巴西专利BR112015030912B1 PROCESS FOR PREPARING AN OLEFIN HOMOPOLYMER OR COPOLYMER

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专利摘要:
process for preparing an olefin homopolymer or copolymer a process for preparing an olefin homopolymer or copolymer by contacting ethylene, an alpha olefin, or a combination, and a catalytic amount of a metal-binder complex catalyst of a particular formula which requires at least one halogen atom to be ortho to a bridging moiety. the strategic location of the halogen atom(s) ensures a product having a molecular weight that is predictable and significantly reduced compared to copolymers produced using identical metal-binder complex catalysts that do not have halogen atoms at specified sites .
公开号:BR112015030912B1
申请号:R112015030912-7
申请日:2014-06-26
公开日:2021-08-03
发明作者:Jerzy Klosin；Ruth Figueroa；Robert Dj Froese
申请人:Dow Global Technologies Llc；
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[001] The invention relates to the control of molecular weight of polyolefins. More particularly, it relates to the preparation of ethylene or alpha-olefin homopolymers or ethylene/alpha-olefin copolymers using a particular family of bis-phenylphenoxy catalysts that predictably change the molecular weight of polymers.
[002] Polyolefins that are polyethylene polymers, poly(ethylene alpha-olefin copolymers), and blends of these polyolefins are examples of types of polyolefins widely used in industry. They are desirable for preparing, for example, containers, tubes, films and sheets for packaging, and synthetic lubricants and other utility fluids. The polymerization of ethylene and the polymerization of ethylene and alpha-olefins by transition metal catalysts is generally known to produce relatively high molecular weight polymers and copolymers. These polymers and copolymers often have molecular weight ranges greater than 100,000 Daltons (Da), and in some embodiments greater than 500,000 Da. At these molecular weight levels, rheological behavior may be undesirable, however, because the products cannot flow as desired and may, furthermore, tend to crystallize from solution.
[003] Those skilled in the art have sought ways and means to control and/or predict the molecular weight. It is recognized that the selection of monomers, catalysts, a and starting processing conditions can affect the weight average molecular weight (Mw) of the polymers or copolymers being prepared. Catalyst choices can also be customized for other distinct or related reasons, such as overall reactivity profile.
[004] For example, United States Patent Numbers (US) 6,869,904 B2 and US 7,060,848 B2 mention catalysts including certain binders, metals and arrangements with bridged bis-aromatic or substituted bridged bis-biaromatic ligands.
[005] PCT International Patent Application Publication Number WO 2007/136494 A2 mentions a catalyst composition comprising a zirconium complex of a polyvalent aryloxy ether and the use thereof in a continuous solution polymerization of ethylene, one or more C3 olefins -C30 and a conjugated or unconjugated diene to prepare interpolymers having improved processing properties. The catalyst system contains a catalyst covalently linked to an activator.
[006] A particular group of catalysts is described in United States Patent Publication US20110282018 as effective to polymerize alpha-olefins and ethylene/alpha-olefins. These metal ligand complex catalysts are described as bis-phenylphenoxy compounds which may or may not contain halogens at certain locations of the formula which are, in some potential embodiments, ortho to a bridging moiety.
[007] There is still a need in the art for convenient, efficient and controllable processes to adjust the rheological behavior of an olefinic product for a wider variety of specific end-use applications.
[008] In a first embodiment, the present invention is a process for preparing an olefin homopolymer or copolymer, comprising contacting ethylene, an alpha-olefin, or a combination thereof, and a catalytic amount of a metal-complex catalyst. formula binder
where 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 independent X is 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 en are selected such that the metal-ligand complex is neutral; each Z moiety is independently O, S, N(C1-C40) hydrocarbyl, or P(C1-C40) hydrocarbyl; L is (C1-C40)hydrocarbylene or (C1-C40) heterohydrocarbylene, as long as it has a part comprising a linker structure of 2 to 8 carbon atoms connecting the Z moieties, each atom of that linker of 2 to 8 atoms being independently a carbon atom or a heteroatom, where each independent heteroatom is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN ); R1a, R1b, or both are a halogen atom; and R2a, R3a, R4a, R2b, R3b, R4b, R6c, R7c, R8c, R6d, R7d, and R8d are independently a hydrogen atom; (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; SC CPN CCi(R)3, Ge(R)3, P(R)2, N(R)2, OR, SR, NO2, CN, F3C, F3CO, RCS(O)-, RCS(O)2- , (RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)- or halogen atom; each of R5c and R5d is independently a (C6-C40)aryl or (C1-C40)heteroaryl and each of the aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene and heterohydrocarbylene groups is independently substituted or unsubstituted with one or more RS substituents ; and each independent RS is a halogen atom, polyfluoro substitution, perfluoro 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 are taken to form an unsubstituted (C1-C18)alkylene, wherein each independent R is an unsubstituted (C1-C18)alkyl; under conditions that an ethylene homopolymer, an alpha-olefin homopolymer or an ethylene/alpha-olefin copolymer is formed as having a weight average molecular weight that is reduced by at least 20 percent as compared to an identical ethylene homopolymer, alpha-olefin homopolymer or ethylene/alpha-olefin copolymer prepared under identical conditions with a catalyst that is identical, but in which neither R1a nor R1b is a halogen atom.
[009] The inventive process surprisingly offers the advantage of greatly reducing the molecular weight of a given ethylene or alpha-olefin homopolymer or ethylene/alpha-olefin copolymer without otherwise significantly modifying the nature of the homopolymerization or copolymerization. This molecular weight reduction, in turn, can offer a significant increase in flow behavior that correspondingly can increase the number and types of applications for using these products.
[010] The advantage is obtained by using as catalysts a particular subset of the bis-phenylphenoxy compounds described in US20110282018. These are termed metal-binder complex catalysts which combine a transition metal center and any of a wide variety of bis-phenylphenoxy containing binders in accordance with formula (I), provided the following limitations are satisfied. First, the bridge, L, between the Z fractions, is 2 atoms to 8 atoms long. Second, the Z fractions can be independently selected from oxygen, sulfur, phosphorus(C1-40)hydrocarbyl, and nitrogen(C1-40)hydrocarbyl. Third, the ligand has a halogen atom located in at least one of the positions on the benzene rings in the R1a and/or R1b position of formula (I), that is, in a position or positions, which are ortho to the Z fractions. bridged. The term "halogen atom" means a fluorine atom radical (F), chlorine atom radical (Cl), bromine atom radical (Br), or iodine atom radical (I). Preferably, each independent halogen atom is a Br, F or Cl radical, and more preferably an F or Cl radical. Fourth, the metal M is preferably selected from zirconium (Zr), hafnium (Hf), and titanium (Ti), and most preferably is Zr or Hf.
[011] Catalyst family members defined as being useful for reducing the weight average molecular weight (Mw) of the homopolymer or copolymer are generally convenient to prepare and can operate efficiently and over a wide thermal operating range, in some non-limiting modalities withstanding temperatures above 200 °C. These catalysts can effectively be of any Mw, but in certain non-limiting embodiments they preferably range from 200 Daltons (Da) to 5,000 Da. The preparation can include, in non-limiting embodiments, construction of a suitable binder structure followed by its reaction with a salt of the desired transition metal, which effects the desired metal-binder complexation. Additional and highly detailed preparation information can be found in the examples included here below, as well as, for example, the previously referenced US20110282018; Serial Number US PCT/US2012/0667700, filed November 28, 2012, claiming priority to US Interim Application 61/581,418, filed December 29, 2011 (Attorney Registry No. 71731); and U.S. Serial Number 13/105,018, filed May 11, 2011, Publication Number 20110282018, claiming priority to U.S. Provisional Application 61/487,627, filed March 25, 2011 (Attorney Registry No. 69,428). Those skilled in the art will recognize that similar and analogous processes can be used to prepare other bis-phenylphenoxy compounds useful within the given general definition.
[012] Such suitable catalysts may generally include, in more specific but not limiting embodiments, metal-binder complexes of formula (I) formula (I)
where 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 independent X is 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 en are selected so that the metal-binder complex is generally neutral; each Z is independently O, S, N(C1-C40)hydrocarbyl, or P(C1-C40)hydrocarbyl; L is (C1-C40)hydrocarbylene or (C1-C40)heterohydrocarbylene, wherein the (C1-C40)hydrocarbylene has a part comprising a linker structure of 2 to 8 carbon atoms connecting the Z and the (C1- C40)heterohydrocarbylene has a part comprising a linker structure of 2 to 8 carbon atoms connecting the Z moieties, wherein each atom of this 2 to 8 atom (C1-C40)heterohydrocarbylene linker independently is a carbon atom or a heteroatom , wherein each independent heteroatom is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN); wherein each RC independently is unsubstituted (C1-C18)hydrocarbyl or the two RC are taken together to form (C2-C19)alkylene, each RP is unsubstituted (C1-C18)hydrocarbyl; and each RN is unsubstituted (C1-C18)hydrocarbyl, a hydrogen atom, or absent; R1a, R1b, or both are a 2a 3a 4a 2b 3b 4b 6c 7c 8halogen atom; and R , R , R , R , R , R , R , R , R , R6d, R7d, and R8d are independently a hydrogen atom; (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl; Si(RC)3,Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, F3C, F3CO, RCS(O)-, RCS(O)2-, ( RC)2C=N-, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)- or halogen atom; each of R5c and R5d is independently a (C6-C40)aryl or (C1-C40)heteroaryl and each of the aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene and heterohydrocarbylene groups is independently substituted or unsubstituted with one or more RS substituents ; and each independent RS is a halogen atom, polyfluoro substitution, perfluoro 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 are taken to form an unsubstituted (C1-C18)alkylene, where each independent R is an unsubstituted (C1-C18)alkyl.
[013] A wide variety of additional substitutions may be present on all other carbons of the at least four phenyl rings included within the catalyst of formula (I) or such may simply be hydrogen. Some examples of preferred R5c and R5d substituents include 3,5-di(tertiary-butyl)phenyl; 3,5-diphenylphenyl; 1-naphthyl, 2-methyl-1-naphthyl; 2-naphthyl; 1,2,3,4-tetrahydronaphthyl; 1,2,3,4-tetrahydro-naphth-5-yl; 1,2,3,4-tetrahydronaphth-6-yl; 1,2,3,4-tetrahydroanthracenyl; 1,2,3,4-tetrahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydroanthracenyl; 1,2,3,4,5,6,7,8-octahydroanthracen-9-yl; phenantren-9-yl; 1,2,3,4,5,6,7,8-octahydrophenanthren-9-yl; 2,3-dihydro-1H-inden-6-yl; naphthalene-2-yl; 1,2,3,4-tetrahydronaphthalen-6-yl; 1,2,3,4-tetrahydronaphthalen-5-yl; anthracen-9-yl; 1,2,3,4-tetrahydroanthracen-9-yl; 1,2,3,4,5,6,7,8-octahydro-anthracen-9-yl; 2,6-dimethylphenyl; 2,6-diethylphenyl; 2,6-bis(1-methylethyl)phenyl; 2,6-diphenyl-phenyl; 3,5-dimethylphenyl; 3,5-bis(trifluoromethyl)phenyl; 3,5-bis(1-methylethyl)phenyl; 3,5-bis(1,1-dimethylethyl)phenyl; 3,5-diphenyl-phenyl); 2,4,6-trimethylphenyl; 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; 1,1-dimethyl-1,2,3,4-tetrahydronaph-talen-5-yl. 1,2,3,4-tetrahydroquinolinyl; isoquinolinyl; 1,2,3,4-tetrahydroisoquinolinyl; carbazolyl; 1,2,3,4-tetrahydrocarbazolyl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl; 3,6-di(tertiary-butyl)-carbazolyl; 3,6-di(tertiary-octyl)-carbazolyl; 3,6-diphenylcarbazolyl; 3,6-bis(2,4,6-trimethylphenyl)-carbazolyl; 3,6-di(tertiary-butyl)-carbazol-9-yl; 3,6-di(tertiary-octyl)-carbazol-9-yl; 3,6-diphenylcarbazol-9-yl; 3,6-bis(2,4,6-trimethylphenyl)-carbazol-9-yl; quin-olin-4-yl; quinolin-5-yl; quinolin-8-yl; 1,2,3,4-tetrahydroquinolin-1-yl; isoquinolin-1-yl; isoquinolin-4-yl; iso-quinolin-5-yl; isoquinolin-8-yl; 1,2,3,4-tetrahydroisoquinolin-2-yl; 1H-indol-1-yl; 1H-indolin-1-yl; 9H-carbazol-9-yl; 1,2,3,4-tetrahydrocarbazolyl-9-yl; 1,2,3,4,5,6,7,8-octahydrocarbazolyl-9-yl; 4,6-bis(1,1-dimethylethyl)pyridin-2-yl; 4,6-diphenylpyridin-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-dimethylphenyl)]-9H-carbazol-9-yl; 3,6-bis(1,1-dimethyl-ethyl)-9H-carbazol-9-yl.
[014] In certain even more specific and preferred embodiments of the inventive process, the metal-binder complex may be selected from compounds represented by any of the following formulae. Additional fractions denoted by abbreviations include Me (methyl); t-Bu (tert-butyl); OMe (methoxy); TMS (trimethylsilyl); Et (ethyl); and iPr(isopropyl).

[015] Once the catalyst is obtained, through purchase or preparation, it is ready for use in the inventive process. Where alpha-olefin homopolymerization or ethylene/alpha-olefin copolymerization is desirable, suitable alpha-olefins can be any selected according to the desired properties of the final copolymer. In non-limiting example only, alpha-olefin can be selected from linear alpha-olefins having 3 to 12 carbons, like propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- nonene, 1-decene, undecene, 1-dodecene, and combinations thereof. Smaller linear alpha-olefins having 3 to 8 carbons are preferred because they allow for a higher branching density of the final product oligomers. Branched alpha olefins may also be employed in the feed process, and may include in non-limiting embodiments single or multiple branched alpha olefin monomers having from 5 to 16 carbons, wherein the first substituted carbon is in the "3" position or position higher than vinyl, and combinations thereof. It is generally preferred that the first substitution be at position “4” or greater.
[016] In order to prepare the homopolymers or copolymers of the invention, ethylene and/or the selected alpha-olefin monomers is/are fed into a suitable reactor, by batch, continuous or semi-continuous production, in which these monomers will enter into contact with the catalyst. In the case of preparing a copolymer, it is noted that the ethylene/alpha-olefin reactivity ratio is distinct for any given catalyst and provides a methodology for determining the amount of alpha-olefin that will be needed to achieve a target copolymer composition. Reactivity ratios can be determined using well known theoretical techniques or empirically derived from actual polymerization data. Suitable theoretical techniques are disclosed, for example, in BG Kyle, Chemical and Process Thermodynamics, 3rd ed., Prentice-Hall (Englewood Cliffs, NJ 1999) and in G. Soave, “Redlich-Kwong-Soave (RKS) Equation of State ,” Chemical Engineering Science, 1972, vol. 27, pp 1197-1203. Commercially available software programs can be used to assist in deriving reactivity ratios from experimentally derived data. An example of such software is Aspen Plus from Aspen Technology, Inc., Ten Canal Park, Cambridge, Massachusetts 02141-2201, USA. It is often preferred in many copolymer compositions that the amount of alpha-olefin included is less than the amount of ethylene, simply for reasons of the relative cost of the monomers. Thus, it is often, though not always, preferred that the target amount of alpha-olefin in a copolymer ranges from 1 to 30 mole percent (mol%); more preferably from 1 to 25% by mol; and even more preferably from 0 to 20% by mol.
[017] The metal-binder complex of formula (I) is made catalytically active by contacting it for, or combining it with, the activation cocatalyst or using an activation technique such as those that are known in the art for use with reactions of polymerization of metal-based olefins. Suitable activation cocatalysts for use herein include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds, including, but not limited to, the use of these compounds under oxidizing conditions. A suitable activation technique might be mass electrolysis. Combinations of one or more of the above activation cocatalysts and/or techniques are also contemplated. The term "alkyl aluminum" means a monoalkyl aluminum dihydride or monoalkyl aluminum dihalide, dialkyl aluminum hydride or dialkyl aluminum halide, or a trialkyl aluminum. Alumoxanes and their preparations are described in, for further understanding, U.S. 6,103,657. Examples of preferred polymeric or oligomeric alumoxanes are methylalumoxane, methylalumoxane modified with tri-isobutylaluminum, and isobutylalumoxane. These can be used so that the ratio of the total number of moles of the one or more metal-binder complexes of formula (I) to the total number of moles of activation cocatalysts is preferably from 1:10,000 to 100:1.
[018] A variety of homopolymerization or copolymerization conditions and combinations thereof can be employed, according to the raw materials, nature of the reaction (batch, semi-continuous, or continuous), installation of apparatus, desired products, and so on. However, in general, suitable polymers or copolymers of the invention can be produced using one or more of the specified catalyst selections at a temperature ranging from 20 degrees Celsius (oC) to 220 oC, and preferably 100 oC to 200 oC, for one time preferably ranging from 10 minutes (min) to 300 min. Other parameters, such as pressure, can be controlled within ranges known to those skilled in the art and are not generally considered to be critical for practicing the present invention, but can be varied according to the wishes and needs of the practitioner. It is generally preferred to carry out the process as a continuous process, using at least one continuous stirred tank reactor (CSTR) or other suitable flasks.
[019] The particular advantage of the invention will be apparent when comparative homopolymers or copolymers are prepared under identical conditions and using identical raw materials, where the inventive process uses one of the defined catalysts that has at least one halogen located in a position that is ortho to the Z moiety as defined, that is, as the R1a and/or R1b substituent, and the comparative process uses a catalyst which is identical, but which does not have a halogen at any of these locations. Surprisingly, it has been found that homopolymers or copolymers produced by the inventive process can have a Mw that is reduced by at least 20%, preferably at least 30%, more preferably at least 40%, and most preferably at least 80%, when compared to homopolymers and copolymers produced using the identical catalyst where neither R1a nor R1b is a halogen atom.
[020] Even more surprising, it was further found that homopolymers or copolymers produced by the inventive process using a catalyst in which both the R1a and R1b substituents are halogen atoms can have a Mw that is reduced by at least 20%, preferably at least 30 %, more preferably at least 40%, and more preferably at least 80%, as compared to homopolymers or copolymers produced by an identical inventive process employing a catalyst having only one halogen at the R1a or R1b position.
[021] Thus, in certain embodiments, the use of a catalyst including a halogen strategically located at the ortho position can surprisingly produce a homopolymer or copolymer having molecular weight that is as low as one-fifth of that produced using an identical catalyst without halogens at any position ortho, while the use of a catalyst including two halogens at these ortho positions can surprisingly produce a homopolymer or copolymer having molecular weight that is as low as one-tenth of that produced using the identical catalyst without halogens at any ortho position. In this context, the inventive process allows a way to predictably reduce the weight average molecular weight (Mw) of the homopolymer or copolymer produced, which means that the rheological behavior is modified and the processing capacity and applications of the homopolymer or copolymer can also be modified. in a way that might be desirable. At the same time, other properties of the resulting homopolymer or copolymer are not comparably affected, although where an ethylene/alpha-olefin copolymer is being prepared, the amount of alpha-olefin incorporation may in some cases be somewhat reduced by the presence of an atom. of halogen at R1a, R1b, or both positions.EXAMPLES 1-6 and Comparative Examples AD
[022] A series of catalysts having the chemical names and formula structures shown below are used to carry out copolymerizations of ethylene/1-octene. Catalyst 1 is (2',2''-(propane-1,3-diylbis(oxy) ))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2- ol)dimethylhafnium It is used for Comparative Example (CEx.) A.Catalyst 2 is 2',2''-(propane-1,3-diylbis(oxy))-1-(3,6-di- tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-3-(3,6-di-tert -butyl-9H-carbazol-9-yl)-3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium. It is used for Example (Ex.) 1.Catalyst 3 is (2',2''-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H- carbazol-9-yl)-3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium It is used for Ex. (2',2''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5 -(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethylhafnium. It is used for CEx. B.Catalyst 5 is 2',2''-(propane-1,3-diylbis( oxy))-1-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2- ol)-3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl- 2-ol)dimethylhafnium. It is used for Ex. 3.Catalyst 6 is 2',2''-(propane-1,3-diylbis(oxy))-1-(2,7-di-tert-butyl-9H-carbazol-9-yl )-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-3-(2,7-di-tert-butyl-9H-carbazol-9-yl) -3'-methyl-5'-fluoro-5-(2,4,4-trimethyl-pentan-2-yl)biphenyl-2-ol)dimethyl-hafnium. It is used for CEx. C.Catalyst 7 is 2',2''-(propane-1,3-diylbis(oxy))-1-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3'- 5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3 '-methyl-5'-fluoro-5-(2,4,4-trimethyl-pentan-2-yl)biphenyl-2-ol)dimethylhafnium. It is used for Ex. 4. Catalyst 8 is (2',2''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9) -yl)-3'-methyl-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium. It is used for CEx. D.Catalyst 9 is ( 2',2''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3'-5'-dichloro -5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium It is used for Ex. 5.Catalyst 10 is (2',2''-(propane-1,3 -diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3'-5'-difluoro-5-(2,4,4-trimethylpentan-2 -yl)biphenyl-2-ol)dimethyl-zirconium It is used for Ex.

[023] Each of the prepared catalysts is used to prepare an ethylene/octene copolymer by the following procedure. A 2 liter (L) Parr reactor is used for polymerizations. All feeds are passed through alumina columns and Q-5™ catalyst (available from Engelhard Chemicals Inc.) prior to introduction into the reactor. Catalyst and cocatalyst (activator) solutions are handled in the glove compartment. A stirred 2L reactor is loaded with about 605 grams (g) of mixed alkanes solvent and 300 g of 1-octene comonomer. The reactor contents are heated to a polymerization temperature of 140°C and saturated with ethylene at 288 pounds per square inch gauge (psig, ~1.99 megapascal, MPa). Catalysts and cocatalysts, such as solutions diluted in toluene, are mixed and transferred to a catalyst addition tank and injected into the reactor. Polymerization conditions are maintained for 10 minutes (min) with ethylene added on demand. Heat is continuously removed from the reaction vessel through an internal cooling coil. The resulting solution is removed from the reactor, quenched with isopropyl alcohol, and stabilized by the addition of 10 milliliters (mL) of a toluene solution containing approximately 67 milligrams (mg) of a hindered phenol antioxidant (Irganox™ 1010 from Ciba Geigy Corporation) and 133 mg of a phosphorus stabilizer (Irgafos™ 168 from Ciba Geigy Corporation). Between polymerization runs, a wash cycle is conducted in which 850 g of mixed alkanes are added to the reactor and the reactor is heated to 150 °C. The reactor is then emptied of the heated solvent just before starting a new polymerization run. Polymers are recovered by drying for about 12 hours (h) in a temperature-raising vacuum oven with an end point set at 140 °C.
[024] Polymer characterization is then performed. Polymer melting and crystallization temperatures are measured by differential scanning calorimetry (DSC 2910, TA Instruments, Inc.). The samples are first heated from room temperature to 180 °C at a ramp rate of 10 °C/min. After being held at this temperature for 2 to 4 minutes, the samples are cooled to -40 °C to 10 °C/min, held for 2 to 4 min, and then heated to 160 °C. Molecular weight distribution information (Mw, Mn) is determined by analysis on a Robot Assisted High Temperature Dilution Gel Permeation Chromatograph (RAD-GPC). Polymer samples are dissolved for 90 min at 160 °C at a concentration of 30 mg/mL in 1,2,4-trichlorobenzene (TCB) stabilized by 300 parts per million (ppm) of butylated hydroxytoluene (BHT) in vials capped with agitation. These are then diluted to 1 mg/mL, just before a 400 microliter (μL) aliquot of the sample is injected. The GPC uses two (2) POLYMER LABSTM PLgelTM 10 μm MIXED-B columns (300 mm (mm) x 10 mm) with a flow rate of 2.0 mL/min at 150 °C. Sample detection is performed using a POLYMER CHARTM IR4 detector in concentration mode. A conventional calibration of narrow Polystyrene (PS) standards is used, with apparent units adjusted for homopolyethylene (PE) using known Mark-Houwink coefficients for PS and PE in 1,2,3-trichlorobenzene (TCB) at this temperature. Absolute Mw information is calculated using a polydispersity index (PDI) static low angle light scattering detector. To determine octene incorporation, 140 μL of each polymer solution is deposited on a silicon plate, heated to 140 °C until the TCB evaporates and analyzed using a Nicolet Nexus 670 Fourier Transform Infrared Spectroscopy (FTIR) instrument with software version 7.1 equipped with an AUTOPROTM autosampler. The results are seen in Table 1.Table 1: Polymerization Results
a Polymerization conditions: 2L batch reactor, 605 mL of IsoparTM-E; temp = 140°C; 300 g of 1-octene; ethylene pressure = 288 psi; catalyst:activator = 1:1.2; activator: [HNMe(C18H37)2][B(C6F5)4]; 1:10 MMAO; reaction time 10 min.
[025] It is noted that reducing the molecular weight through the use of single (Catalyst 2, 5 and 7) or double (Catalyst 3, 9 and 10) halogenated catalysts [in the ortho position] also proportionally reduces octene incorporation in the copolymer when compared to copolymers prepared using non-halogenated catalysts [in the ortho position] (Catalyst 1, 4, 6 and 8). In addition, halogenation with fluorine atoms appears to be more effective in these examples than halogenation with chlorine atoms.EXAMPLE 7
[026] This Ex. 7 illustrates a sample catalyst preparation. Those skilled in the art will understand that similar and analogous methods can be carried out to prepare other catalysts suitable for use in the present invention. Confirmation of each product is performed by 1H NMR and 19F NMR.(a) Step 1: Preparation of 2-(3-bromopropoxy)-1,5-difluoro-3-iodobenzene

[027] A mixture of 2-iodo-4,6-difluorophenol (10.00 g, 38.28 millimoles (mmol)) [repared according to WO/2012/027448], 1,3-dibromopropane (155 g, 765 mmol), potassium carbonate (10.582 g, 76.566 mmol) and acetone (250 mL) is heated to reflux for 1h. The mixture cools to room temperature and is concentrated. The residue is partitioned into a 50/50 methylene chloride/water mixture and extracted with methylene chloride. The combined organic phases are washed with 2N NaOH (300ml), brine (300ml), water (300ml), dried over MgSO4, filtered through a silica gel pad and concentrated. The resulting oil is purified via column chromatography using a hexanes:ethyl acetate gradient to give 12.5 g (86.8%) of the product as a slightly yellow oil. As used herein, "hexanes" refers to a commercially obtained mixture of hexane isomers.(b) Step 2: Preparation of 1,5-difluoro-2-(3-(4-fluoro-2-iodophenoxy)propoxy)- 3-iodobenzene

[028] A mixture of 2-(3-bromopropoxy)-1,5-difluoro-3-iodobenzene (4.00 g, 10.6 mmol), 2-iodo-4-fluorophenol (2.525 g, 10.61 mmol) ) [repared according to WO/2012/027448], potassium carbonate (3.094 g, 22.39 mmol), and acetone (80 mL) is heated to reflux and stirred overnight. The mixture is cooled to room temperature and filtered. The pie is washed with acetone. The filtrate is concentrated to give the crude as a dark brown oil which is purified by column chromatography using 5% ethyl acetate in hexanes to give 3.69 g (65.1%) of the product as a colorless oil. (c) Step 3: Preparation of 3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2'-(3-((3'-(3,6-di-tert-butyl-9H-) carbazol-9-yl)-5-fluoro-2'-hydroxy-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propoxy) -3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol

[029] A mixture of 1,2-dimethoxyethane (69 ml), 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4 ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazol (4.00 g , 5.71 mmol) [repared according to US2011/0282018], 1,5-difluoro-2-(3-(4-fluoro-2-iodophenoxy)propoxy)-3-iodobenzene (1.524 g, 2.711 mmol), a solution of NaOH (0.6849 g, 17.12 mmol) in water (16 mL) and tetrahydrofuran (THF) (40 mL) is purged with nitrogen (N2) for 15 min, then Pd(PPh3)4 ((Ph) = phenyl, 0.1318 g, 0.1142 mmol) is added and heated to 85 °C overnight. The mixture is cooled to room temperature and concentrated. The residue is taken up in methylene chloride (200 mL), washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad and concentrated to give the crude protected binder To the crude is added THF (50 mL), methanol (MeOH, 50 mL) and approximately 100 mg of p-toluenesulfonic acid monohydrate (PTSA). it is heated to 60 °C overnight then cooled and concentrated. The crude binder is added methylene chloride (200 mL), washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, and concentrated to give brown crystalline powder. The solid is purified by column chromatography using a methylene chloride:hexanes gradient to give 1.77 g (52.4%) of the product as a white solid. (d) Step 4: Metal-Binder Complex Formation

[030] To a mixture of HfCl4 (0.117 g, 0.37 mmol) and binder (0.4573 g, 0.37 mmol) suspended in toluene (4 mL) is added 3 M MeMgBr (Me = methyl, 0.52 mL, 1.56 mmol) in diethyl ether. After stirring for 1 hour at room temperature, hexane (10 ml) is added and the suspension is filtered, giving a colorless solution. Solvent is removed under reduced pressure to generate 0.4125 g (77.4%) of the product metal-binder complex. EXAMPLE 8 Catalyst 4 is prepared as follows: (a) Step 1: Preparation of 2,7-di-tert- butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-

[031] A mixture of 2-(2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy)tetrahydro-2H-pyran (21.74 g, 52.22 mmol) [repared according to with WO/2012/027448, 2,7-di-tert-butylcarbazole (8.03 g, 28.73 mmol) [repared according to (full citation needed here) Synthesis 1979, 49-50], K3PO4 (23 .40 g, 110.24 mmol), anhydrous CuI (0.22 g, 1.16 mmol), dry toluene (85 mL) and N,N'-dimethylethylenediamine (0.45 mL, 4.18 mmol) is heated at 125 °C. After 24h, additional slurry of anhydrous CuI (0.2 g, 1.05 mmol) in dry toluene (0.9 mL) and N,N'-dimethylethylenediamine (0.45 mL, 4.18 mmol) is added and stirring is continued at 125 °C for an additional 72 h. After 96 h the reaction is cooled to room temperature and filtered through a small plug of silica, washed with THF and concentrated to give the crude product as a dark brown oil. The crude is crystallized from hot hexanes (50 mL) to give 13.48 g (90.9%) of the product as an off-white powder. (b) Step 2: Preparation of 2,7-di-tert-butyl-9- (2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4 ,4-trimethylpentan-2-yl)phenyl)-9H-

[032] A solution of 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-5-(2,4,4-trimethylpentan-2-yl )-phenyl)-9H-carbazole (7.70 g, 13.56 mmol) and dry THF (90 mL) under N2 atmosphere is cooled to 0-10 °C (ice water bath) and 2.5 molar ( M) n-BuLi (Bu = butyl) in hexanes (14.0 mL, 35.0 mmol) is added slowly. After 4 h, 2-iso-propoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.0 mL, 34.3 mmol) is added slowly. The mixture is stirred for 1 h at 0-10°C before allowing the reaction to warm to room temperature and then stirred for an additional 18 h. To the reaction mixture cold saturated aqueous sodium bicarbonate (75 ml) is added and then the mixture is extracted with four 50 ml portions of methylene chloride. The combined organic phases are washed with cold saturated aqueous sodium bicarbonate (200 mL), brine (200 mL), dried over anhydrous MgSO4, filtered and concentrated to give the crude as a golden foam. This crude is made into a paste in acetonitrile (75 mL) and allowed to rest for 1 hour at room temperature. The solid is isolated, washed with a small portion of cold acetonitrile and dried under high vacuum to give 8.12 g (86.3%) of the product as a white powder. (c) Step 3: Preparation of 6',6'''-(propane-1,3-diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol)

[033] A mixture of 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (4.00 g, 5.24 mmol adjusted based on a purity of 90.9% by high performance liquid chromatography, HPLC), 1,2-dimethoxyethane (65 mL), a solution of NaOH (0.67 g, 17.25 mmol) in water (19 mL), THF (22 mL) ), and 1,3-bis(4-fluoro-2-iodophenoxy)propane (1.28 g, 2.49 mmol) [repared according to WO/2012/027448] is purged with N2 for approximately 15 min. Then, Pd(PPh3)4 (202 mg, 0.18 mmol) is added and heated to reflux. After 48 h, the mixture cools to room temperature. The precipitate is isolated and dried under high vacuum for about 1 h to generate the crude protected binder. The crude is dissolved in a mixture of THF (100 mL) and MeOH (100 mL) and then heated to 60 °C. To the solution PTSA is added until the solution becomes acidic (measured by pH paper), then stirred at 60 °C for 8 h and then cooled. The precipitate is isolated by vacuum filtration, washed with cold acetonitrile (25 mL) and dried to give about 1 g of binder. Meanwhile, the filtrate develops a precipitate which is isolated and dried under high vacuum to generate an additional approximately 1 g of binder. Cultures are combined using chloroform (50 mL) and concentrated to generate 2.37 g (77.6%) of binder as white powder.(d) Step 4: Metal-Binder Complex Formation

[034] To a solution of toluene (40 mL) cold (-30 °C) binder (0.545 g, 0.44 mmol) and HfCl4 (0.142 g, 0.44 mmol) is added 3 M MeMgBr in diethyl ether (0.64 mL, 1.92 mmol). After stirring for 2 h, the black suspension is filtered using medium glass frits generating a colorless solution. The solvent is removed under reduced pressure yielding 0.589 g (92.5%) of the product. EXAMPLE 9(a) Step 1: Preparation of 3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-2 '-(3-((3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2'-hydroxy-5'-(2,4,4-trimethylpentan -2-yl)-[1,1'-biphenyl]-2-yl)oxy)propoxy)-3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1 ,1'-biphenyl]-2-ol

[035] A mixture of 1,2-dimethoxyethane (69 ml), 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4 ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazol (4.00 g, 5.708 mmol), 1,5-difluoro-2-(3-(4-fluoro-2-iodophenoxy)propoxy)-3-iodobenzene (1.524 g, 2.711 mmol), a NaOH solution (0.6849 g, 17.12 mmol) in water (16 mL) and TF (40 mL) is purged with N2 for 15 min, then Pd(PF3)4 (0.1318 g, 0.1142 mmol) is added and heated to 85 °C overnight , then cooled. To the residue methylene chloride (200 mL) is added, then it is washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, and concentrated to give the crude protected binder. For the crude is added THF (50 mL), MeOH (50 mL) and approximately 100 mg PTSA, added until the solution is acidic by the pH paper. The solution is heated to 60 °C overnight then cooled and concentrated. To the crude mixture methylene chloride (200 mL) is added, washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, and concentrated to give brown crystalline powder. The crude is purified via column chromatography, eluting with a gradient of methylene chloride:hexanes to give 2.63 g (81.2%) of the binder as a white solid.(b) Step 2: Formation of metal-complex binder
(reaction sequence 10)
[036] To a cold (-25 °C) slurry of HfCl4 (0.1038 g, 0.3241 mmol) in toluene (20 mL) is added 3.0 M MeMgBr in diethyl ether (0.45 mL, 1, 35 mmol) and stirred vigorously for 2 min. To the mixture the binder (0.4022 g, 0.3229 mmol) is added as a solid using toluene (3.0 mL) to wash. The brown mixture is stirred for 2 h at room temperature, then hexanes (20 mL) is added and the mixture is filtered. The filtrate, a colorless solution, is concentrated under high vacuum. To the solid is added hexanes (10 mL) and stirred for about 10 min. The off-white solid is collected by filtration and dried under high vacuum to give 0.4112 g (87.7%) of product. EXAMPLE 10A Step 1: Preparation of 1-(3-bromopropoxy)-4-fluoro-2-iodobenzene

[037] A mixture of 4-fluoro-2-iodophenol (7.0020 g, 29.420 mmol), potassium carbonate (8.2954 g, 60.020 mmol), 1,3-dibromopropane (59.00 mL, 581,262 mmol) , and acetone (200 ml) is stirred and refluxed overnight. After 16.5 h the reaction cools to room temperature and is filtered by vacuum filtration. The solids are washed with acetone (2 x 20 ml) and filtered as well. The filtrate is concentrated and the yellow solution that remains is distilled under vacuum to remove the remaining 1,3-dibromopropane. The brown crude oil is dissolved in a small amount of hexanes and is purified by column chromatography using a 0-5% gradient of ethyl acetate in hexanes to give 8.99 g (85.1%) of the product as an oil. yellow.(b) Step 2: Preparation of 5-fluoro-2-(3-(4-fluoro-2-iodophenoxy)propoxy)-1-iodo-3-methylbenzene

[038] A mixture of 1-(3-bromopropoxy)-4-fluoro-2-iodobenzene (8.9856 g, 25.032 mmol), 4-fluoro-2-iodo-6-methylphenol (6.3096 g, 25.036 mmol) ), potassium carbonate (7.400 g, 53.542 mmol), and acetone (165 mL) is stirred and refluxed overnight. After 16 h, the reaction cools to room temperature and is filtered by vacuum filtration. The solids are washed with acetone (2 x 20 ml) and filtered as well. The filtrate is concentrated to give the crude product as a dark brown oil. The oil is dissolved in a small amount of hexanes and purified by column chromatography using a 0-5% gradient of ethyl acetate in hexanes to give 11.55 g (87.1%) of the product as a yellow solid. (c) Step 3: Preparation of 3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-2'-(3-((3'-(2,7-di-tert-) butyl-9H-carbazol-9-yl)-5-fluoro-2'-hydroxy-5'-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl) oxy)propoxy)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol

[039] A mixture of 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazol (9.4182 g, 13.575 mmol), 1,2-DME (170 mL), a solution of NaOH (1.8145 g, 45.438 mmol) in water (49 mL), TF (57 mL), and 5-fluoro-2-(3-(4-fluoro-2-iodophenoxy)propoxy) -1-iodo-3-methylbenzene (3.4233 g, 6.458 mmol) is stirred and purged with N2 for approximately 15 min, then Pd(PF3)4 (0.5432 g, 0.470 mmol) is added. The mixture is heated to reflux for 19 h, and cooled to room temperature. The phases are separated and the organic phase is dried over anhydrous MgSO4, filtered, and concentrated to give a foamy golden orange solid as a crude protected binder. The crude is dissolved in a mixture of THF (250 mL) and MeOH (250 mL), and then heated to 60 °C. To the solution PTSA (3.0380 g, 15.971 mmol) is added until the solution becomes acidic. The reaction is stirred at 60 °C overnight, then cooled to room temperature, and concentrated to give a brown sticky solid. The crude product is dissolved in chloroform and silica gel is added. The slurry is concentrated to generate a dry powder mixture which is purified by flash column chromatography using a gradient of 2-5% ethyl acetate in hexanes to give the product as a pale yellow crystalline solid. To remove traces of ethyl acetate, the solid is dissolved in dichloromethane and concentrated to give a pale yellow crystalline solid (repeated twice). The solid is dried under high vacuum to generate 6.17 g (77.0%).(d) Step 3: Formation of metal-binder complex

[040] To a cold (-25 °C) slurry of HfCl4 (0.1033 g, 0.3225 mmol) in toluene (20 mL) is added 3.0 M MeMgBr in diethyl ether (0.45 mL, 1, 35 mmol) and stirred vigorously for 2 min. To the mixture the binder (0.4000 g, 0.3221 mmol) is added as a solid, washing with toluene (2.0 mL). After stirring for 1.5 h, the reaction mixture is filtered using a medium-fried funnel. The pie is washed with two 10 ml portions of toluene. To the colorless filtrate is added hexanes (5 mL) and concentrated in vacuo to give a white solid. To the solid toluene (30 ml) is added and stirred until almost all of the solid goes into solution. Then hexanes (25 mL) is added. The cloudy yellowish solution is filtered (syringe filter) and concentrated under high vacuum to give 0.4317 g of the product as a brown solid. EXAMPLE 11(a) Step 1: Preparation of 2-(3-(2,4-difluoro) -6-

[041] A mixture of 2-(3-bromopropoxy)-1,5-difluoro-3-iodobenzene (4.00 g, 10.6 mmol), 4-fluoro-2-iodo-6-methylphenol (2.674 g, 10.61 mmol) [repared according to US2011/0282018], potassium carbonate (3.094 g, 22.39 mmol), and acetone (80 mL) is heated to reflux and stirred overnight. The reaction is cooled to room temperature, filtered, solids washed with acetone, and concentrated to give a dark brown oil. The oil is mixed with acetonitrile and allowed to crystallize in the freezer. After filtration, the brown solid is dried in vacuo to give 4.47 g (76.9%) of the product.(b) Step 2: Preparation of 3-(2,7-di-tert-butyl-9H-carbazol- 9-yl)-2'-(3-((3'-(2,7-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2'-hydroxy-5'- (2,4,4-trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)propoxy)-5'-fluoro-3'-methyl-5-(2,4,4 - trimethylpentan-2-yl)-[1,1'-biphenyl]-2-ol

[042] A mixture of 1,2-dimethoxyethane (60 ml) is added 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazol (3.50 g, 4.69 mmol), 2-(3-(2,4-difluoro-6-iodophenoxy)propoxy)-5-fluoro-1-iodo-3-methylbenzene (1.246 g, 2.228 mmol), a solution of NaOH(0.563 g, 14.08 mmol) in water (14 mL) and TF (35 mL) is purged with N2 for 15 min, then Pd(PF3)4 (0.1083 g, 0.0983 mmol) is added and heated to 85°C °C overnight. The mixture is cooled and methylene chloride (200 mL) is added, then washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, and concentrated to give the crude protected binder. For the crude THF (50 mL), MeOH (50 mL) and about 100 mg PTSA are added until the solution is acidic by the pH paper. The solution is heated to 60 °C overnight then cooled and concentrated. For the crude methylene chloride (200 mL) is then added, washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, and concentrated to give the brown crystalline powder. The solid is purified by two flash column chromatography elutions with a hexanes:ethyl acetate gradient for the first column and a methylene chloride:hexanes gradient for the second column to give 1.42 g (50.6%) of the ligand as white crystals.(c) Step 3: Formation of the metal-ligand complex

[043] To a cold (-25 °C) slurry of HfCl4 (0.1031 g, 0.3219 mmol) and toluene (20 mL) is added 3.0 M MeMgBr in diethyl ether (0.45 mL, 1, 35 mmol). The mixture is stirred vigorously for 2 min and the binder (0.4012 g, 0.3185 mmol) is added as a solid, washing with toluene (3.0 mL). The reaction mixture is stirred at room temperature for 2 h. To the yellowish mixture a mixture of hexanes (20 ml) is added and filtered. The filtrate, a colorless solution, is concentrated under high vacuum. To the solid, the mixture of hexanes (10 mL) is added and stirred for about 10 min. The solid is collected by filtration and dried to generate a mixture of the desired product and a minor component attributed to insufficient alkylation. The filtrate is concentrated and recombined with the solid. The mixture is dissolved in toluene (15 mL) and 3.0 M MeMgBr (0.10 mL, 0.30 mmol) is added. The mixture is stirred for 1h, filtered and concentrated. The brown solid is dissolved in toluene (15 mL), and hexanes are added (25 mL). The cloudy solution is filtered and concentrated to generate a brown solid. To the solid, the mixture of hexanes (30 mL) is added and stirred vigorously for 1 h. The white solid is collected and dried under high vacuum to give 0.2228 g (47.7%) of product. EXAMPLE 12(a) Step 1: Preparation of 2',2'''-(propane-1,3- diylbis(oxy))bis(3-(2,7-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan- 2-yl)-[1,1'-biphenyl]-2-ol)

[044] A mixture of 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazol (7.52 g, 9.89 mmol adjusted based on a purity of 91.2% by HPLC), 1,2-dimethoxyethane (120 mL), a solution of NaOH (1.30 g, 32.5 mmol) in water (35 mL), TF (60 mL), and 1.3 -bis(4-fluoro-2-iodo-6-methylphenoxy)propane (2.56 g, 4.70 mmol) [repared according to US 2011/0282018] is purged with N2 for approximately 15 minutes and Pd(PF3) 4 (303 mg, 0.26 mmol) is added. The mixture is heated to reflux for 48 h, then cooled to room temperature. Once cooled, a precipitate is formed which is isolated and dried under high vacuum for 1h to generate 6.10 g of crude protected binder. For the crude it is added to a mixture of 1:1 MeOH/THF (200 mL) and approximately 100 mg PTSA. The solution is heated at 60 °C for 8 h, then cooled and concentrated. To the residue methylene chloride (200 mL) is added, then washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, then concentrated to give 4.92 g of crude binder. This crude is purified by flash chromatography eluting with 2% ethyl acetate in hexanes to give 4.23 g (71.7%) of the product as a white powder. (b) Step 2: Formation of metal-binder complex

[045] To a cold (-30 °C) solution of toluene (30 mL) of binder and ZrCl4 is added 3 M MeMgBr in diethyl ether (4.1 mL, 12.3 mmol). After stirring overnight, the black suspension is filtered using medium glass frits, generating colorless solution. The solvent is removed under reduced pressure giving 0.456 g (61.7%) of the product as a white solid.

[046] A mixture of 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazol (3.50 g, 5.16 mmol), 1,2-dimethoxyethane (200 mL), a solution of NaOH (0.62 g, 15.47 mmol) in water (60 mL), TF (60 mL), and 1,3-bis(2,4-dichloro-6-iodophenoxy) propane (1.51 g, 2.45 mmol) [repared according to US 2011/0282018] is purged with N2 for approximately 15 min and Pd(PF3)4 (0.12 g, 0.10 mmol) is added. The mixture is heated to reflux for 48 h, then cooled and concentrated. To the residue methylene chloride (200 mL) is added, washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica pad, and concentrated to give crude protected binder. The crude is dissolved in a mixture of THF (100 mL) and MeOH (100 mL), heated to 60°C and PTSA is added until the solution becomes acidic (pH paper). The mixture is stirred at 60°C for 8h, then cooled to room temperature and concentrated. To the residue methylene chloride (200 mL) is added, washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, and concentrated to give the crude binder. The crude is purified by flash chromatography eluting with 40% methylene chloride in hexanes to give 2.57 g (78.9%) of the binder as a white powder.(b) Step 2: Formation of metal-binder complex

[047] To cold toluene (20 mL) containing ZrCl4 (0.105 g, 0.45 mmol) is added 3.0 M MeMgBr in diethyl ether (0.63 mL, 1.90 mmol). After stirring for 3 min, the binder (0.60 g, 0.45 mmol) is added as a solid. After stirring for 2 h, hexanes (20 mL) is added and the black suspension is filtered. The solvent is removed under reduced pressure, generating an off-white solid. To this solid, hexanes (20 mL) is added and stirred for 10 min. The product is collected over the fritter, washed with hexanes (5 mL) and dried under reduced pressure to give (0.5032 g, 77%) of white solid. EXAMPLE 14 Preparation of Fluoro Analog of Catalyst 9:(a) Step 1: binder preparation

[048] A mixture of 1,2-dimethoxyethane (50 ml), 2,7-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4 ,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (3.068 g, 4.17 mmol), 1,3-bis(2,4-difluoro-6-iodophenoxy)propane (1.05 g, 1.98 mmol) [repared according to US 2011/0282018], a solution of NaOH (0.56 g, 14.0 mmol) in water (14 mL), and TF (14 mL) is purged with N2 for about 15 min, then Pd(PF3)4 (145 mg, 0.13 mmol) is added. The reaction mixture is heated to 85 °C for 36 h and then cooled. Once cooled, a precipitate is formed which is isolated and dried under high vacuum for 2 h, resulting in crude protected binder. For the crude it is added to a mixture of 1:1 MeOH/THF (50 mL) and approximately 100 mg PTSA. The solution is heated to 60 °C for 8 h, then cooled and concentrated. To the residue methylene chloride (200 ml) is added, washed with brine (200 ml), dried with anhydrous MgSO4, filtered through a silica gel pad, and concentrated. The residue is dissolved in hexanes and purified by flash column chromatography using a gradient of 2-5% ethyl acetate in hexanes to give the product as a white powder.

[049] To cold toluene (30 mL) containing ZrCl4 (0.055 g, 0.24 is added 3.0 M MeMgBr in diethyl ether (0.33 mL, 1.0 mmol) After stirring for 5 min, the binder (0.300) g, 0.24 mmol) is added as a solid. After stirring for 1 h, a quantity of hexane (15 mL) is added and the black suspension is filtered. The solvent is removed under reduced pressure yielding 0.312 g (85.6 %) of the product as a white solid.

权利要求:
Claims (3)
[0001]
1. A process for preparing an olefin homopolymer or copolymer, characterized in that it comprises contacting ethylene, an alpha-olefin, or a combination thereof, and a catalytic amount of a metal-binder complex catalyst of the formula:
[0002]
2. Process according to claim 1, characterized in that R1a, R1b or both are a halogen atom selected from fluorine, chlorine, iodine, or combinations thereof.
[0003]
3. Process according to any one of claims 1 or 2, characterized in that the alpha-olefin is selected from the group consisting of linear alpha-olefins having from 3 to 12 carbons, branched alpha-olefins having from 5 to 16 carbons and combinations thereof.

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JP2016524024A|2016-08-12|

JP6441332B2|2018-12-19|

SG10201802443VA|2018-05-30|

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引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

GB1069848A|1965-05-17|1967-05-24|Imp Chemical Imdustries Ltd|Process for the polymerisation of vinyl chloride|

US5153157A|1987-01-30|1992-10-06|Exxon Chemical Patents Inc.|Catalyst system of enhanced productivity|

US7163907B1|1987-01-30|2007-01-16|Exxonmobil Chemical Patents Inc.|Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization|

US5064802A|1989-09-14|1991-11-12|The Dow Chemical Company|Metal complex compounds|

JP2545006B2|1990-07-03|1996-10-16|ザダウケミカルカンパニー|Addition polymerization catalyst|

US5721185A|1991-06-24|1998-02-24|The Dow Chemical Company|Homogeneous olefin polymerization catalyst by abstraction with lewis acids|

US5296433A|1992-04-14|1994-03-22|Minnesota Mining And Manufacturing Company|Trisborane complexes and catalysts derived therefrom|

US5350723A|1992-05-15|1994-09-27|The Dow Chemical Company|Process for preparation of monocyclopentadienyl metal complex compounds and method of use|

US5372682A|1993-06-24|1994-12-13|The Dow Chemical Company|Electrochemical preparation of addition polymerization catalysts|

US5625087A|1994-09-12|1997-04-29|The Dow Chemical Company|Silylium cationic polymerization activators for metallocene complexes|

EP0889912B1|1996-03-27|2000-07-12|The Dow Chemical Company|Highly soluble olefin polymerization catalyst activator|

KR20000005027A|1996-03-27|2000-01-25|그레이스 스티븐 에스.|Solution polymerization process with dispersed catalyst activator|

CA2253804C|1996-05-02|2005-07-26|Lyondell Petrochemical Company|Catalyst system containing reaction product of liquid silicone and polyamine|

US5783512A|1996-12-18|1998-07-21|The Dow Chemical Company|Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same|

US6103657A|1997-07-02|2000-08-15|Union Carbide Chemicals & Plastics Technology Corporation|Catalyst for the production of olefin polymers|

US6696379B1|1997-09-19|2004-02-24|The Dow Chemical Company|Supported modified alumoxane catalyst activator|

JP2000159829A|1998-11-27|2000-06-13|Tosoh Corp|Catalyst for olefin polymerization and production of polyolefin using same|

US7060848B2|2002-04-24|2006-06-13|Symyx Technologies, Inc.|Bridged bi-aromatic catalysts, complexes, and methods of using the same|

US6897276B2|2002-04-24|2005-05-24|Symyx Technologies, Inc.|Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom|

AR048104A1|2004-03-17|2006-03-29|Dow Global Technologies Inc|CATALYZING COMPOSITION THAT INCLUDES A LINK AGENT FOR THE FORMATION OF OLEFIN'S TOP COPOLYMERS IN MULTIPLE BLOCKS|

WO2007136495A2|2006-05-17|2007-11-29|Dow Global Technologies Inc.|High efficiency solution polymerization process|

JP5330414B2|2008-02-29|2013-10-30|ダウグローバルテクノロジーズエルエルシー|Oriented film containing ethylene / α-olefin block interpolymer|

US8372930B2|2008-06-20|2013-02-12|Exxonmobil Chemical Patents Inc.|High vinyl terminated propylene based oligomers|

WO2010061630A1|2008-11-28|2010-06-03|三菱レイヨン株式会社|Processing assistant for expansion molding, vinyl chloride resin composition for expansion molding, and expansion molded body|

EP2473538B1|2009-08-31|2017-07-26|Dow Global Technologies LLC|Catalyst and process for polymerizing an olefin and polyolefin prepared thereby|

US8802774B2|2009-10-02|2014-08-12|Dow Global Technologies Llc|Block composites and impact modified compositions|

US8716400B2|2009-10-02|2014-05-06|Dow Global Technologies Llc|Block composites and impact modified compositions|

SG2014006266A|2010-02-19|2014-03-28|Dow Global Technologies Llc|Process for polymerizing an olefin monomer and catalyst therefor|

CN103038281B|2010-03-02|2015-11-25|陶氏环球技术有限责任公司|Based on the polymer composition of ethene|

US8609794B2|2010-05-17|2013-12-17|Dow Global Technologies, Llc.|Process for selectively polymerizing ethylene and catalyst therefor|

US9643900B2|2011-03-25|2017-05-09|Dow Global Technologies Llc|Hyperbranched ethylene-based oils and greases|

WO2011146044A1|2010-05-17|2011-11-24|Dow Global Technologies Llc|Process for selectively polymerizing ethylene and catalyst therefor|

KR20130089165A|2010-07-06|2013-08-09|티코나 게엠베하|Ultra-high molecular weight polyethylene, its production and use|

EP2609123B1|2010-08-25|2017-12-13|Dow Global Technologies LLC|Process for polymerizing a polymerizable olefin and catalyst therefor|

JP5171907B2|2010-09-13|2013-03-27|株式会社東芝|Information processing apparatus and information processing program|

US20120116034A1|2010-11-08|2012-05-10|Dow Global Technologies, Inc.|Solution polymerization process and procatalyst carrier systems useful therein|

SG190985A1|2010-12-03|2013-07-31|Dow Global Technologies Llc|Processes to prepare ethylene-based polymer compositions|

EP2797963B1|2011-12-29|2019-07-03|Dow Global Technologies LLC|Hyperbranched olefin oil-based dielectric fluid|

EP2797962B1|2011-12-29|2015-11-18|Dow Global Technologies LLC|Process for producing low molecular weight ethylene- and alpha-olefin-based materials|

JP6408481B2|2012-11-30|2018-10-17|ダウグローバルテクノロジーズエルエルシー|Ethylene / α-olefin / non-conjugated polyene composition and foam formed therefrom|

KR20150100844A|2012-12-27|2015-09-02|다우 글로벌 테크놀로지스 엘엘씨|An ethylene based polymer|

JP6393693B2|2012-12-27|2018-09-19|ダウグローバルテクノロジーズエルエルシー|Catalytic system for olefin polymerization.|

ES2731574T3|2012-12-27|2019-11-18|Dow Global Technologies Llc|A polymerization process to produce ethylene-based polymers|

US9527940B2|2012-12-27|2016-12-27|Dow Global Technologies Llc|Polymerization process for producing ethylene based polymers|

MX2015016913A|2013-06-28|2016-04-04|Dow Global Technologies Llc|Hyperbranched ethylene-based oligomers.|

US10072172B2|2013-09-25|2018-09-11|Mitsubishi Chemical Corporation|Flexible vinyl chloride resin composition, molded product, electric wire coating material, and coated electric wire|

JP6327471B2|2013-09-25|2018-05-23|三菱ケミカル株式会社|Wire covering material and covered wire|JP6393693B2|2012-12-27|2018-09-19|ダウグローバルテクノロジーズエルエルシー|Catalytic system for olefin polymerization.|

ES2731574T3|2012-12-27|2019-11-18|Dow Global Technologies Llc|A polymerization process to produce ethylene-based polymers|

US9527940B2|2012-12-27|2016-12-27|Dow Global Technologies Llc|Polymerization process for producing ethylene based polymers|

US10519260B2|2014-06-30|2019-12-31|Dow Global Technologies Llc|Polymerizations for olefin-based polymers|

US9975975B2|2014-07-24|2018-05-22|Dow Global Technologies Llc|Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers|

EP3317312B1|2015-06-30|2020-06-10|Dow Global Technologies LLC|A polymerization process for producing ethylene based polymers|

CN107787336B|2015-06-30|2021-05-28|陶氏环球技术有限责任公司|Polymerization process for preparing ethylene-based polymers|

WO2017058981A1|2015-09-30|2017-04-06|Dow Global Technologies Llc|Procatalyst and polymerization process using the same|

WO2017058858A1|2015-09-30|2017-04-06|Dow Global Technologies Llc|A polymerization process for producing ethylene based polymers|

EP3601387A1|2017-03-31|2020-02-05|Dow Global Technologies LLC|Germanium-bridged bis-biphenyl-phenoxy catalysts for olefin polymerization|

US11242415B2|2017-09-29|2022-02-08|Dow Global Technologies Llc|Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility|

EP3688042A1|2017-09-29|2020-08-05|Dow Global Technologies LLC|Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility|

BR112020005407A2|2017-09-29|2020-09-29|Dow Global Technologies Llc|bis-phenyl-phenoxy polyolefin catalysts with a methylenethialalkylsilicon binder in the metal for enhanced solubility|

WO2021091983A1|2019-11-04|2021-05-14|Dow Global Technologies Llc|Biphenylphenol polymerization catalysts|

WO2021127150A1|2019-12-19|2021-06-24|Dow Global Technologies Llc|Gas-phase biphenylphenol polymerization catalysts|

法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2020-11-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|

2021-08-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

US201361840624P| true| 2013-06-28|2013-06-28|

US61/840,624|2013-06-28|

PCT/US2014/044374|WO2014210333A1|2013-06-28|2014-06-26|Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts|

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