above for R1a and R1b, respectively. When R4a or R4b is as defined above for R1a and R1b, respectively, or both, R4a and R1a may independently be the same or different and R4b and R1b may independently be the same or different. In some embodiments, at least one, and in some embodiments, each of R4a and R4b is independently methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 1,1-dimethyl-ethyl, cyano, dimethylamino, methoxy, trifluoromethyl, bromine atom, fluorine atom, or chlorine atom.
[061] Certain R5d and R5d are preferred. In some embodiments R5d and R5d are the same. In some embodiments R5d and R5d are different.
[062] In some embodiments, at least one, and more preferably each of R5d and R5d is independently C6-C40 aryl. Preferably, the C6-C40 aryl group is a C6-C18 aryl and more preferably C6-C12 aryl. In some embodiments, the C6-C40 aryl group is a substituted phenyl group and preferably a 2,4-disubstituted phenyl group where each substituent is RS, 2,5-disubstituted phenyl where each substituent is RS, or 2,6-disubstituted phenyl group where each substituent is RS, and more preferably where each RS is independently phenyl, methyl, ethyl, isopropyl, or t-butyl, and even more preferably 2,6-dimethyl-phenyl or 2,6-diisopropyl-phenyl. In some embodiments, the C6-C40 aryl group is a 3,5-disubstituted phenyl group where each substituent is RS, and more preferably where each RS is independently phenyl, methyl, ethyl, isopropyl, or t-butyl, plus more preferably 3,5-di(t-butyl)phenyl or 3,5-diphenyl-phenyl. In some embodiments, the C6-C40 aryl group is a 2,4,6-trisubstituted phenyl group in which each substituent is RS, and more preferably in which each RS is independently phenyl, methyl, ethyl, isopropyl, or t- butyl. In some embodiments, the C6-C40 aryl group is naphthyl or substituted naphthyl in which each substituent is RS, and more preferably in which each RS is independently phenyl, methyl, ethyl, isopropyl, or t-butyl, and even more preferably 1-naphthyl, 2-methyl-1-naphthyl, or 2-naphthyl. In some embodiments, the C6-C40 aryl group is 1,2,3,4-tetrahydronaphthyl, and more preferably 1,2,3,4-tetrahydronaphth-5-yl or 1,2,3,4-tetrahydronaphth-6- there. In some embodiments, the C6-C40 aryl group is anthracenyl, and more preferably anthracen-9-yl. In some embodiments, the C6-C40 aryl group is 1,2,3,4-tetrahydro-anthracenyl, and more preferably 1,2,3,4-tetrahydro-anthracen-9-yl. In some embodiments, the C6C40 aryl group is 1,2,3,4,5,6,7,8-octahydro-anthracenyl, and more preferably 1,2,3,4,5,6,7,8-octahydro- anthracen-9-ila. In some embodiments, the C6-C40 aryl group is phenanthrenyl, and more preferably phenanthrene-9-yl. In some embodiments, the C6-C40 aryl group is 1,2,3,4,5,6,7,8-octahydro-phenanthrenyl, and more preferably 1,2,3,4,5,6,7,8- octahydro-phenantren-9-yl. As mentioned above, each of the C6-C40 aryl groups is independently unsubstituted or substituted by one or more RS substituents. In some embodiments, the C6-C40 aryl group is unsubstituted. Preferred unsubstituted C6-C40 aryl is unsubstituted inden-6-yl, 2,3-dihydro-1H-inden-6-yl, naphthalen-2-yl, or 1,2,3,4-tetrahydro-naphthalen-6 -yl, and more preferably unsubstituted naphthalen-1-yl, 1,2,3,4-tetrahydro-naphthalen-5-yl, anthracen-9-yl, 1,2,3,4-tetrahydro-anthracen-9- ila, or 1,2,3,4,5,6,7,8-octahydro-anthracen-9-yl. As mentioned above for C6-C40 aryl, each of the aforementioned C6-C40 aryl groups is independently unsubstituted or substituted by one or more RS substituents. In some embodiments, aryl C6-C40 is replaced by 1 to 4 RS, where RS is as described above. Preferably there are 1 or 2 RS substituents on each substituted C6-C40 aryl, and more preferably 2 RS substituents on each substituted phenyl. Preferably, each RS of the substituted C6-C40 aryl of R5c and R5d is independently an unsubstituted C3-C10 hydrocarbyl, more preferably an unsubstituted C4-C8 hydrocarbyl, even more preferably phenyl or an unsubstituted C4-C10 alkyl, and even more preferably an unsubstituted C4-C8 tertiary alkyl (for example, t-butyl or t-octyl (i.e., 1,1-dimethylhexyl)). Examples of preferred C6-C40 substituted aryl include 2,6-disubstituted phenyl having the same RS substituent (e.g., 2,6-dimethyl-phenyl, 2,6-diethyl-phenyl, 2,6-bis(1-methylethyl) phenyl, and 2,6-diphenyl-phenyl); 3,5-disubstituted phenyl having the same RS substituent (for example, 3,5-dimethyl-phenyl, 3,5-bis(trifluoro-methyl)phenyl, and 3,5-diphenyl-phenyl); 2,4,6-trisubstituted phenyl having the same RS substituent (for example, 2,4,6-trimethyl-phenyl, and 2,4,6-tris(1-methylethyl)phenyl); 1-methyl-2,3-dihydro-1H-inden-6-yl; 1,1-dimethyl-2,3-dihydro-1H-inden-6-yl; 1-methyl-1,2,3,4-tetrahydro-naphthalen-5-yl; and 1,1-dimethyl-1,2,3,4-tetrahydro-naphthalen-5-yl.
[063] In some embodiments at least one, and more preferably each of R5c and R5d is independently heteroaryl. Preferably, the heteroaryl has at least one nitrogen-containing aromatic ring. More preferably, the heteroaryl is pyridinyl, indolyl, indolinyl, quinolinyl, 1,2,3,4-tetrahydro-quinolinyl, isoquinolinyl, 1,2,3,4-tetrahydro-isoquinolinyl, carbazolyl, 1,2,3,4- tetrahydro-carbazolyl, or 1,2,3,4,5,6,7,8-octahydro-carbazolyl. In some embodiments, the heteroaryl is carbazolyl or substituted carbazolyl, preferably 2,7-disubstituted carbazolyl or 3,6-disubstituted carbazolyl, and more preferably 2,7-disubstituted 9H-carbazol-9-yl or 9H-disubstituted carbazolyl-9-yl 3,6-disubstituted, with each substituent being RS, more preferably each RS being independently phenyl, methyl, ethyl, isopropyl, or t-butyl, most preferably 3,6-di(t-butyl)- carbazolyl, 3,6-di(t-octyl)-carbazolyl, 3,6-diphenyl-carbazolyl, or 3,6-bis(2,4,6-trimethyl phenyl)-carbazolyl, and more preferably 3,6-di (t-butyl)-carbazol-9-yl, 3,6-di(t-octyl)-carbazol-9-yl, 3,6-diphenyl-carbazol-9-yl, or 3,6-bis(2, 4,6-trimethyl phenyl)-carbazol-9-yl. Examples of 2,7-disubstituted carbazolyl are 3,6-disubstituted carbazolyl where the 3,6-substituents move to the 2,7-positions, respectively. t-octyl is 1,1-dimethylhexyl. In some embodiments, the heteroaryl is 1,2,3,4-tetrahydro-carbazolyl, preferably 1,2,3,4-tetrahydro-carbazol-9-yl. As mentioned above for heteroaryl, each of the aforementioned heteroaryls is independently unsubstituted or substituted by one or more RS substituents. Preferably, each of indolyl, indolinyl, and heteroaryl containing tetrahydro- or octahydro- is attached via its ring nitrogen atom to phenyl rings having R5c or R5d in formula (I). In some embodiments, heteroaryl is unsubstituted. Preferred unsubstituted heteroaryl is unsubstituted quinolin-4-yl, unsubstituted quinoline-5-yl, or unsubstituted quinoline-8-yl (the N of quinolinyl being in position 1); 1,2,3,4-tetrahydro-quinolin-1-yl (the N of tetrahydro-quinolinyl being in position 1); isoquinolin-1-yl, isoquinolin-4-yl, isoquinolin-5-yl, or isoquinolin-8-yl (the N of isoquinolinyl being in position 1); 1,2,3,4-tetrahydro-isoquinolin-2-yl (the N of tetrahydro-isoquinolinyl being in position 1); 1H-indol-1-yl (the indolyl N being at position 1); 1H-indolin-1-yl (the indolinyl N being at position 1); 9-carbazol-9-yl (the N of carbazolyl being in position 9), which may also be called dibenzo-1H-pyrrole-1-yl; 1,2,3,4-tetrahydro-carbazolyl-9-yl (the N of tetrahydro-carbazolyl being at position 9); or 1,2,3,4,5,6,7,8-octahydro-carbazolyl-9-yl (the N of octahydro-carbazolyl being at position 9). In some embodiments, heteroaryl is substituted for 1 to 4 RS. Preferably there are 1 or 2 RS substituents on each substituted heteroaryl. Preferably, each RS of the substituted heteroaryl of R5c and R5d is independently an unsubstituted C3-C10 hydrocarbyl, more preferably an unsubstituted C4-C8 hydrocarbyl, even more preferably phenyl or an unsubstituted C4-C10 alkyl, and still more preferably C4-C8 tertiary alkyl (for example, t-butyl or t-octyl (i.e., 1,1-dimethylhexyl)). Preferably, the substituted heteroaryl is 2,7-disubstituted quinolin-4-yl, 2,7-disubstituted quinolin-5-yl, or 3,6-disubstituted quinolin-8-yl; 1,2,3,4-tetrahydro-quinolin-1-yl 3,6-disubstituted; 4-monosubstituted isoquinolin-5-yl; 1,2,3,4-tetrahydro-isoquinolin-1-yl 2-monosubstituted; 3-monosubstituted 1H-indol-1-yl; 3-monosubstituted 1H-indolin-1-yl; 2,7-disubstituted 9H-carbazol-9-yl; 9H-carbazol-9-yl 3,6-disubstituted; 1,2,3,4-tetrahydro-carbazol-9-yl 3,6-disubstituted; or 1,2,3,4,5,6,7,8-octahydro-carbazol-9-yl 3,6-disubstituted. Examples of preferred substituted heteroaryl include 4,6-bis(1,1-dimethyl ethyl)pyridin-2-yl; 4,6-diphenyl-pyridin-2-yl; 3-phenyl-1H-indol-1-yl; 3-(1,1-dimethylethyl)-1H-indol-1-yl; 3,6-diphenyl-9H-carbazol-9-yl; 3,6-bis[2',4',6'-tris(1,1-dimethyl phenyl)]-9H-carbazol-9-yl; and more preferably each of R5c and R5d is 3,6-bis(1,1-dimethylethyl)-9H-carbazol-9-yl. The term "t-butyl" means 1,1-dimethyl-ethyl. More preferably R5c and R5d are defined as in any of the Examples described below.
[064] In some embodiments of the metal-ligand complex of formula (I) each Z is O, each of R2a and R2b is a hydrogen atom, and each of R5c and R5d is independently heteroaryl. In such embodiments the most preferred is a metal-binder complex according to any one of formulas (Ia) to (Ie):

in which M, X, R1a, R1b, R3a, R3b, R7c, R7d, and L are as defined above and each of R55 and R65 is as defined above. Preferably, each of R55 and R65 is independently a hydrogen atom or an unsubstituted C1-C12 alkyl group.
[065] In some embodiments of the metal-ligand complex of formula (I) each Z is O, each of R1a and R1b is a hydrogen atom, and each of R5c and R5d is the heteroaryl. In such embodiments the most preferred is a metal-binder complex according to any one of formulas (If) to (Ij):

in which M, X, R2a, R2b, R3a, R3b, R7c, R7d, and L are as defined above and each of R55 and R65 is as defined above. Preferably, each of R55 and R65 is independently a hydrogen atom or an unsubstituted C1-C12 alkyl group.
[066] In some embodiments of the metal-ligand complex of formula (I) each Z is O, each of R2a and R2b is a hydrogen atom, and each of R5c and R5d is independently C6-C40 aryl. In such embodiments most preferred is a metal-binder complex according to any one of formulas (Ik) to (Io):

in which M, X, R1a, R1b, R3a, R3b, R7c, R7d, and L are as defined above and each of R55 and R65 is as defined above. Preferably, each of R55 and R65 is independently a hydrogen atom or an unsubstituted C1-C12 alkyl group
[067] In some embodiments of the metal-ligand complex of formula (I) each Z is O, each of R1a, R1b, R2a and R2b is a hydrogen atom, and each of R5c and R5d is independently aryl C6-C40 or C6-C40 heteroaryl. In such embodiments the most preferred is a metal-binder complex according to any one of formulas (Ip) to (It):

in which M, X, R3a, R3b, R7c, R7d, and L are as defined above and each of R55 and R65 is as defined above. Preferably, each of R55 and R65 is independently a hydrogen atom or an unsubstituted C1-C12 alkyl group.
[068] As mentioned above for the metal-ligand complex according to any one of the formulas (Ia) to (Io), 1a 2a 3a 1b 2b 3b 7c 7d M, X, L, R , RR , R , R , R , R and R , when applicable, are defined as the same as in formula (I) (ie 1a 2a 3a 1b 2b 3b 7c 7d as M, X, L, R , R , R , R , R , R , R and R of formula (I)). Preferably M is hafnium or zirconium, and more preferably hafnium. Preferably each X is a monodentate linker. In some embodiments of the metal-ligand complex according to any one of formulas (Ia) to (t), n is 2 or 3 and at least two X are independently mono-anionic monodentate ligands and a third X, if present, is a neutral monodentate binder. In some embodiments L is -CH2CH2-, -CH(CH3)CH(CH3)-, -CH2C(CH3)2-, or -CH2Si(CH3)2-. In some embodiments each of R1a, R2a, R3a, R1b, R2b, R3b is independently hydrogen, methyl, ethyl, 2-propyl, 1,1-dimethyl-ethyl, mono-, di-, or trifluoro-atom -methyl, methoxy, ethoxy, 1-methyl-ethoxy, mono-, di- or trifluoro-methoxy, halogen atom, cyano, nitro, dimethylamino, aziridin-1-yl, or cyclopropyl, with at least one of R1a, R2a, and R3a independently is not the hydrogen atom and at least one of R1b, R2b, and R3b independently is not the hydrogen atom. In some embodiments, each of R7c and R7d is independently C4-C8 alkyl.
[069] The process of the invention employs catalytic amounts of the catalyst of the invention. When employing more than one catalyst, each catalyst will be present in a catalytic amount. The term "catalytic amount" means less than a stoichiometric amount, based on the number of moles of a product-limiting stoichiometric reagent employed in the process of the invention. The catalytic amount is also greater than or equal to the minimum amount of the metal-ligand complex of formula (I) necessary to form and detect (for example, by mass spectroscopy) at least some product of the catalyzed reaction. Preferably, the minimum catalytic amount is 0.0001 mole percent of the number of moles of a product limiting stoichiometric reagent. In the process of the invention the product-limiting stoichiometric reagent for the catalyst of the invention will typically be ethylene. Preferably, the catalytic amount of the metal-binder complex of formula (I) used to prepare the catalyst of the invention is from 0.001 mol% to 50 mol% ethylene or C3-C40 α-olefin, whichever is smaller. . More preferably, the catalytic amount of the metal-binder complex of formula (I) is at least 0.01 mol%, even more preferably at least 0.05 mol%, and even more preferably at least 0.1% molar. Also more preferably, the catalytic amount of the metal-binder complex of formula (I) is less than or equal to 40 mol%, and even more preferably less than or equal to 35 mol%.
[070] Preferably, the catalyst has a minimum or greater catalytic efficiency. Catalytic efficiency is calculated by dividing the number of polyethylene or poly(co-ethylene-α-olefin) grains prepared by the number of grams of metal (M) in ingredient (a) (ie, M in the metal-complex). binder of formula (I)) employed (i.e. catalytic efficiency = g PE prepared/g M in the metal-binder complex of formula (I) employed). Preferably, when determining catalytic efficiency using ethylene and 1-octene at a polymerization reaction temperature of 170°C and 0.10 μ mol of the metal-ligand complex of formula (I), 0.12 μ mol of the activation cocatalyst , bis(octadecyl)methyl ammonium tetrakis(penta-fluorophenyl)borate ([HNMe(C18H37)2] [B(C6F5)4], abbreviated as BOMATPB), and 1.0 μ mol of another activation cocatalyst that is methyl-aluminoxane-3A modified with triisobutyl aluminum (MMAO-3A), hydrogen gas, and a mixed alkanes solvent, the catalytic efficiency is greater than 740,000, more preferably greater than 960,000, even more preferably greater than 1,480,000, and even more preferably greater than 1,900,000. Preferably, when determining the catalytic efficiency using ethylene and 1-octene as described below at a polymerization reaction temperature of 170°C and 0.08 μ mol of the metal-binder complex of formula (I), 0.096 μ mol of the BOMATPB, and 0.8 μ mol of MMAO-3A, the catalytic efficiency is greater than 1,480,000. Preferably, when determining the catalytic efficiency using ethylene and 1-octene as described below at a polymerization reaction temperature of 170°C and 0.075 μ mol of the metal-binder complex of formula (I), 0.09 μ mol of the BOMATPB, and 0.75 µ mol of MMAO-3A, the catalytic efficiency is greater than 970,000, more preferably greater than 1,060,000, and even more preferably greater than 1,090,000. Preferably, when determining the catalytic efficiency using ethylene and 1-octene as described below at a polymerization reaction temperature of 170°C and 0.05 μ mol of the metal-binder complex of formula (I), 0.06 μ mol of BOMATPB, and 0.5 µ mol of MMAO-3A, the catalytic efficiency is greater than 920,000, more preferably greater than 940,000, and even more preferably greater than 2,900,000. More preferably, catalytic efficiency is defined as in any of the Examples described below.
[071] In some embodiments, the catalyst, catalyst system or composition or both further comprise one or more solvents, diluents, or a combination thereof. In other embodiments, they can further comprise a dispersant, for example, an elastomer, preferably dissolved in the diluent. In these embodiments, the catalyst is preferably homogeneous.
[072] The invention further requires a cocatalyst for activating the metal-ligand complex. Where there are two or more such cocatalysts, they can be activated by the same or different ones. Many cocatalysts and activation techniques have previously been taught with respect to different metal-binder complexes in the following United States (US) patents: US 5,064,802, US 5,153,157, US 5,296,433, US 5,321,106, US 5,350 ,723, US 5,425,872, US 5,625,087, US 5,721,185, US 5,783,512, US 5,883,204, US 5,919,983, US 6.696,379, and US 7,163,907. Preferred cocatalysts (activation cocatalysts) for use herein include aluminum alkyl, oligomeric or polymeric aluminoxanes (also known as alumoxanes); neutral Lewis acids; and non-coordinating, non-polymeric ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is, for example, bulk electrolysis, which is well known to those skilled in the art. Combinations of one or more of the cocatalysts and prior techniques are also considered. The term "alkyl aluminum" means a monoalkyl aluminum dihydride or monoalkyl aluminum dihalide, a dialkyl aluminum hydride or a dialkyl aluminum halide, or a trialkyl aluminum. Preferably, the alkyl of the above aluminum alkyls is from 1 to 10 carbon atoms. Most preferred is triethyl aluminum. Aluminoxanes and their preparations are known, for example, from US 6,103,657. Examples of preferred oligomeric or polymeric aluminoxanes are: methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane. Other preferred cocatalysts are tri(C6-C18 aryl)boron compounds and halogenated (including perhalogenated) derivatives thereof (for example, tris(penta-fluorophenyl)borane, trityl tetrafluoroborate, or more preferably tetrakis Bis(octadecyl)methyl ammonium (penta-fluor-phenyl)borate ([HNMe(C18H37)2] [B(C6F5)4], abbreviated as BOMATPB)). In some embodiments, at least two of the cocatalysts are used in combination with each other.
[073] The ratio of the total number of moles of one or more metal-ligand complexes of formula (I) to the total number of moles of one or more of the activation cocatalysts is from 1:10,000 to 100:1. Preferably the ratio is at least 1:5000, more preferably 1:1000 and less than or equal to 10:1, more preferably less than or equal to 1:1. When using an aluminoxane alone as the activation cocatalyst, preferably the number of moles of the aluminoxane employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). When using tris(penta-fluor-phenyl)borane alone as the activation cocatalyst, preferably the number of moles of the tris(penta-fluoro-phenyl)borane employed to the total number of moles of the one or more metal-binder complexes of formula (I) may range from 0.5:1 to 10:1, more preferably from 1:1 to 6:1, and even more preferably from 1:1 to 5:1. The remaining activation cocatalysts are generally employed in molar amounts that are approximately equal to the total molar amounts of the one or more metal-binder complexes of formula (I).
[074] In certain circumstances, one can directly determine the comonomer incorporation index, for example, by using NMR spectroscopic techniques described above or by IR spectroscopy. If NMR and IR spectroscopic techniques cannot be used, then any difference in comonomer incorporation will be determined indirectly. For polymers formed from multiple monomers this indirect determination can be performed by various techniques based on the reactivity of monomers.
[075] The olefin polymerization conditions employed herein refer independently to reaction conditions such as solvent, atmosphere, temperature, pressure, time, and the like that are preferred to produce after a reaction time of 15 minutes, yield of at least 10 %, more preferably at least 20%, and even more preferably at least 30% of the poly-α-olefin or poly(co-ethylene/α-olefin) having a molecular weight of less than 2500 Da of the process of the invention. Preferably, the process takes place independently in an inert atmosphere (for example, in an inert gas consisting essentially of nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof). However, other atmospheres are considered and these include sacrificial olefin in the form of a gas and hydrogen gas (eg as a polymerization terminating agent). In some aspects, the process can take place neat, without solvent and with or without additional ingredients (for example, catalyst stabilizer such as triphenyl phosphine). In still other aspects, the process may take place with a solvent or a mixture of two or more solvents, for example an aprotic solvent. Preferably, the pure process or solvent-based process takes place at a temperature of the pure mixture or solvent-containing mixture of at least 100°C. A convenient temperature is approximately 120°C, preferably 140°C to about 250°C, preferably 230°C, more preferably 190°C (for example, at 150°C or 170°C or 190°C ). Preferably, the process takes place at a pressure of from 0.9 atmosphere (atm) to 10 atm (i.e., from about 91 kPa to about 1010 kPa). More preferably the pressure is about 1 atm (i.e., about 101 kPa).
[076] In some embodiments, polymerizable olefins useful in the process of the invention are C2-C40 hydrocarbons consisting of carbon and hydrogen atoms and containing at least 1, and preferably no more than 3, and more preferably no more than 2 carbon-double bonds carbon. In some embodiments, 1 to 4 hydrogen atoms of C2-C40 hydrocarbons are replaced with halogen atoms, preferably fluorine or chlorine to give C2-C40 hydrocarbons substituted with halogen atoms as the useful polymerizable olefins. C2-C40 hydrocarbons (unsubstituted by halogen atoms) are preferred. Preferred polymerizable olefins (i.e., olefinic monomers) useful to prepare the polyolefins are ethylene and C3-C40 polymerizable olefins. C3-C40 olefins include an α-olefin, a cyclic olefin, styrene, and a cyclic or acyclic diene. In some embodiments, at least one of the other polymerizable olefins is an α-olefin, and more preferably a C3-C40 α-olefin. In some embodiments, the C3-C40 α-olefin is a C4-C40 α-olefin, more preferably a C6-C40 α-olefin, even more preferably a C7-C40 α-olefin, and even more preferably a C8 α-olefin -C40. Preferably, the α-olefin comprises a C3-C40 α-olefin, more preferably a branched-chain C3-C40 α-olefin, even more preferably a straight-chain α-C3-C40 α-olefin, even more preferably a C3 α-olefin straight-chain -C40 of formula (A): CH2=CH2-(CH2)zCH3 (A), in which z is an integer from 0 to 40, and even more preferably a straight-chain C3-C40 α-olefin which is 1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 - pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, or a straight-chain C20-C24 α-olefin. Preferably, the cyclic olefin is a C3-C40 cyclic olefin. Preferably, the cyclic or acyclic diene is a C4-C40 diene, preferably an acyclic diene, more preferably a C4-C40 acyclic conjugated diene, more preferably a C4-C40 acyclic 1,3-conjugated diene, and even more preferably 1,3 -butadiene.
[077] Polyolefins that can be prepared by the process of the invention include, for example, interpolymers comprising ethylene residues and one or more C3-C40 polymerizable olefins. Preferred interpolymers are those prepared by copolymerizing a mixture of two or more polymerizable olefins such as, for example, ethylene/propylene, ethylene/1-butene, ethylene/1-pentene, ethylene/1-hexene, ethylene/4-methyl-1- pentene, ethylene/1-octene, ethylene/styrene, ethylene/propylene/butadiene and other EPDM terpolymers. Preferably, the polyolefin is an ethylene homopolymer (eg a high density polyethylene), an ethylene/α-olefin interpolymer (i.e., poly(co-ethylene-α-olefin) such as, for example, a poly(ethylene/1-octene)), or an ethylene/α-olefin/diene interpolymer (i.e. a poly(ethylene/α-olefin/diene terpolymer such as, for example, a poly(ethylene/1- octene/1,3-butadiene)).
[078] Preferably, the molar ratio of (moles of α-olefin C3-C40)/(moles of ethylene) is greater than or equal to 0.1, more preferably greater than or equal to 0.30, even more preferably greater than or equal to to 0.50, and even more preferably greater than or equal to 0.75 (eg greater than or equal to 1.0).
[079] In another embodiment, the present invention is a polyolefin, preferably polyethylene (for example, in an isolated form or as part of an intermediate mixture with the α-olefin) prepared by the process of the invention.
[080] The inventive process can take place in one reactor or in multiple reactors. For example, multiple catalyst processes in a single reactor are useful in the present invention. In one embodiment, two or more catalysts are introduced into a single reactor under the conditions of olefin polymerization, at least the first of the catalysts being a catalyst from the group specified herein, and each catalyst inherently produces a mixture or composition of different polyolefin copolymers. The terms "mixture" and "composition" when applied to polyolefin copolymers are synonymous. The use of different catalysts within the invention may result in similar or different comonomer incorporation, but the products within the invention will fall within a weight average molecular weight range of less than 2500 Da, preferably less than 1500 Da. more catalysts within a single reactor will vary the product ratio, and knowledge of such is within the knowledge of those skilled in the art. See also, US 6,924,342. The catalysts of the invention are compatible with other olefin polymerization catalysts, including Ziegler-Natta catalysts. Because of this compatibility, an additional catalyst included in a reaction may comprise a metallocene or other π-bonded binding group-containing metal-ligand complex (including constrained geometry metal-ligand complexes), or a group-containing metal-ligand complex polyvalent heteroatom ligand, especially complexes based on polyvalent pyridylamine or imidazolylamine and Group 4-metal complexes based on tetradentate oxygen-linked biphenyl-phenol. Preferably, the catalyst of the invention is prepared, and the process of the invention employs, from three or less, more preferably two, and even more preferably one metal-binder complex of formula (I) per reactor. Further discussion of the above subject matter can be found in co-pending U.S. patent publication No. 2011/0282018 A1, filed May 11, 2011, attorney document No. 69428.
[081] In some embodiments, a preferred inventive process may achieve a polydispersity index (PDI) or minimum molecular weight distribution of the polyolefin product so produced. In some incorporations the PDI is greater than 2.4, in other incorporations the PDI is greater than 4.0, in other incorporations the PDI is greater than 6.0 and in still other incorporations the PDI is greater than 8.0. In some developments, the PDI is less than 11.
[082] In some embodiments, a preferred inventive process may achieve a productivity ratio of weight polyolefin produced per weight of ethylene employed, determined using ethylene and 1-octene as described later at a polymerization reaction temperature of 170°C, the productivity ratio of the polyolefin produced to the ethylene employed being greater than 1.00, preferably greater than 1.10, more preferably greater than 1.40, and even more preferably greater than 2.50. Examples General Analysis Procedure
[083] Gel Permeation Chromatography (GPC) - Determines the weight average molecular weight (Mw) and the polydispersion index: Mw and the ratio of Mw/Mn (polydispersion index or PDI) are determined using a permeation chromatograph in high temperature 210 gel from Polymer Labs™. Samples are prepared using 13 mg of polyethylene polymer which is diluted with 16 ml of 1,2,4-trichlorobenzene (stabilized with butylated hydroxy toluene (BHT), heated and stirred at 160°C for 2 hours.
[084] Melting and crystallization temperatures and heat of fusion are determined by differential scanning calorimetry (DSC; DSC 2910, TA Instruments, Inc.): First the samples are heated from room temperature to 180°C at a rate of heating at 10°C/minute. After keeping the samples at this temperature for 2 to 4 minutes, the samples are cooled to -40°C at a cooling rate of 10°C/minute, and this temperature is maintained for 2 to 4 minutes, and then the mixtures are heated. up to 160°C.
[085] Abbreviations (meanings): rt (room temperature); g (gram); mL (milliliter); °C (degree Celsius); mmol (millimol); MHz (mega Hertz); Hz (Hertz). Synthesis Procedures for Metal-Binder Complexes Sequence of Reaction 1
Step 1: Preparation of 3,6-bis(1,1-dimethylethyl)-9H-carbazole.
[086] In a 500 mL three-neck round bottom flask equipped with an overhead stirrer, nitrogen gas bubbler, and an addition funnel, add 20.02 g (120.8 mmol) of carbazole, 49.82 g (365.5 mmol) of ZnCl2, and 300 mL of nitromethane at room temperature (rt). To the resulting dark brown slurry is added dropwise 49.82 g (365.5 mmol) of 2-chloro-2-methyl-propane from the addition funnel over a period of 2.5 hours. After the addition is complete, the resulting slurry is stirred for an additional 18 hours. The reaction mixture is poured into 800 ml of ice/cold water, extracted with 3 x 500 ml of methylene chloride, the extracts are then combined and dried with anhydrous magnesium sulphate and then filtered, and the filtrate is then concentrated by rotary evaporation and then evaporated in high vacuum to remove nitromethane. The resulting residue is dissolved in hot methylene chloride (70 ml) followed by hot hexanes (50 ml). The resulting solution is cooled to room temperature and then placed in a refrigerator overnight. The solids formed are isolated and washed with cold hexanes and then vacuum dried to yield 10.80 g (32.0%) of ivory crystals. 1H NMR shows the product is as desired. Reaction Sequence 2
Step 2: Preparation of 2-iodo-4-(2,4,4-trimethyl-pentan-2-yl)phenol.
[087] To a stirred solution of 10.30 g (50.00 mmol) of 4-(2,4,4-trimethyl-pentan-2-yl)phenol in 125 ml of methanol at 0°C are added 7, 48 g (50.00 mmol) of NaI and 2.00 g (50.00 mmol) of NaOH. To the resulting mixture, 86 ml of a 5% aqueous NaOCl solution (commercial bleach) are added over a period of one hour. The resulting slurry is stirred for an additional hour at 0°C. A 10% Na2S2O3 solution (30 mL) is added and acidified by addition of dilute hydrochloric acid. The resulting mixture is extracted with methylene chloride and the resulting organic layer is washed with brine and dried over anhydrous magnesium sulfate. Volatiles are removed and the resulting residue is purified by flash silica gel chromatography, eluting with 5% by volume ethyl acetate in hexanes to yield 11.00 g (66%) of product as a viscous oil. 1H NMR shows the product is as desired. Reaction Sequence 3
Step 3: Preparation of intermediate, 2-(2-iodo-4-(2,4,4-trimethyl-pentan-2-yl)phenoxy)tetrahydro-2H-pyran.
[088] In a stirred solution of 4.91 g (14.78 mmol) of 4-(2,4,4-trimethyl-pentan-2-yl)phenol and 1.50 g (17.83 mmol) of 3, 4-dihydro-pyran in 5 ml of methylene chloride at 0°C are added 0.039 g (0.205 mmol) of para-toluenesulfonic acid monohydrate. The resulting solution quickly turns purple. The solution is allowed to warm to room temperature and stir for approximately 10 minutes. Triethylamine (0.018 g, 0.178 mmol) is added and the resulting mixture turns yellow. The mixture is diluted with 50 mL of methylene chloride, and washed successively with 50 mL each of 1M NaOH, water, and brine. The organic phase is dried with anhydrous magnesium sulfate, filtered, and the filtrate concentrated to give a crude material. The crude material is purified by flash silica gel chromatography using 5% by volume ethyl acetate in hexanes to yield 5.18 g (93.12%) of product as a golden oil. 1H NMR shows the product is as desired. Reaction Sequence 4
Step 4: Preparation of Intermediate, 3,6-ditertiobutyl-9-(2-(tetrahydro-2H-pyran-2-yloxy)-5-(2,4,4-trimethyl-pentan-2-yl)phenyl)- 9H-carbazole.
[089] In a 50 mL three-necked round bottom flask equipped with a stir bar and condenser under N2 atmosphere 20 mL of dry toluene, 5.00 g (12.01 mmol) of 2-( 2-iodo-4-(2,4,4-trimethyl-pentan-2-yl)phenoxy)tetrahydro-2H-pyran, 3.56 g (12.01 mmol) of ditertiobutyl carbazole, 0.488 g (2.56 mmol) ) of CuI, 7.71 g (36.22 mmol) of K3PO4, and 0.338 g (3.84 mmol) of N,N'-dimethyl-ethylenediamine. The reaction mixture is refluxed for 48 hours, cooled, filtered through a bed of silica gel, the silica gel then rinsed with tetrahydrofuran (THF), and the organics are concentrated to give a crude residue. The crude residue is crystallized from acetonitrile to yield 4.57 g (67.01%) of product as a white solid. 1H NMR shows the product is as desired. Reaction Sequence 5
Step 5: Preparation of 1,2-bis(4-fluoro-2-iodo-6-methyl-phenoxy)ethane.
[090] In a round bottom flask under N2 atmosphere 10.33 g (40.99 mmol) of 2-iodo-4-fluoro-6-methyl-phenol, 11.34 g (82.05 mmol) are added of K 2 CO 3 , 80 mL of DMF, and 7.59 g (20.49 mmol) of ethylene glycol ditosylate (obtained from Aldrich). The reaction mixture is stirred and refluxed for 18 hours, cooled and concentrated. The residue is treated with 50/50 methylene chloride and water until complete dissolution of the solids and then the mixture is transferred to a separatory funnel where the compound is extracted into methylene chloride. The organic solution is washed with 2N NaOH, water, then brine, dried over anhydrous magnesium sulfate, filtered through a bed of silica gel and concentrated to give 9.93 g (91.4%) of a white solid. 1H NMR shows the product is as desired. Reaction Sequence 6
Step 6: Preparation of 2',2"'-(ethane-1,2-diyl-bis(oxy)bis(3-(3,6-ditertiobutyl-9H-carbazol-9-yl)-5'-fluor- 3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-ol).
[091] To a stirred solution of 5.0 g (8.82 mmol) of 3,6-ditertiobutyl-9-(2-(methoxy-methoxy)-5-(2,4,4-trimethyl-pentan-2 -yl)phenyl)-9H-carbazole in 75 ml of tetrahydrofuran at 0°C under nitrogen atmosphere, 8.1 ml (20.25 mmol) of n-butyl lithium (2.5M solution in hexanes) are added during a period of 10 minutes. The solution is stirred at 0°C for another three hours. To this solution, triisopropyl borate (4.8 mL, 20.8 mmol) is added and stirring is continued at 0°C for 1 hour. The mixture is slowly warmed to room temperature and stirred for a further 3 hours at room temperature. The reaction mixture is concentrated to dryness by rotary evaporation and 100 ml of ice cold water are added. The mixture is acidified using 2N hydrochloric acid and extracted with methylene chloride. The methylene chloride solution is washed with water and brine. The solvent is removed by rotary evaporation and the residue is dissolved in 90 ml of dimethoxyethane. This solution is then treated with a solution of 1.06 g (26.5 mmol) of NaOH in 25 mL of water, 25 mL of tetrahydrofuran and 2.2 g (4.15 mmol) of 1,2-bis(4). -fluor-2-iodo-6-methyl-phenoxy)ethane. The system is purged with nitrogen and 0.30 g (0.26 mmol) of Pd(PPh3)4 is added. Afterwards, the mixture is heated at 85°C for 36 hours in a nitrogen atmosphere. The precipitated product is collected by filtration. The solid thus obtained is dissolved in methylene chloride, washed with brine, and dried over anhydrous magnesium sulfate. After removing the solvent, the reaction products are dissolved in 150 ml of THF/MeOH (1:1) and stirred for 5 hours at 50°C after the addition of 100 mg of PTSA. The solvent is removed and the solid obtained is dissolved in 300 ml of 10% ethyl acetate in hexanes. This solution is passed through a small bed of silica gel. Removal of solvent followed by drying under reduced pressure gives 4.65 g (85%) of pure binder as a white solid. 1H NMR shows the product is as desired. Reaction Sequence 7
Step 7: Preparation of 1,2-bis(4-fluoro-2-iodo-phenoxy)ethane
[092] In a round bottom flask under N2 atmosphere 3.00 g (12.61 mmol) of 2-iodo-4-fluoro-phenol, 3.49 g (25.25 mmol) of K2CO3 are added. mL of DMF, and 2.34 g (6.32 mmol) of ethylene glycol ditosylate. The reaction mixture was refluxed for 18 hours, cooled and concentrated. The residue was treated with 50/50 methylene chloride and water until complete dissolution of the solids and then the mixture transferred to a separatory funnel where the compound was extracted into methylene chloride. The organic solution was washed with 2N NaOH, water and then brine, dried over anhydrous magnesium sulfate, filtered through a bed of silica gel and concentrated to give 3.07 g (97.0%) of pure bridged compound (1 ,2-bis(4-fluoro-2-iodo-phenoxy)ethane) as a white solid. 1H NMR shows the product is as desired. Reaction Sequence 8
Step 8: Preparation of 6',6"'-(ethane-1,2-diyl-bis(oxy))bis(3-(3,6-ditertiobutyl-9H-carbazol-9-yl)-3'-fluorine -5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-ol.
[093] In a stirred solution of 2.5 g (4.41 mmol) of 3,6-ditertiobutyl-9-(2-(methoxy-methoxy)-5-(2,4,4-trimethyl-pentan-2- yl)phenyl)-9H-carbazole in 40 ml of tetrahydrofuran at 0°C under nitrogen atmosphere, 4.05 ml (10.12 mmol) of n-butyl lithium (2.5M solution in hexanes) are added over a period of time. 10 minute period. The solution is stirred at 0°C for a further three hours. Triisopropyl borate (2.4 mL, 10.4 mmol) is added to the solution and stirring is continued at 0°C for 1 hour. The mixture is slowly warmed to room temperature and stirred for a further 3 hours at room temperature. The reaction mixture is concentrated to dryness by rotary evaporation and 100 ml of ice cold water are added. The mixture is acidified using 2N hydrochloric acid and extracted with methylene chloride. The methylene chloride solution is washed with water and brine. The solvent is removed by rotary evaporation and the residue is dissolved in 50 ml of dimethoxyethane. This solution is then treated with a solution of 0.53 g (13.25 mmol) of NaOH in 15 mL of water, 15 mL of tetrahydrofuran and 1.05 g (2.09 mmol) of 1,2-bis(4 -fluor-2-iodo-phenoxy)ethane. The system is purged with nitrogen and 0.15 g (0.13 mmol) of Pd(PPh3)4 is added. The mixture is then heated to 85°C for 36 hours under a nitrogen atmosphere. The reaction mixture is cooled and volatiles are removed by rotary evaporation. The residue is treated with 100 ml of water and extracted with methylene chloride. The methylene chloride solution is washed with water and brine, and dried over anhydrous magnesium sulfate. After removing the solvent, the reaction products are dissolved in 100 ml of THF/MeOH (1:1) and stirred for 5 hours at 50°C after the addition of 50 mg of PTSA. The solvent is removed and the product is purified by flash chromatography eluting with 5% ethyl acetate in hexanes to obtain 2.2 g (82.4%) of the binder as a white solid. 1H NMR shows the product is as desired.
Metal-Binder Complex 1 Step 9: Preparation of (6',6"-(ethane-1,2-diyl-bis(oxy))bis(3'-fluor-3-(3,6-ditertiobutyl-9H-) carbazol-9-yl)-5-(2,4,4-trimethyl-pentan-2-yl)biphenyl)dimethyl-hafnium (Metal-Binder Complex 1)
[094] In 1.571 g (1.29 mmol) of 6',6"-(ethane-1,2-diyl-bis(oxy))bis(3-(3,6-ditertiobutyl-9H-carbazol-9-) yl)-3'-fluoro-5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-ol) and 0.415 g (1.29 mmol) of HfCl4 suspended in 35 ml of toluene, 1.94 ml (5.82 mmol) of 3M solution of MeMgBr in diethyl ether are added. After stirring for 2 hours at room temperature, the solvent is removed under reduced pressure. To the residue 20 ml of toluene and 30 ml of hexane are added and the suspension is filtered. The solvent is removed under reduced pressure, leaving an ivory colored solid. To the residue 30 ml of hexane are added and the suspension is stirred for 20 minutes. The white solid is collected on a frit, washed with 4 ml of cold hexane and dried under reduced pressure to give 1.07 g of product. The filtrate is placed in a freezer (-30°C) for 3 days. The solvent is decanted and the resulting crystals are washed with cold hexane (2 x 3 ml) and dried under reduced pressure to obtain 345 mg of additional material. The combined product was 1.415 g (77%). 1H NMR shows the product is as desired. Binder-Metal Complex 2 Alternative Step 9: Preparation of (6',6"-(ethane-1,2-diyl-bis(oxy))bis(3'-fluor-3-(3,6-ditertiobutyl-9H) -carbazol-9-yl)-5-(2,4,4-trimethyl-pentan-2-yl)biphenyl)dimethyl-zirconium (Metal-Binder Complex *2. Additional data relating to this complex is not included in the Examples bellow).
[095] In a mixture of 6',6"'-(ethane-1,2-diyl-bis(oxy))bis(3-(3,6-ditertiobutyl-9H-carbazol-9-yl)-3'- fluorine -5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-ol) (1.989 g, 1.64 mmol) and ZrCl4 (0.382 g, 1, 64 mmol) in 50 ml of toluene, 2.57 ml (5.82 mmol) of 3M solution of MeMgBr in diethyl ether are added. After stirring for 1 hour, the solvent is removed under reduced pressure. To the residue are added 30 ml of toluene followed by 30 ml of hexane and the suspension is filtered to give a colorless solution. The solvent is removed under reduced pressure, giving a colorless solid. To this solid 20 ml of hexane are added, dissolving the residue. Solvent is removed under reduced pressure. To the residue 15 ml of hexane are added and the suspension is stirred for 1 hour. The solid is collected on the frit, washed with 5 ml of cold hexane and dried under reduced pressure to give 1.223 g of product. Yield of 56.0%. 1H NMR shows the product is as desired.
Metal-Binder Complex 3 Alternative Step 9: Preparation of (2',2"-(ethane-1,2-diyl-bis(oxy))bis(5'-fluor-3-(3,6-ditertiobutyl-9H) -carbazol-9-yl)-5-(2,4,4-trimethyl-pentan-2-yl)biphenyl-2-ol) dimethyl-hafnium (Metal-Binder Complex 3)
[096] In an ice-cold (-25°C) suspension of 2',2"-(ethane-1,2-diyl-bis(oxy))bis(3-(3,6-ditertiobutyl-9H-carbazol-9- yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-ol) (3.03 g, 2.44 mmol) and HfCl4 (0.782 g, 2.44 mmol) in 70 mL of toluene, 3.5 mL (10.5 mmol) of 3M solution of MeMgBr in diethyl ether are added. After stirring for 1 hour, the solvent is removed under reduced pressure. To the residue 20 ml of toluene and 30 ml of hexane are added. The suspension is filtered, giving a gray solution. The solvent is removed under reduced pressure, leaving a light gray solid. The residue is suspended in 8 ml of hexane and the suspension is stirred for 30 minutes. The solid is collected on the frit, washed with 3 ml of hexane and dried under reduced pressure to give 2.87 g of product as an ivory solid. The yield is 81.2%. 1H NMR shows the product is as desired.
Binder-Metal Complex 4 Alternative Step 9: Preparation of (2',2"-(ethane-1,2-diyl-bis(oxy))bis(5'-fluor-3-(3,6-ditertiobutyl-9H) -carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)biphenyl-2-ol)dimethyl-zirconium (Metal-Binder Complex 4)
[097] In a suspension of 2',2"'-(ethane-1,2-diyl-bis(oxy))bis(3-(3,6-ditertiobutyl-9H-carbazol-9-yl)-5'- fluoro-3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)-[1,1'-biphenyl]-2-ol) (0.75 g, 0.59 mmol) and ZrCl4 (0.137 g, 0.59 mmol) in 50 mL of toluene, 0.84 mL (2.53 mmol) of 3M solution of MeMgBr in diethyl ether is added. After stirring for 1 hour, the solvent is removed under reduced pressure. To the residue 20 ml of toluene are added followed by 30 ml of hexane. The suspension is filtered, giving a colorless solution. The solvent is removed under reduced pressure, leaving a white solid. The residue is suspended in 15 ml of hexane and the suspension is stirred for 30 minutes. The solid is collected on the frit, washed with 3 ml of hexane and dried under reduced pressure to give 0.545 g of product as a white solid. The yield is 66.5%. 1H NMR shows the product is as desired. polymerization procedure
[098] Polymerizations are performed in a 2 L PARR™ batch reactor. The reactor is heated by an electrical heating mantle, and is cooled by an internal coil cooling coil containing cold water. The reactor and heating/cooling system are controlled and monitored by a CAMILE™ TG process computer. The bottom of the reactor is equipped with a discharge valve, which empties the reactor contents into a stainless steel (SS) discharge container, which is pre-filled with a catalyst poison solution (typically 5 mL of an IRGAFOS™ mixture /IRGANOX™/toluene). The discharge vessel discharges to a purge tank, and both the vessel and tank are purged with N2. All chemicals used for polymerization or catalyst preparation run through purification columns to remove any impurities that might affect the polymerization. The 1-octene passes through 2 columns, the first containing alumina Al2O4, the second containing reagent Q5 to remove oxygen. Ethylene also passes through 2 columns, the first containing Al2O4 alumina and 4 Angstrom (Â) pore size molecular sieves, the second containing Q5 reagent. The N2, used for transfers, passes through a single column containing Al2O4 alumina, 4 Â pore size molecular sieves and Q5 reagent.
[099] First, load the reactor from the loading tank containing 1-octene, depending on the desired reactor load. The loading tank is filled to prescribed load values by using a scale on which the unloading tank is mounted. After addition of liquid feed, the reactor is heated to the prescribed polymerization temperature. If ethylene is used, it will be added to the reactor when at reaction temperature to maintain the prescribed reaction pressure. Ethylene addition amounts are monitored by a micro motion flowmeter.
[100] The catalyst and activators are mixed with the appropriate amount of purified toluene for a desired molarity of solution. Catalyst and activators are handled in an inert glove box, wrapped in a syringe and transferred under pressure to the catalyst loading tank. This is followed by 3 toluene rinses of 5 ml each.
[101] Immediately after addition of catalyst, the timing starts. If ethylene is used then it will be added by CAMILE™ to maintain the set pressure in the reactor. These polymerizations take place for 10 minutes, then the stirrer is stopped and the bottom discharge valve is opened to empty the reactor contents into the discharge vessel. The contents of the discharge container are poured into trays placed in a laboratory hood where the solvent is evaporated overnight. The trays containing the remaining polymer are then transferred to a vacuum oven, where they are vacuum heated to 140°C to remove any remaining solvent. After cooling trays to room temperature, polymers are weighed for yield/efficiencies, and subjected to polymer testing.
[102] Melting and crystallization temperatures are measured by differential scanning calorimetry (DSC 2910, TA Instruments, Inc.). First, the samples are heated from room temperature to 210°C at 10°C/min. After being held at this temperature for 4 minutes, the samples are cooled to -40°C at 10°C/min and then heated to 215°C at 10°C/min after being kept at -40°C for 4 minutes .
[103] For ethylene/1-octene copolymers: Molecular weight distribution information (Mw/Mn, PDI) is determined by analysis on an Agilent Series 1100 Gel Permeation Chromatograph (GPC). Polymer samples are dissolved for at least 5 minutes at room temperature (~25°C) at a concentration of 25 mg/ml in tetrahydrofuran (THF), with brief swirling after solvent addition, but without any further agitation. A 1 μL aliquot of the sample is injected through the Agilent Automated Sample Collector. The GPC used two (2) 10 µm PLgel MIXED-D columns from Polymer Labs at a flow rate of 1.0 ml/min at 35°C. Sample detection is performed using a differential refractive index detector. A conventional calibration of narrow poly(ethylene glycol) (PEG) standards (Mp range: 106-21.030) is used, with data reported in apparent PEG units.
[104] Gas chromatography-mass spectrometry (GC/MS) is performed in the modes of electronic impact (EI) and positive ion ammonia chemical ionization (NH3-CI). The instrumentation used is an Agilent 6890N GC coupled to a MICROMASS SN CA095 GCT, GC/MS system leak time in EI and PCI-NH3 modes. The following analysis conditions were used: Column is Rxi-5SilMS 30 mx 0.250 mm (0.24 µm film), column temperature is 100°C (2 minutes) at 330°C at 15°C/ min, injector at 320°C, GC reparticipant at 300°C, source at 180°C/120°C (EI/CI), flow is 1.2 mL/min (He) (constant flow, division - 50:1), detector is 2400V MCP, mode is +TOFMS, holding mass is 201.9609 C6F5Cl (+EI/+CI). Examples 1-3
[105] Using the polymerization procedure and metal-binder complex synthesis procedures for Metal-Binder Complexes 1,3, and 4, ethylene and 1-octene are copolymerized to form a polydielectric fluid composition. (co-ethylene-α-olefin). Table 1 below shows polymerization conditions, identification of activation cocatalysts, and results. Table 1. Copolymerization of ethylene/1-octene
Polymerization conditions-temperature: 140°C; 650 g of 1-octene; precatalyst:activator = 1:1.2; activator: [HNMe(C18H37)2] [B(C6F5)4]; 15 moles of MMAO; reaction time: 10 minutes. Comparative Example A
[106] Tests are carried out to determine neutralization index, pour point, and burn point in the dielectric fluid compositions of Examples 1-3, and also mineral oil, which is designated as Comparative Example A. Table 2 below shows the results. Table 2. Characterization of dielectric fluids from Table 1 and Comparative Example A
Example 4
[107] Ethylene and 1-octene are again copolymerized using the polymerization procedure and the Binder-Metal Complex 3 synthesis procedure. Table 3 below shows the conditions and identification of activation cocatalysts. Figure 1 shows the GC chromatographic analysis, illustrating an incorporation of the extensive isomer formation that characterizes the inventive dielectric fluid compositions. Table 3. Ethylene/1-octene copolymerization
Polymerization conditions-temperature: 100°C; 750 g of 1-octene; pre-catalyst: activator: 1 mmol MMAO; reaction time: 30 minutes. Figure 1. Sample GC-MS chromatogram from Examples 4.
Examples 5-6
[108] A poly-α-olefin dielectric fluid composition is prepared using the polymerization procedure and the Metal-Binder Complexes 3 and 4 synthesis procedures. Table 4 shows the results, and Figure 2 shows GC-MS chromatographic analysis of Example 5. Table 4. Polymerization of 1-octene
Polymerization conditions-temperature: 140°C; 650 g of 1-octene; precatalyst:activator:1:1,2; activator: [HNMe(C18H37)2] [B(C6F5)4]; 20 moles of MMAO; reaction time: 10 minutes. Figure 2. Sample GC-MS chromatogram from Example 5.

权利要求:
Claims (9)
[0001]
1. Dielectric fluid composition, characterized in that it comprises a poly-α-olefin or a poly(co-ethylene/α-olefin) having a weight average molecular weight greater than 200 and less than 5,000 Dalton (Da) prepared from of a process including a step of contacting together (1) a monomer selected from (a) an α-olefin; or (b) a combination of an α-olefin and ethylene; and (2) a catalytic amount of a catalyst, wherein the catalyst includes a mixture or reaction product of ingredients (2a) and (2b) that is prepared prior to the contacting step, wherein ingredient (2a) is at least a metal-ligand complex of the formula (I):
[0002]
2. Dielectric fluid composition according to claim 1, characterized in that the weight average molecular weight of a poly-α-olefin or poly(co-ethylene/α-olefin) is less than 1500 Dalton.
[0003]
3. Dielectric fluid composition according to claim 1, characterized in that each Z of the metal ligand complex of formula (I) is O.
[0004]
4. Dielectric fluid composition according to claim 1, characterized in that R1a and R1b of the metal ligand complex of formula (I) are methyl, ethyl or isopropyl.
[0005]
5. Dielectric fluid composition according to claim 1, characterized in that R1a and R1b of the metal ligand complex of formula (I) are fluorine atoms, chlorine atoms, bromine atoms or iodine atoms.
[0006]
6. Dielectric fluid composition according to claim 1, characterized in that L of the metal ligand complex of formula (I) is -CH2CH2-, -CH(CH3)CH(CH3)-, 1,2-cyclopentanediyl or 1,2-cyclohexanediyl.
[0007]
7. Dielectric fluid composition according to claim 1, characterized in that R5d of the metal ligand complex of formula (I) is independently a 2,7-disubstituted 9H-carbazol-9-yl or 3,6-disubstituted 9H - carbazol-9-yl with each substituent being RS.
[0008]
8. Dielectric fluid composition according to claim 1, characterized in that R5d of the metal ligand complex of formula (I) is independently a C6-C40 aryl which is a 2,4-disubstituted phenyl, each substituent being LOL; a 2,5-disubstituted phenyl, each substituent being RS; a 2,6-disubstituted phenyl, each substituent being RS; a 3,5-disubstituted phenyl, each substituent being RS; a 2,4,6-trisubstituted phenyl, each substituent being RS; naphthyl or substituted naphthyl each substituent being RS; 1,2,3,4-tetrahydronaphthyl; anthracenyl; 1,2,3,4-tetrahydro-anthracenyl; 1,2,3,4,5,6,7,8-octahydro-anthracenyl; phenantrenyl; or 1,2,3,4,5,6,7,8-octahydrophen-antrenyl.
[0009]
9. Dielectric fluid composition, according to claim 1, characterized in that the contact of the monomer and the catalyst is under conditions that include a temperature ranging from 40°C to 300°C.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-01| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161581402P| true| 2011-12-29|2011-12-29|

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US61/581,402|2011-12-29|

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PCT/US2012/066700|WO2013101376A1|2011-12-29|2012-11-28|Hyperbranched olefin oil-based dielectric fluid|

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