HUACUJA RAFAEL (US)
OZEROV OLEG (US)
DE MOTT JESSICA (US)
TEXAS A & M UNIV SYS (US)
| US5387660A | 1995-02-07 | |||
| US6448447B1 | 2002-09-10 | |||
| US5278119A | 1994-01-11 |
| What is eiaimed is: 1 , A catalyst system comprising the reaction product of at feast the following: A) a procaiaiyst: and B) at least one coeaiaiyst structure selected from the following I) through isl): I} at least one eocaiaiysi comprising an anion having Structure i as shown below: (Struciure 1 },. wherein ; through 52 are each independently selected from the following: a halogen, a substituted or unsubstituted (C^-C^hydrbcarbyl, or a substituted or Si(OiRc)2)3, Ge( c>3< Qe(NiRc}2}3, Ge( {Rc)2)3. P(RC)2. P(N(RG)2)2, P(ORc)2, N(RC)2> NH(RC), NH¾ OH. SH, ORct S C, N02, CN, CF3, CF2RC, CF(RC)2, RcS(0)-, RcS(0)2-, (RC)2C~N-, RcC{GJGs RcOC(G)- RcG{0)N{R)-i (R^NCiO)-, or hydrogen, wherein each Rc is independently a substituted or unsubstituted unsubstituted (C-j -G35)heterohyd ocarbyi; and wherein two or more of Ri through R12 may optionally form one or more ring structures; and wherein one or more hydrogen atoms may optionally be substituted with deuterium; and wherein, optionally, one of R< throug f½ may be selected from a P'H.{R¾, PH{N{RC}2}2! PH{ORc . ΜΗ ¾, NH(Rc)2s H3, OH2, SH2s OHRc SHRC, to form a neutral struciure; and wherein each Re is independentiy a substituted or unsubstituted (C^-C jgjhydrocarby!, Of a substituted or unsubstituted (C^-Cggjheterohydrocarby!; and wherein at least one of Ri through ί½ is a halogen; or is) at least one cocatalyst comprising an anion having Structure 2 as shown below: (Structure 2), wherein R53 through R¾ are each independently selected from the following: a halogen, a substituted or unsubstiiuted {C^-C Q) rocarb i or a substituted or unsubsStuted (C-j 6e(R¾ Ge{H(R%)z, Ge(0(RG}2)3, P(RC)2, P(N(RC)2)2, P(ORc)2, N(RC)2, HH{R NM¾ OH, SH, ORc, SRC, N02, CN, CF3> CF2RC, CF(RC)2, RcS(0)-, RcS(0)2-, (Rc¼jC«N-, RcC(0}0-< RcGC(0}~, RGC{0}N{R)-; (Re)2 C(0)-, or hydrogen, and wherein each Rc Is independently a substituted o unsubststuted C-i-Ggglhydroc f, or a substituted or unsubststuted (C ^ ~C 35 Jheterohy ύ mm rb i ; and wherein two or more of through R2 ma optionally form one or more ring structures; and wherein one or more hydrogen atoms may optionally be substituted with deuterium; and wherein, optionally, one of « through R¾* may be selected from a PH(R¾. PH{N(RC)2)2. PH{ORc)>. NH(Rc)2, HH{R , NH¾ OH¾ SH2, OHRc, SHRC, to form a neutral structure; and wherein each Rc is independently a substituted or unsubststuted (C^-Cgglhydrocarbyl,. or a substituted or unsubststuted (C -G35)iiet roi d ocarb !; an wherein at feast one of R« through R24 is a halogen; or iii} a combination of i and Si, 2. The catalyst system of claim 1 , wherein, for Structures 1 or 2, the hydrocarbyl and/or the heterohydrocarbyl is/are each independently substituted with one or more subststuents Rs; and each Rs is independently a halogen atom, po!yfluoro substitution, perfSuoro substitution, F3G-, FCH20-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS-. RS(Oh RS(0)2-, R2P-, R2N-, R2C=N-, NC-, RC(0)0-, ROC(O)-, RC(0)N(R)-, or R2NC(0}-, wherein each independently is an unsubstituted (C-i -C-^alkyl. 3. The catalyst syslem of dai 1 , wherein, for Structure 1 , each of F¾ through R^ is Lmsubstiiuted; arid/or wherein, for Structure 2, eac of R« through R24 is unsuhstifuted. 4. The catalyst system of claim 1 and 2, wherein, for Structure 1 , two or more of Ri through R« form one or more ring structures, wherein said ring structures have from 3 to SO atoms in the ring excluding any hydrogen atoms; and/or wherein for Structure 2, two or more Of r½ through R¾ form, one or more ring structures, wherein said ring structures have from 3 to 50 atoms in the rirsg, excluding any hydrogen atoms. 5. The catalyst system of any one of claims 1 , 2 and 4, wherein, for Structure 1 , none of R: through R½ form ring structures; and/or wherein for Structure 2, none of f½ through R24 form ring structures. 8, The catalyst system of any one of the previous ciaims, wherein, the anion of the cocataiyst comprises at feast three halogen atoms. ?, The catalyst system of any one of the previous claims, wherein, the cocatalyst comprises a structure selected from the following 1 } through 86); -38- -37- 8. The catalyst system of any one of the preceding claims, wherein th eocatalyst structure comprises at least one anion having Structure 1 and/or at least one anion having Structure 2, the eocatalyst structure further comprises at least one cation selected from the following: 1 ** ml , wherein X is selected from B, C, N, O, At, Si, P, or S; each Y is independently selected a (C^^gi-hydrocarb !, (C^-C^heterohydrocarby!, SifR0^, Ge{R%„ {H%: H{R OR* SRC, N02..CN, CF3, RcS{Oh RcS<0}2», {R^C^ -.- RcC(0)0-, RcOC(0)-, RcC{0)N(R)-( (R^NCODh halogen atom, or a hydrogen atom, wherein each of the hydrocarbyl, heterohydrocarbyl, Si{ G)3< Ge{Rc)3, P(RC)2> M(RC')2- Rc SRC, RCS{Q>, CS{0>2-, (Rc)2ON-, Rc'C{0)0-, RcOC(0)-, RcC(0}fM{R)-, (R^NCiOh is unsubststuted or substituted with one or more R$' substftuents, each Rs independently is a halogen atom, polyfiuoro substitution, perfiuoro substitution, unsubstiiuted (G-j-C1g)a!kyl: F3C-, FCH20-, F2HCO-, F3CO-, R3S1-, R3Ge-, RO-, RS-, RS(O)-, RS(D)2-, R2P-> R^. R2C=N-, NC-, RC(0)0-, ROC(O)-, RC(0)N(R)-, or R2NC(0)-, or two of the Y groups are together with X form a (C-j-C -j g}hydrocarbylerie optionally substituted with one or more Rs substituertts, and wherein each Rc is (C^^hydr earbyl-, and R independently is an unsubstituted (Ci~C-jg}hydrocarbyS; m is independently 0, 1, 2 or 3; I is a neutral Lewis base, and when m = 0, L is not present; n is independently 2, 3, 4 or S; and where two or thre f «Xfc9irt optionally be linked together by Joining two o more (C^-Cggjhydrocarbyi, (C1-C35)heterohydrocarbyi or an Rc. 9. The catalyst system of any of the proceeding claims, wherein the eocatalyst structure comprises at. least one anion having Structure 1 and/or at least one anion having Structure 2, and the eocatalyst structure further comprises at least one cation selected from formula (I). formula 01), and formula (ill) where each RN is independently selected from (Ct~C3o)aikyi and {Cs~i¾4}aryl; wherein ring A is a 5-7 membered heterocycloaikyl ring having 1 or 2 hetero atoms selected from oxygen, nitrogen, and sulfur, and the hetetOcydoalkyl ring is optionall substituted with 1 or more halogen atoms, unsubstituted (C^ -C^ gja!kyf, ha!o(Cr Cs)alkoxy( R3Sh R3Ge-, RCK RS-, RS{0 , RS(0)2«, R2P-, R2N-, R2C=N-, NC-, RC(0)Ch ROC(O)-, RC(0)N(R or R2NC{0}~ wherein each R is independently unsubstituted (C ^ -C ^ g)hydrocarbyl ; wherein ring B is a 5-7 membered heteroaryi group having 1 or 2 hetero atoms selected from oxygen, nitrogen, and sulfur, and the heteroaryi group is optionally substituted with 1 or more halogen atoms, unsubstituted (C^ -C^ g)a!kyi, hal0(Cr Csja!koxy, R3Sh R3Ge~5 RO-, RS-S RS{0 , RS{0) -, R2P-, R N-, R2C=N- NC-» RC(0)0-s ROC(O)-, RC{0)N{R}-, or R2NC{0)~ wherein each R is independently unsu bstituted (C -C ^ g)hydrocarbyS . 10. The catalyst system of any of the proceeding claims, wherein the cation is +N{H)R! where at !east two R are chosen from (Cta~C«>)alkyL 1 1. The catalyst system of claims 1-8, wherein the cation is fC(CgH5)3. 12, The catalyst system of claims 1 -8, wherein the cation is *C(CsH*RG)$, where R is 13. The catalyst system of claims 1-8. wherein the cation is fAK ^COR^ * , where each RN is chosen from (C r~C3o)aikyl or (Cs-Cz^aryS and n is 1 or 2, or two RN together wit the Al atom to which they are attached form a cyclic structure. 14, The catalyst system of claims 1-8, wherein the cation is [FeiCp{Rs)r!)2r, two or more RN together with the group to which they are attached form a cyclic structure. 15, The cataiyst system of claims 1-7,■ wherein wherein the cocataJyst structure comprises at least one anion having Structure 1 and/or at least one anion having Structure 2» and and the coeatafyst structure further comprises at least one cation selected from : (m) n) (o) (P> <u). 16. A polymer composition comprising the polymer product of the following: ethylene or propySene wit one or more a-oiefin copolymers and/or one or more dsenes, and wherein the polymer product is polymerized in the presence of the catalyst system of any one of the previous claims, 17. A process for producing a polymer composition, said process comprising: seieciing ethylene 'or propylene; and poiymerizing said eibyierie or propylene, with one or more ct-oiefin copoiymers and/or one or more dienes, in the preserice of the caiaiysi system of any one of claims 1 to 16. 18. The catalyst system of claim 1 ; wherein the cocata!yst structure comprises (a) at Seast one anion having Structure 1 , wherein Ri is CH2-CH}-D- and D represents Ci-C;s ydracarbyiene or Ci-Cis heierohydrocarbylene or (b) at ieasf one anion having Structure 2, wherein at least one of f½ through ?½ is independently seiected from {CH2-GH}~D- artsi each D independently represents C?-Ci# hydrccafbyleiie or O Cis heterohydrocarbyiene. |
CROSS-REFERENCE TO RELATED APPLICATIONS
This applicatio claims the benefit of priority to U.S. Provisional Application No.
62/579,413, filed October 31. 2017, the disclosure of which is incorporated herein in its entirety.
BACKGROUND
To be catai tically active, olefin polymerization procatalysts need to be activated with an appropriate eocataiyst. A eocataiyst has a tremendous effect on catalyst performance. Conventions! eocataSysts are based on MAO and ammonium fetrakis{pentafiuorophenyl}~ borate compounds. The weakly coordinating nature of fetrakis(pehtafluoro-phenyS}borate anion is the main reason for its usefulnes in ofef$n-based polymerizations. Other ionic polymerization eataiyst systems, comprising of buiky anions, derived from polynuciear boranes, carboranes or metailacarboranes, are described in U.S. Patent 6,245,706.
However, there remains a need for hew "weakly coordinating" catalyst systems thai can efficiently polymerase olefin-based polymers at high polymenzation temperatures {for example, T 1:70*C). This need has been met .by the following invention.
SUMMARY OF THE INVENTION
A catalyst system is provided, which comprises the reaction product of at least the following: A) a procataiyst; and
S) at least one eocataiyst structure selected from the f ollowing i) through in): 1} at least one eocataiyst comprising an anion selected from Structur 1 as shown below:
R « (Structure 1 ),
wherein 5 through f½ are each independently selected from the feiiowing: a halogen, a substituted or unsubstituted (C-O^hydrocarbyl, or a substituted or unsubstituted
(C r C4 0 )heferohydrocarbyi, $i(R%, Si(N(R c ) 2 } 3 , Si{0(R ¾) 3> Ge(R c } 3 , Ge(N{R c } 2 )3, Ge(d(R¾) 3 > P(f¾ P(N{R C ) 2 ) 2 . P(OR¾, N{R C ) 2 , NH(R C ), NH 2 , OH, SH, OR c , SR C > Q 2 > CH, CF 3 , CF 2 R C , CF{R C ) 2 , R c S(0)-, R c S(0) 2 -, (R C ) 2 C=N-, R c C(0)0-, R c OC(0)-,
R c C(0}N{R}~, {R c ) 2 NC(O or hydrogen, wherein each R G is independently a substituted or unsubstituied (C- ~C3 }h drocarb ! ! or a substituted or unsubstituied.
(C-j-CgsJhetefohydrocarbyl; and wherein two or more of R s through i¾ may optionally form one or more ring structures; and wherein one or more hydrogen atoms may optionally be substituted with deuterium; and wherein, optionally, one of Rs through R« may be selected from a PH(R C } 2 , PH{N(R C ) 2 } 2 , PH{OR G }, NH(R G } 2 , NH(R C ) 2 , NH 3 ,. OH 2 » SH 2 , OHR c , SHR C , to form a neutral structure; and wherein each R c is independently a substituted or unsubstituied (Cj -C3g)hydrocarbyl , or a substituted or unsubstituied
(C -Cjgjheterohydrocarbyt; and
wherein at least one of Rs through Ru is a halogen; or
ii) at ieast one cocataSysi comprising an anion selected from Structure shown below:
wherein « through R24 are each independently selected from the following: a halogen, a substituted or unsubstituied (Cj^Qjh ocarbyl, or a substituted or
unsubstituied (C r G4 0 )heterohydrocarbyl, Si(R c ) 3 , Si(N(R c ) 2 ) 3 , Si(0{R i: ) 2 } 3 , GeiR 0 ^,
G©( {R D } 2 }3 i Ge(0{R c ) 2 ) 3 , P(R C ) 2 , P(N(R C ) 2 ) 2> P(OR c ) 2 , N(R C ) 2 , NH{R C ), NH¾ OH. SH,
OR c , SR C , N0 2 , C , CF 3 , CF 2 R C , CF(R C ) 2 , R c S(0)-, R c S(0) 2 -, (R c ) 2 C=hh R c G(0)G--,
R c OC(0)-, R c C(0)N(R)- ; {R c ) 2 NC(Qh or hydrogen, and wherein each R c is independently ' substituted or unsubstituied (C-i "C-jgJhydrocarbyL or a substituted or unsubstrtuted
(C-j -C35)hete o droc rbyl; and
wherein two or more of Ru, through R-ii may optionally form one or more ring structures; and wherein one or more hydrogen atoms may optionally be replaced with deuterium; and wherein, optionally, one of R-13 through R2 may be selected from a PH{R C ) 2 ,
ΡΗ( {Β¾} 2ι PH(OR°), NH{R C } 2: H{R c ) 2l NH 3 , OH 2< SH 2 , OHR c , SHR C , to form a neutral structure; and wherein each R c is independently a substituted or unsubstituted {G-j-Cggjhydroearbyi, or a substituted or unsubsiiiuted (C-i-CjgJheieroriydrocar yi; and wherein at least one of R« through f¾ is a halogen; or
iii) a combination of i and ii. DETAiLED DESCRIPTION OF THE INVENTION
it has been discovered that haiogenated earboranes can be used to effectively catalyze the polymerization of olefins at high temperatures.
As discussed above, a catalyst system is provided, which comprises the reaction product of: A) a procata!yst; and B) at Seast one cocataiyst structure selected from the following i} through iii). each as discussed above.
The catalyst system may comprise a combination of two or more embodiments as described herein.
In one embodiment, Embodiment A hereinafter, the cocatalyst structures Structure 1 and Structure 2 further comprise at least one cation selected from the following: 1
, wherein X is se!ected from B, C, M, O t AS, Si, P, Or S; each Y is independently selected from a (C C 40 )~hydrocarbyi, {C 1 -C4 0 )heterohydrocarbyl. S¾R C ) 3 , Ge(R c } 3 , P(R C } 2! M(R%,
OR q , SR C , N0 2 , CN, CF 3 , R¾{0}-.. R c S{0} 2 - (R¾ON-, R c C{0)0-, R c OC{0)- i
R°C(0)N(RK {R C: }2 C{0}- 1 halogen atom, or a -hydrogen atom, wherein each of the hydrocarbyi, heterahydrocarbyS, S¾R% Ge(R c } 3 , P(R C } 2! N{R¾, QR c vSR c , R¾(OK
R?$(0) r , (R°) 2 C=N- ! R c C{0)0-, R c OC{0}~, R¾CQ}N(Rh (R c ) 2 NC{OK is unsubstituted or substituted with one or more R s substituents, each R s independeniSy is a haSogeri atom, polyfiuoro substitution, perfluoro substitution, unsubstituted (C^-C^Jalk f. -FjG-, FGH G-,
F 2 HCQ-, F 3 CC-. R 3 Si-, R 3 Ge-, RO-, RS-, RS(O)-, RS(0) 2 -, R 2 P-, R 2 N-, R 2 C~N-, NC-.
RC(0)0-, ROC(O)-, RC(0)N(R)-, or R 2 NC(0)-, or two of the Y groups together with X form a hetero(C-j-C-jg}hydrocarbylene {i.e„ a heteroaryl or heterocycloalkyl group} optionally substituted with one or more R s substituents, and wherein each R c is (C 1 -C Q) yd oc rby!, and R independently is an unsubstituted (G^-C^g)hydrocarbyi; m is independently 0, 1 , 2 or
3; L is a neutral Lewis base, and when m : = 0, L is not present; n is inde ende t 2, 3, 4 or 5;
or where two or three ]Υ η Χ3* can optionaliy be linked together by joining two or more
{C -C3g)hydroc¾rbyi , . (C-j -Cgglheterohydrocarbyi or an R
In certain embodiments of Embodiment A, cation [Y n -X-L m ] + is selected from the folio wing:
(u).
in other embodiments of Embodiment A each hydrocarbyi and/or heierohydrocarbyi of in [Y, r X~U,3 ' is indeperidentSy substiiuted with one or more subsiituen!s R 8 ; and each R 8 is independeniiy a ha!ogen atom s po yfiuoro substitution, peri!uoro substitution, FgC-, FCH2O-,
F 2 HCO-, F3CO-. «351-, R 3 Ge-, RO-, RS-, RS<G}~, RS{O) 2 -> ¾Ρ-> ¾ -, F½C=N-, C -
RC(0)0-, ROC(0 ; RC{0)N{RK or R 2 NC(Oh wherein each R independently is an unsubstkuted (C r C 18 )aikyi. In one embodiment, ' for Structure 1 , Embodiment 8 hereinafter, each of R ; through i2 is unsubstituted; and/or wherein, for Structure 2, Embodiment C hereinafter, each of R« through !¾ is unsubstituted, in one embodiment, for Structure 1 , two o more of R¾ through Rn form on or more ring structures, wherein said ring structures have from 3 to SO atoms in the ring excluding any hydrogen atoms; and/or wherei for Structure z, two or more of R« through H?A form one or more ring structures, wherein said ring structures have from 3 to 50 atoms in the ring, excluding any hydrogen atoms.
in some Embodiments of Embodiment B, R¾ is hydrogen, ha!ogen or unsubstituted C- Ctrs aikyl, Ci-Ce alkoxyf Cr-Ce)aiky|amino 5 diiC Cslalkyl-CCa-CeJaikeniyfsilyi, haio{C¾- Cs)aikoxy, tri{Ci-Gs}aSkyisiiyl, tri (C i -C 6 )aikyisiiyioxy , halo(Ci-C 6 )aikyi, tri{di(Ci- Cg)aSkyiamino}silyi, C1-C6 alkoxy, C -C6 alkyithio, thio, C2-C6 alkanoy!, tri{Ci--Ce}a!kyloxysiiy!, di(Ci-C6)a!ky!amino, triCCi-CsJaiky!gerrnyi, tri{di(CrCe}a!kylamino)g8fmyS, tri{C
Ce}aikyioxygermyi, di{Ci-Cg}aikyIphosphaneyl, diidifCrCjaikylamineiphosphaney!, mono- or phenyl, or frifiuormet anesuifonyioxy,
!n other Embodiments of Embodiment 8, i is a ' hydrocarbyi containing a terminal olefin. Examples of hydrocarbyi groups containing a terminal oiefin can be represented by
Examples of such hydrocarbyi groups include aiiy!, 3-buten-l-yl, S-hexen-1-yl, and - vinyfbenzyi.
in other Embodiments- of Embodiment B, Ri is a heterohydrocarbyi containing a terminal oiefin. Examples of hydrocarbyi groups -containing a terminal olefin can be represented by the formula (CH 2 =CH)-D- where D represents C 1 -C13 aikyl where at least one carbon atom, CH group, or CH2 group is replaced with a hetera atom selected from N, O, S, or Si or a beteroaryi or heterocycioaikyi group. Examples of such hydrocarPyi groups include (l-vinyf i eridin-4-y!}methyi, 4-(vinyiamino)butyi, (2-{vinylamsnoJethoxy)methyi, and (4- penien-1-yloxy)meihyl, {1-ai!yi-i H-imida2o!~4-yl)methyi, and ({6-aiiyipyridin-3- yl)methoxy)methyl.
In some Embodiments of Embodiment C, Ri is hydrogen, halogen or unsubstituted Gi-Gis aikyl, -CrCe aikoxyfCi-CeJalkyiamino, di(Ci-Cs}a!kyl-{Ca-G6}aikenylsslyi 5 haio(G ~ Cs)aikoxy, tri{CrCs}aikyisiSy!, fri{Ci-Ce}aikyisily!oxy, ha!o(Ci-Ce}aiky! f frs{di{Ci~
Cg}aikylamino)sslyi i CrCs alkoxy, C Cs alkyithio, thio, C C 8 aikanoyi. th(G Cs)aikyjQxysiiyi, difC CsJaikyiamino, tri{CrCe)aikyigermyi, tri{di{Ci- ¾)aSkylam!no}gemiyi, ih(C
Cgjaikyjoxygermyl, di(Ci-G6)aiky!phosphaneyi ( di{di(Ci~C)alky!amino}phosp janeyl, mono- or di(CrCi:o , 5a!kySaminQ, amino, hydroxy, phenyl, ortrt iuonTiethanesuifdnyioxy,
in other Embodiments of Embodiment C, Ri is a hydrocarbyi containing a terminal oiefin. Examples of such hydrocarbyi groups include ally], 3-buten-1-yi, 5-hexen-1-yi, and 4- viny! benzyl In other Embodiments of Embodiment C, Rt is a heterohydrocarbyS containing a terminal olefin. Examples of hydrocarbyl groups containing a terminal olefin can be
carbon atom, CH group, or CHb group is replaced with a hetero atom selected from M, O, S, or Si or a heteroaryi or heterocyoioalkyi group. Exampfes of such hydrocarbyi groups inciutle {1~vSnylpsperidin-4-yS}methyS, 4-(vinyiamino}buiy!, {2-{vsnyiarr)!no}eihoxy)methyi, and (4~ penten-1 -yioxyJmeihyS, { -3l!yi-1 H-imSda oi-4-yl)rriethyi, and ({8-3iiyfpyridin-3- yl)methoxy}methyi
In one embodiment, for Structure 1 , none of Ri through R12 form ring structures; and/or wherein for Structure 2, none of R« through Rs4 form ring structures. In one embodiment, for Structures 1 or 2, the cocaiaiysi comprises at ieast three halogen atoms, or at least 4 halogen atoms, or at least 5 halogen atoms, or at least 6 halogen atoms. In one embodiment, the cocatalysl comprises a structure selected from the following 1 ) through 95} (in each structure below, each black clot represents a boron atom):
in one embodiment, the CGcatalysf comprises a structure selected from the following 1 ) through 10} above, or from 1 ) through 5), or from 1 ) or 2} above.
Examples of suitable procatalysfs includ phenoxy type transition metal complexes (see, for example, 02G07/136497, WO2007/136496 and \A G20O7/136494), constrained geometry transition metal complexes (see for example, US 6034022, US6268444 and US 6121185), and bls-metallocene transition metal compiexes (see, for example, US 824570SJ. Each patent reference is incorporated herein by reference.
In one embodiment, the pracata ysts is selected from the following; (Structure c),
wherein for each of the Structures a through c, each M is independently, titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; and each n ' is an integer of from 0 to 3, and wherein When n is 0. X is absent; and each X independently is a monodentate ligand that is neutral, monoanionic, or dianionie; or two Xs are taken together to form a bideniate iigand that is neutral, monoanionic, or dianionie; and X and n are chosen in such a way that the metai-Sigand complex of formula (I) is, overall, neutral; and wherein for Structure a, Rt through R?, and for Structure b, Ri through -?, and for Structure e,. R-i through Ri e, are each, independently selected from the following: a {C^ ~C fj) ydro- carby!, a {C-j~¾Q)hetero-hydrocarbyl, a SiC 0 ^, a Ge(R fi )g, a P(R P ) 2> a NfR^, an OR c , a
SR C , a 0 2 , a CM, a CF 3 , a R c S{0)-, a R c S{0} 2 -. a (R c ) 2 OH~, a R c C(0)0- s a R c GC{Gh a
R C(0)N{R>, a (R^ CCO)-, a halogen atom, , a hydrogen atom, and wherein each of the hydrocarby!, heterohydrocarbyS, Si(R c ) 3! ' Ge(R¾, P(H , N{R N } 2 , OR c , SR C , R c S{0}- ! ?S{0)2-. (R C' ¾G*N-, c C(0)0-, R c OC{0}-, R c e{0}N{RK <R?) 2 NG(OH and wherein each
R group, independently, is unsubstituted or substituted with one or more s substituents, each R s independently is selected from halogen atom, a poiyfluoro substitution, a perfiuoro substitution, a F 3 C- , a FCH 2 0-, a F 2 HCO-, a F 3 CO-, a R 3 Si-, a R 3 Ge-, a RO-, a RS-, a
RS{0}- : a RS{0) 2 -, a R 2 P-. a ¾Ν-, a R 2 C=N-, a NC-, a RC{0)0-, a ROC(O)-, a
RC(0)N{R)-, or a R 2 NC(0)-; and
wherein for Structure a, R through R?, and for Structure b, R-s through Ry, and for Structure c, Rt through R;«, independently, optionally two or more R groups can combine together into one or more ring structures, with such ring structures having from 3 to 50 atoms in the ring excluding any hydrogen atoms; and wherein for Structure c, each Z independently is O, S ; N(C^~C Q)h ioc l, or
wherein for Structure c, L !« ■ (C- C^hydrocarbylene or (C^-C^ Q jheiero ydfo- carbyiene, wherein the {C^^^Jhydra arbyiene has a portion thai comprises a 3-carfeon atom to IQ-carfcon atom linker backbone linking the Z atoms in Structure c (to which L is bonded), and the (C^^Qjheterohydrocarbyiene has a portion that comprises a 3-atom to
10-atom linker backbone linking the Z atoms in formula {!}, wherein each of the 3 to 10 atoms
independently is a carbon atom or heieroatom, wherein each heteroatom independently is O, S, S(0), S{0> , S R¾, Ge( c ) 2> P{& or H{R ), wherein independently each c is, independently,
in one embodiment, the proeaiaSyst is selected from Structure e, as described abox'e. Some examples of the phenoxy type complexes (Structure e) include, but are not limited to, the following: bis( 2-oxoy1-3-{1 , 2,3,4 ,6,7,8,9-octahydroanthraceh-5-y1}-5- <IV) dimethyl; bis({2-Qxoyt-3- (1 ,2,3,4 ,6,.7,8,9-octahydroant racen-S-yl -5-(me!r¾yl)p eny1 )-2-phenoxy)propane-1.2- diyizirconium (IV) dichforide; bis((2-oxoy 1 -S-Cdibenzo- ί H-pyn'oSe+y 1 )-5-{methyf)pheny1 )-2- pbenoxy}propane-1 ,2-diyizirconium (iVJ dimethyl; bi$((2-oxoy 1-3-fdibenzo-l H-pyrroie-1 -y 1 }~ bie((2-oxoyi-3- {1 ,1 -dimethyiethy})piier ~S -y 1 )-5-{methy{)pheny 1 }~2-p ven oxyJprQpasie- ,2-diy izirconium (IV) dimethyl; bis((2-oxoy1-3~(1,l-dtm8thySe{hyS)phen-!-y1)-5-{m
propane- 1 ,2-diylzirconium (IV) dichioride; bis({2-oxoy1~3-{1 ,2,3,4,6,7, S,9-octahydro~ anthracen-5-y1)-5~(methyijpheny1 )-2~phenox y}-trans-cycSoh©xane-1 i 2-dimethyien 1~1 ;2~ diylzireortium (|V) dimethyl; bts((2-bxoy1~3-(1 ,2,3 i 4 i 6,7,8 i 9>octahy<lroarjfiiraiceivS--y1 >-5~ (methyl)pheny )-2-phenoxy)-transcyclohexane-1 ,2-dimethylenyl-1 ,2-dtySzirconium (IV) dichioride; bis((2-oxQy 1 -3-.{dibenzo-1 H-pyrrote-l -y 1 )-5n(methyj)pheny1 }*2-pftenpxyHrans « cydohexane-1 ,2-dimethy!enyl.l ,2-diy 1 zirconium (IV) dimethyl; bis({2~oxoy1 ~3-{dibenzo- 1H-pyrrpte- i-y1)-5 -(methyl )phenyi )-2-phenoxy)-trans-cyclohexane-1 f 2-dimethyieny1-1 ,2- diylziroonium (IV) dichioride; b!s((2 « oxoy1 -3-(1 ,1 » dimefhySethyl}phen » yi }-5-(methyi)- phenyl >2-phenoxy)-trans-cyeiohexaoe-1 ,2-dimethy!eny1-1 ,2-ciiylzirconium (IV) dimethyl; bis{{2*oxoy1-3-(l ,1-^methvie hy!¾rfjervl-y1)-S-<me{hy { )ph©ny1 )H2*pfceRGx )~
transcyc!ohexane- 1 ^-dimeihylenyl-l ,2-d|ylz|rconium (IV) dichioride; bis((2-oxoy1 - S » (I^S^.ej^S-oct h S o-anthracen-S^
,3-dsylzirconlum (NJdlmethy!; bis((2-oxoy1-3~(1 ,2,3,4,6,7, 8.,9-oct h ydroanthracen-S-yl }-5 - (methy!)pheny )-2-phenox y)~cis-cycloh®xane-1 ( 3~diyizirconfum (IV). dichioride; bis((2~oxoyi- 3~(dtbenzo-i ' H-pyrro e- 1-yl}~S-( fethyl}pheny1 }~2-phenoxy}~eis-cyc!Qhexane- 1.3- diylzirconiu (N) dimethyl; and bss{{2-oxQy1-3-{d bsnio- H-pyrrole- 1-y1)-5- {methy!}pheny1 )-2-phenoxy)-Gss-cyc!ohexane-1 ,3-dfy! irconium (IV) dichloride.
In one embodiment, the procataiysts is selected from Structure a, as described
S above.
Some examples of the constrained geometry complexes (Structure a) Inciude, but ere not limited to, the following: (tert-butylamido)(1 -dimeihyS~2,3 5 4 t 9-hexahydronaphihai~eny1) dimethylsiianeiiianiumdimethyi; (iert-but^amidoK1 » l i 2 > 3-tetramett5y1-2,3 » 4.9 ! 10-l l- 1 ,4,S,e,7,8hhexahydr!CH»afrf»tiiate.oyl) dfmethylsiianetitaniumdimethyi; {tert-butyiamido}-
10 (tetrameihyl -6-cycSopentadienyi) dimethylsilanetitanium dibenzyl; {terl-biiiylamido}-
{ietra ethyl -15-cyelopentadienyl) dimethylsilanetitanium dimethyl; (tert-butyiamidGXtetra- methy1~5-cydopentadieny1 )-1 ,2-ethanediyltitanium dimethyl; (tert-bu!ylamidG}(tetra~methy1~ 1 S-cyeSopentadienyl) dimethylsilane titanium (III) 2-(dimethylamino)benzyl; (tert- butyiamido)(tetrametby1-15-cyclo-peotaciienyl} dimethylsilanetitanium (Hi) 2,4~dimethyi-
! 5 pentadienyi: (tert-buty!amido)--(tetramethyl-IS-cyclopeiitadieny!} dimethyisiianetitanium (IS) 1 ,4~diphenyl- 1 ,3-butadiene; (terf-butyiamidoXietramethy 1-T5~cyciopentadienyi} dimethylsilanetitanium {il} 1 ,3-pentadiene; (tert-buiy!amido}(2-methy!Sndenyl} di nethy!- silanetitahium {!!) 1 ,4-diphenyi- 1 ,3-butadiene; (tert-butytamsdo}{2 methyiindenyl}- dimethylsiianetiianium {11} 2,4-he adiene; and {tertbutyl-amid }(2~methyitndenyi)
0 dimethylsiianetltanium {SV} 2,3-dimethyi- 1 ,3-butadiene.
In one embodiment, the procataiysts is seiected from Structure fa, as described above.
Some examples of the bia-metallocene complexes (Structure b) include, but are not limited to, the following; bis(cyciopentadfenyi} zirconium dimethyl,; bis(cyclopentadienyi} 5 zirconium diethyl; bis{cyclopentadienyl)zirconiurn dipropyi; bis{cyclopentadienyf) zirconium difouty!; bis{cycfc>pentadienyl) zirconium diphenyi; bis(cyciopentadieny!) zirconium dineopentyl; bis(cyclopentadienyl) zirconium di(m-tolyl); bis(cyclopentadienyf} zirconium di{p~toiyi); bls butyicyciopentadienyi) zirconium dimethyl; bis-(tbu ylcyclo-peniadienyi) zirconium dimethyl; and bis(cyc!ohexyimethyicyciopentadieny!} zirconium dimethyl, 0 In on embodiment, the cocataiyst comprises a structure seiected from Structure 1 , in a further embodiment, the cocataiyst structure further comprises at least one cation seiected from the following structures a)-f), r) o q), each as described above.
in one embodiment, for Structure 1 . the hydrocarbyi and/or the heterahydroc byl is/are each independently substituted with one or more substituents RS; and each RS Is 5 independently a halogen atom, poiyfiuoro substitution, perfiuoro substitution, F3C-, FCH20-, FgHCO-, F3CO-, R 3 Si-, R 3 Ge-, RO-, RS-, RS(O)-, RS(0) 2 -, R 2 P-, 2 N ". 2C= -, NC-, RC(G)0-, OC(Oh RC{0)N(Rh or R 2 NC{Ok wherein each R independentiy is an unsubstituted (C-j -C j g)aikyl.
In- one embodiment, for Structure 1, wherein each of R through R¾ is unsubstituted, in one embodiment, for Stascture 1, two or more of Ri through f½ term one or more ring structures, wherein said ring structures have from 3 to 50 atoms in the ring, excluding any hydrogen atoms,
in one embodiment, for Structure 1, none of R¾ through F½ form ring structures, in one embodiment, for Structure 1, the cocataiyst comprises at ieast three haiogen atoms, or at ieast 4 haiogen atoms, or at least 5 halogen atoms, or at feast 6 haiogen aioms, Structure may comprise of a combination of two or more embodiments described herein.
In one embodiment, the cocataiyst comprises a structure selected from Structure 2. in a further embodiment, the cocataiyst structure further comprises at least one cation selected from the following structures k)-p), each as described above.
In one embodiment, for Structure 2, the hyolrocarbyi and/or the heterohydfocar yi is/are each independently substituted with one or more substituents R S ; and each R S is independently a haiogen atom, poiyfiuoro substitution, perfiuoro substitution, F j G-, FCH 2 Q-,
FgHCO-, F3CO-, R 3 Sk R 3 G « , RCh RS-, RS(O)-, RS{0} 2 -, R 2 P « . ¾ N ">
RC{0}0-, ROC{0)-, C(0)N(R}-, orR 2 NC0)-, wherein each R independently is an unsubstituted {C^-C†g}alk !.
!n one embodiment, for Structure 2, each of RK through R;« is unsubstituted, in one embodiment, for Structure 2, two or more of 13 through R ¾ form one or more ring structures, wherein said ring structures have from 3 to 50 atoms in the ring excluding any hydrogen atoms, in one embodiment, for Structure 2, none of K« through ¾ form ring structures,
in one embodiment, for Structur 2, the cocataiyst comprises at Ieast three halogen atoms, further a ieast 4 halogen atoms, further at ieast 5 halogen atoms, further at Ieast 6 halogen atoms.
Structure 2 may comprise of a combination of two or more embodiments described herein.
Also is provided is a polymer composition comprising the poSymer product of the following: ethylene or propylene with one or more a-o!efin copolymers and/or one or more dishes, and wherein the polymer product is polymerized in the presence of the cataiyst system of any one of the previous claims. Also is provided a process for producing a polymer com osition, said process comprising; selecting ethylene or propylene; and polymerizing said ethylene or propylene, with one or more o-olefin copolymers and/or one or more dienes, in the presence of the catalyst system of any one of claims 1 to 23,
in one embodiment, the polymerization ' temperature Is from -20*0 to 350 * C.
Also Is provided is an article comprising at least one component formed from an inventive polymer composition.
X - substiiuerrt such as haiogen or a!kyi grou
L<3 ~ tea ving group
Definitions
Unless stated io the contrary, all test methods are current as of the filing date of this disclosure.
The term "substituted," as used herein, with respect to a chemical compound, refers to a substituent, i.e., a group that replaces hydrogen on, for example, a carbon atom, that comprises at least one carbon atom or, preferably, at least one heteroatom (for example, Θ, S, N, P, etc.), Substituents Include, but are not limited to, the R s substituents, as noted above, as the following', a halogen atom, a polyfluoro substituent, a perfiuoro substituent, F 3 C~, FCH 2 Ch F 2 HCO-, F 3 CCh {R) 3 Sk (R) 3 <3e-, ( )O-, (R)S~, (R}S{0) (R)S(0) 2 - ;
(R} 2 P- > (R½N., (R} 2 C=M«, NC, (R)G{0}0-, (R)OC(O} CR}C(G)N£R} -, and (R) 2 NC(0) wherein each " independently is an unsubstftuted {C^-C^g)alkyl.
The term "unsubstituted," as used herein, with respect to a chemical compound, refers to the lack of a substituent that comprises at least one heteroatom (for example, Q, S, N. P, etc.).
The term "hydrocarbyi," as used herein, refers to a monovalent (monoradicai or radical) chemical group containing onl hydrogen and carbon atoms. Examples of
hydrocarbyi groups are alky! groups, aikenyl groups, cye!oaikyl groups, and aryl groups. The term "substituted hydrocarbyi," as used herein, refers to a hydrocarhy!, in which at (east one hydrogen atom is substituted with a substituent that comprises ai least one heteroatom.
The term "heterahydrocarbyi," as used herein, refers to a hydrocarbyi, in which at least one carbon atom, or CH group, or CH2 group, is replaced with a heteroatom or a chemical group containing at least one heteroatom. Examples of such heterohydrocarbyi groups are CH3O- (methoxy), CH 3 CH 2 NH- (ethylamino), (Ch^CI^^NCgH^
{ imethylaminophenyl), CH3OCH2CH2OCH2- (methoxyethoxymethyl), Heteroatoms include, but are not limited to, O, N, P, Si and S, Other examples of heterehydrocarbyi groups include heterocycloaikyi groups such as pipertdinyl, piperazinyi, rnorphoisnyt, furyl, pyrrotidin- 1 -yimet yS, azepan-1-yl methyl, and thiazolidin-3-ylmethyl, and heteroaryi groups such as pyridiny!, pynrnidirsyS, pyridin-4-ylmethyl, imidazolyl, imidazolylmethyi. thiazolyt and oxazoiyl.
The term "substituted heterohydrocarbyl, " as used herein, refers to a seterohydro- carfoyl in which at least one hydrogen atom is substituted with a substituent that comprises at least one heteroatom.
The term "hydrocarbyiene," as used herein., refers to a divalent (diradicaS) chemical grou containing only hydrogen and carbon atoms. The term "substituted hydrocarbyiene," as used herein, refers to a hydrocarbyiene, in which at least one hydrogen atom is substituted with a substituent that comprises at least one heteroatom.
The term "heterohydrocarbySene," as used herei . refers to a hydrocarbyiene, in which at least one carbon atom, or CH group, or CH 2 group, is substituted with a heteroatom or a chemical group containing at least one heteroatom, e.g. -C^C^OCf-^Ch^- (oxydi-
{2 -eihane)etiy!}, -CH2CH2CH2CH2O- (4-butaneyl-1-oxy), -OCH2CH2O- {1 ,2-efhanediyi- bis{Qxy)}. Heteroatoms include, but are not limited to, O, N, P, Si and S. The term
"subst tuted heterohydrocarbytene," as used herein, refers to a heterohydrocarby!ene in which at least one hydrogen atom is substituted with a substituent that comprises at least one heteroatom.
The term "aryi," as used herein, means a phenyl (i.e., monocyclic aryl), or a bicyclic ring system containing at least one phenyl ri g or an aromatic bicyclic r ng containing only carbon atoms in the aromatic bicyclic ring system. The bicycle aryi can be azu!enyl, napbtbyl, or a phenyl fused to a monocyclic cycloalkyi, a monocyclic c c!oalkenyl, or a monocyclic heterocyclyl. The bicyclic aryl is attached to the parent molecular moiety through any carbon atom contained within the phenyl portion of the bicyclic system, or an carbon atom with the napt yl or a uienyl ring. The fused monocyclic cycloalkyi or monocyclic heterocyclyl portions of the bicyclic aryi are optionally substituted with one or two oxo and/or thioxo groups. Representative examples of the bicyclic aryis include, but are not limited to, azuienyS, naphfhyi, dihydroinden-l-yi, dihydroinden-2-yi, dfhydroind¾n-3-yl, dihydrQinden~4-yS, 2,3-dihydroindol-4-yl, 2,3-dihydroindol-5-yl, 2,3-dihydroindol-6-yl, 2,3-dihydroindoi-7-yl, inden- 1 -yl, inden-2-yl, inden-3-yl, inden-4-yl, dihydronaphthalen-2-yl, dihydronaphthaien-3-yl, dihydronaphthalen-4-yi, dihydronaphthaien-1 -y!, 5,8,7,&4etrahydronaphthaien-1 -yl, 5,6,7,8- tetrahydronaphthalen-2-yl, 2,3-dihydro:benzofuran-5-yl, 2 ) 3-dih drobenzofuran-6-yl, 2,3-dihydrobenzofuran-7-yl, benzo[d][1 ,3]diQxo!-4~yi,
benzoidj[1 ,3]dioxGf-5- l, 2H-chromen-2-on-5-yl, 2H-chromen-2-on-6-yi, 2H-chromen-2-on-7- y!, 2H-chromen-2-on-8-yl, isoindoline-1 ,3-dion-4-yl, isoindoline-1 ,3-dion-5-yi t ind8n-1-on- -yl t inden-1-on-5-yi. inderv1-on-6-yl, inden-1-on-7-yl, 2,3-d!hydrobenzo[b|i 4]dioxan-S-y!, 2,3- dihydroberszo[b][1 ,4jdloxan-6-yl 5 2H-benzo{b][1 ,43oxazin3(4H)-on-5-yl, 2H- beriZo|b 1 ,43oxazin3{4H)-ofi-6~y! I £H~ben2o[b]|[l i 4]oxazin3{4H)-on~7-yl ! 2H~
benzofbIi j 4 oxazin3(4H}-on-e~y! ! benzojo axazin^iSHJ-on-S-yl, benzo|d3oxazin-2{3H}-on-6- yj, benzo[d]oxazin-2{3H)-on-7-yl, benzo[d]oxazin-2(3H)-on-8-yl, quinazoiin-4(3H)-on-5-yi, qu!nazolin-4(3H)-on-6-yl, quinazolin-4(3H)-on-7-yl, quinazolin-4(3H)-an-S-yl > qyinoxaiin- 2(1 Η}-οη~5-ν1, quihoxalio-2{1 H)-on-6-yl « quinoxalin-2{1 H)-on-7-yl, q«tn xalin-2(1 H)*oi 8-y!, benzofd|thiazoi-2(3H}-on-4-yi, benzo[dJthiazoS-2{3H -on-S-yi, benzoid3thfazo!-2(3H)-on-6 » l > and, benzo{djthiazoi-2(3H)-on-7-yi in certain embodiments, the bicyciic afyl is (s) naphthyi or (si) a phenyl ring fused to either a 5 or e membered monocyclic cycioalkyi, a 5 or δ membered monocyclic eycloaikenyi, or a § or 6 membered monocyclic hetefoe c!yl, wherein the fused cyeloaikyl, eycioalkeny!, and heterocyciyi groups are optionally substituted with one or two groups which are . independently oxo or thioxo.
The term "cyc!oaSky or "cyc!yf as used herein, means a monocyclic or a bicyciic cycloaiky! ring system. Monocyclic ring systems are cyclic hydrocarbon groups containing from 3 to S carbon atoms, where such groups can be saturated or unsaturated, but not aromatic. I certain embodiments, cyctoaikyi groups are fully saturated. Examples of monocyclic cyclaaikyis Include cydopropyi, cyclobutyi, cyeiapeotyi, cyclopentenyi, cycfohexyl, cyciohexenyi, cycloheptyl, and cycioocty!. Bicyciic cycloa!kyf ring systems are bridged monocyclic rings or fused bicyciic rings. Bridged monocyclic rings contain a monocyclic cycloaiky! ring where two non-adjacent carbon atoms of the monocyclic ring are linked by an alky!ene bridge of between one and three additional carbon atoms ( .©., a bridging group of the form -(CH¾V. where w is 1 , 2, or 3). Representative examples of bicyciic ring systems include, but are not limited to, bicycto[3>1.Ijheptane, btcycio{2.2, ijheptane,
icycto 2.2,23oetane, bicyclo[3.2.2]nonane, bicycio[3.3.1]nonane, and bjcyc!o[4.2, 3nonane. Fused bicyciic cycioalkyi ring systems contain a monocyclic cycloaiky! ring fused to either a phenyl, a monocyclic cycioalkyi, a monocyclic cyc!oa!kenyl, a monocyclic heterocyciyi, or a monocyciic heteroaryS. The bridged or fused bicyciic cycfoaSky! is attached, to the parent molecular moiety through any carbon atom contained within the monocyciic cydoaikyi ring. Cyctoaikyi groups are optionally substituted with one or two groups which are independently oxo or ' thtoxo. In certain embodiments, the fused bicyciic cycioalkyi is a 5 or 8 membered monocyciic cycloaiky! ring fused to either a phenyl ring, a 5 or 6 membered monocyclic cycioalkyi, a 5 or 6 membered monocyclic cycioalkeny!, a 5 or 6 membered monocyclic heterocycSyS, or a 5 or 6 membered monocyclic heteroaryl, wherein the fused bicyciic eycloaikyi is optionally substituted b one or two groups which are independently oxo or thioxo.
The term "halo" or "ha!ogen" as used herein, means -Ci, -Br. -! or -F.
The terms "haioatkyf and "haloaSkoxy" refer to an alky! oralkoxy group, as the case may be, which is substituted with one or more halogen atoms.
The term 6 heteroary!, s as used herein, means a monocyclic heteroaryl or a bieyciic ring system containing at feast one heteroaromatic ring. The monocyclic heteroaryl can be a
5 or 6 membered ring. The 5 membered ring consists of two double bonds and one, two, three or four nitrogen atoms and optionally one oxygen or sulfur atom. The 6 membered ring consists of three double bonds and one, two, three or four nitrogen atoms. The 5 or 8 membered heteroaryl is connected to the parent molecular moiety through any carfco atom or any nitrogen atom contained within the heteroaryl. Representative examples of monocyclic heteroaryi include, but are not limited to, furyl, imidazolyi, ssoxa o!yl, isothiazoSyl, oxadiazo!yi, oxazofyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrazoiyi, pyrrolyi, tetrazo!yi, thiadiazolyl, thiazolyl, thienyl, triazolyl, and triazinyl. The bicyciic heteroaryi consists of a monocyclic heteroaryl fused to a phenyl, a monocyclic cycioalkyi, a monocyclic ' cycloaikenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl. The fused cycioalkyi or heterocyelyl portion of the bicyciic heteroaryi group is optionally substituted with one or two groups which are independently oxo or thioxo. When the bicyciic heteroaryi contains a fused cycioalkyi, cycioalkenyl, or heterocyclyl ring, then the bicyciic heteroaryl group is connected to the parent molecular moiety through any carbon or nitrogen atom contained within the monocyclic heteroaryi portion of the bicyciic ring system. When the bicyciic heteroaryi is a monocyclic heteroaryi fused to a benzo ring, then the bieyciic heteroaryi grou is connected to the parent molecular moiety through any carbon atom or nitrogen atom within the bicyciic ring system. Representative examples of bicyciic heteroaryi include, but are not limited to, benamidazo!y!, benzofuranyi, enzothienyl, benzoxsdiazoiyl, benzoxathiadiazoly!,
.benzoihjgzpjy!, cinnoiiny!, S.e-dihydroquinoiin-S.-yi, S,6~dihydroisQquinolin-1-yi, furopyrldlny!, indazoiyl, Indoly!, isoquiholiny}, naphthyridinyi, quinolinyl, purinyi, 5,8,7;8"te»ahydro juinojln- 2-yl, 5A7 > .8-tetrahydroquirto!in-3~yi, 5,8 > ?,8-tetrahydroquino!in-4-yl, 5,6,7,8- tetrahydroisoquinolin-1-yl, fhienopyridinyi, 4,5,S,?-tetrahydrobenzo c l ,2,5loxadiazoiyS, 2,3- dihydroihieno[3,4-o¾1 ,4]diqxan-5-yl, and 6,7-dihydrobenzo c|l ,2,53oxadfazo!-4(5H)-onyi, in certain embodiments, the fused bicyciic heteroaryi is a 5 or 6 membered monocyclic heteroaryl ring fused to either a phenyl ring, a 5 o 6 membered monocyclic cycioalkyi, a 5 or 6 membered monocyclic cycloaikenyl, a 5 or 8 membered monocyclic heierocyciyi, or a 5 or
6 membered monocyclic heteroaryi, wherein the fused cycioalkyi, cycloaikenyl, and heterocyclyl groups are optionally substituted with one or two groups which are
independently oxo or thioxo.
The terms "heterocyclyl" and "heterocycloalkyl" as used herein, mean a monocyclic heterocycie or a bicyclic heterocycie. The monocyclic heterocycle is a 3, 4, 5, S or 7 membered ring containing at least one rseteroaicm independently seiected from the . group consisting of O, N, and S where the ring is saturated or unsaturated, but not aromatic. The 3 or 4 membered ring contains 1 heteroatom seiected from the group- consisting of O, N and S, The 5 membered ring can contain zero o one double bond and one, two or three heteroatoms selected from the group consisting of O, N and S. The 6 or 7 membered ring contains zero, one or t o double bonds and one, two or three heteroatoms selected from the grou consisting of 0, N and S, The monocyclic heterocycle is connected to th parent molecular moiety through any carbon atom or any nitrogen atom contained within the monocyclic heterocycle. Representative examples of monocyclic heterocycle include, but are not limited to, azetidinyl, azepanyl, aziridinyl, diazepanyl, 1 ,3-dioxanyt 1 ,3-dioxoianyS, 1 ,3-dithio!anyl, 1 ,3-dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyS, isoiiliazolidinyl, isoxazo!inyi, isoxaEoiidinyl, morpholinyl, oxadiazolinyl, oxadiazolidiny!, oxazolinyi, oxazo!idinyi. psperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrroiinyl, pyrrolidinyl, tetfahydrofuranyi. fetrahydrothienyl, thiadiazolinyl, thiadiazolidinyl, thiazolinyl, thiazolidinyl, thiomorpholinyl, 1 ,1-dioxidothiomorpholinyl (thiomorpholine sulfone), thiopyranyi, and trithianyl. The bicyclic heterocycle is a monocyclic heterocycie fused to either a phenyl, a monocyclic cycioalkyl, a monocyclic cyctoafkeny!, a monocyclic heterocycle, or a monocyclic heteroaryi. The bicyclic heterocycle is connected to the parent molecular moiety through any cartoon atom or any nitrogen atom contained within the monocyctic heterocycle portion of the bicyclic ring system. Representative examples of bicyclic heteroeyciyis include, but are not imited to, 2,3-dihydrobenzofuran-2-y1, 2,3-dihydrobenzofufan-3-yl, Molin-1-yS, sndo!in-2~yl s indolin-S-yl, 2.3-dihydrobenzothien-2-yl, decahydroquinoiinyl, decahydroisoquinolinyl, QCtahydro-IH-indoh/i, and octahydrobenzofuranyl. Heterocyclyl groups are optionally substituted with one or two groups which are independently oxo or thioxo, in certain embodiments, the bicyclic heterocyciyi is a 5 or 6 membered monocyclic heteroeyciyS ring fused to phenyl ring, a 5 or 6 membered monocyclic cycioaiftyi, a S or 6 membered monocyclic cycloalkeny!, a 5 or 8 membered monocyclic heterocyclyl, or a 5 or 8 membered monocyclic heteroaryi, wherein the bicyclic heterocyclyl is optionally substituted by one or two groups which are independently oxo or thioxo. The term "composition," as used herein, includes a mixture of materials which comprise the composition, a well as reaction products and decomposition products formed from the materials of the composition.
The term "polymer, * as used herein, refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces th term homopoiyroer {employed: to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorpo-rated into the polymer structure), and the term interpoSymer as defined hereinafter. Trace amounts of Impurities, for example, catalyst residues, may be incorporated into and/or within the polymer.
The term "interpolymer," as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term Inferpoiymer thus includes copolymers- (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
The term, '"oiefin-based polymer," as used herein, refers to a polymer that comprises, in polymeri ed form, a majority amount of olefin monomer, for example ethylene or propylene (based on the weight of the polymer), and optionally may comprise one or more
comonomers. The term, "olefin-based interpolymer," as used herein, refers to an interpolymer that comprises, in polymerized form, a majority amount of olefin monomer, for example ethylene or propylene (based on th weight of the interpolymer), and at least one comonomer. The term, "olefin-based copolymer," as used herein, refers fo a copolymer that comprises, in polymerized form, a majority amount of olefin monomer, for example ethylene or propylene (based on the weight of the copolymer), and a comonomer, as the only two monomer types.
The term, "ethylene-based polymer," as used herein, refers to a polymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the polymer), and optionally may comprise one or more comonomers. The term, "ethyiene- ased interpolymer," as used herein, refers to an interpolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the interpolymer), and at Seast one comonomer. The term, "ethylene-based copolymer;" as used herein, refers to a copolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the copolymer), and a comonomer, as the only two monomer ty pes .
The term, "ethylene/a-olefin interpolymer," as used herein, refers to an interpoiymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the interpolymer), and at least one a-olefln. The term, "ethylene/a-olefin copolymer," as used herein, refers to a copolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the copoiymer), and an ø- olefin, as the only two monomer types.
The term, "propylene-based polymer," as used herein, refers to a polymer thai comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the polymer), and optionally may comprise one or more comonomers. The term, "propyiene-based inierpo!yn ." as used herein, refers to an interpolynw that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the interpolymer), and at least one comonomer. The term, "propylene-based copoiymer," as used herein, refers to a copoiymer that compnses, in polymerized form, a majority amount of propylene monomer (based on the weight of the copoly mer), and a comonomer, as the only two monomer types.
The term, "propylene/a-olefin interpolymer," as used herein, refers to an interpoiyme that comprises, in polymerized form, a majority amount of propylene monomer (based on th weight of the interpoiymer), and at least one a-oiefin. The term, "propylene/a-o efin copoiymer," as used herein, refers to a copolymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the copolymer), and an a- oiefin, as the oniy two monomer types.
The term, "prepylene/eihyiene interpolymer," as used herein, refers to an interpoiymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of ' the Interpolyfner), and ethylene. The term, "propylene/ethylene copoiymer;' as used herein, refers to a copolymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the copoiymer), and ethylene, as the oniy two monomer types.
The term "proeatatyst" a used herein refers to a transition metal complex, which when activated with a cocataiyst, is capabl of polymerizing one or more aipha-otefins. Examples, or proeata!ys s include, but are not limited to, bis-metafiocene complexes, constrained geometry complexes, and phenoxy type complexes.
The terms "comprising," "including," "having," and the r derivatives, ar not intended to exclude the presence of any additional component, ste ' or procedure , whether or not the same is specifically disclosed, in order to avoid any doubt, aii compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary, in contrast, the term, "consisting essentiaiiy of excludes from the scope of any succeeding recitatio any other component, step or procedure, excepting those that ar not essentia! to operabiiity. The term "corv sisting of excludes any component, step or procedure not specifically delineated or listed.
Test Method Deristfy - Samples that are measured for density are prepared according to ASTM D-1928, Measurements are made within one hour of sample pressing using ASTM D-792, Method 8.
M&it index - e!t index (fe) is measured in accordance with ASTM-D 1238, Condition 190 °C/2.16 kg, and is reported in grams eiuted per 10 minutes . Melt flow rate (lio) is measured in accordance with ASTM-D 1238, Condition 190 *C/10 kg, and is reported in grams e!uted per 10 minutes,
Ge! Permeation Chromatography (GPC)
The ethyiene alpha-Diefin interoa!ymers were tested for their properties via GPC, according to the foSlowing procedu e. The GPC system consists of a Waters ( Hford, MA) 150"C high temperature chromatograph (other suitable high temperatures GPC instruments include Polymer laboratories (Shropshire, UK} Model 210 and Mode! 220} equipped with an on-board differential refractometer (Rl). Additional detectors can Include an I 4 Infra-red detector from Polymer ChAR (Valencia, Spain}, Precision Detectors (Amherst, MA) 2-ang!e laser light scattering detector Model 2040, and a Vlscotek (Houston, TX) 150R 4-capiary solution viscometer. A GPC with the last two independent detectors and at least one of the first detectors is sometime referred to as "SD-GPC, while the term "GPC alone generally refers to conventional GPC. Depending on the sample, either the 15-degree angle or the 90- degree angle of the light scattering detector is used for calculation purposes. Data collection is performed using Viscotak TriSEC software, Version 3, and a 4-channel Vlscotek Data Manager DM400.
The system is also equipped with an on-line solvent degassing device from Polymer Laboratories (Shropshire, UK). Suitable high temperature GPC columns can be used such as four 3Q cm Song Shodex HTS03 13 micron columns or four 30 cm Polymer Labs columns of 20-micron rnixed-pore-stee packing (MixA LS, Polymer Labs}. The sample carousel compartment is operated at 140 ^C and the column compartment is operated at 150 C C The samples are prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and the sample preparation solvent contain 200 ppm of butylated hydroxytoiuene (BHT), Both solvents are sparged with nitrogen. The polyethylene samples are gently stirred at ISO : *G for four hours. The injection volum is 200 microliters. The flow fate through the GPC is set at 1 ml/minute.
The GPC column set is calibrated before running the Examples by running twenty- on narrow molecular weight distribution polystyrene standards. The molecular weight (MW) of the standards ranges from 580 to 8,400,000 grams per mole, and the standards are contained in 6 "cocktail" mixtures. Each standard mixture has at least a decade of separation between individual molecular weights. Th standard mixtures are purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at "0,025 g in 50 ml of solvent * for molecular weights equal to, or greater than, 1 ,000,000 grams per mole, and at "0,05 g in 50 mi of soivenf for molecular weights less than 1 ,000,000 grams per mole. The polystyrene standards were dissolved at Q"C with gentle agitation for 30 minutes. The narrow standards mixtures are run first and in order of decreasing highest molecular weight component to minimize degradation . The polystyrene, standard peak molecular weights are converted to polyethylene using the Mar&Houwink K and a {sometimes referred to as o) vaiues mentioned iater for polystyrene and polyethylene. See the Examples section for a demonstration of this procedure.
With 3P-GPC, absolute weight average molecular weight f Mw, . ') and intrinsic viscosity are also obtained independently from suitable narrow polyethylene standards using the same conditions mentioned previously. These narrow linear polyethylene standards may be obtained from Polymer Laboratories (Shropshire, UK; Part No.'s PL2650-0101 and PL2650-0 02},
The systematic approach for the determination of mufti-detector offsets is performed in a manner consistent with that published by Baike, Mourey, et al. ( ourey and Baike,
Chromatography Poiyffi,, Chapter 12, (1992)} {Baike, Thitirafsakul, Lew, Cheung, Mourey, Chromatography Poiym., Chapter 13, {1992}}, optimizing triple detector log (Mw and intrinsic viscosity) results from Dow 883 broad polystyrene (American Polymer Standards Corp.; Mentor, OH) or its equivalent to the narrow standard column calibration results from the narrow polystyrene standards calibration curve. The molecular weigh data, accounting for detector volume off-set determination, are obtained in a manner consistent wit that published hy Zimm (Zsmm. B.H„ J. Chem. Rhys., 16, 1099 (1948)} and Kratochvli (Kratochvli, P„ Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY {1987}). The overall injected concentration used in the determination of the molecular weight is obtained from the mass detector area and the mass detector constant derived from a suitable linear polyethylene homopolymer, or one of the polyethylene standards. The calculated molecular weights are obtained using a light scattering constant derived from one or more of the polyethylene standards mentioned and a refractive index concentration coefficient, dn/dc, of 0.104. Generally, the mass detector response and the light scattering constant should be determined from a linear standard with a molecular weight in excess of about 50,000
Daitons, The viscometer calibration cart be accomplished using the methods described by the manufacturer or alternatively by using the published values of suitable linear standards such as Standard Reference Materials (SR!Vfj 1475a, 1 828, 1483, or 1484a, The chromatographic concentrations are assumed low enough to eliminate addressing 2 nd viral coefficient effects (concentration effects on molecular weight).
Determination To obtain values, the chromatographic system consist of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-22G. The column arid carousel compartments are operated at 140¾. Three Polymer Laboratories 10-μτη ixeci-B cofumns are used with a solvent of 1.,2,4-tncft!orobenzene. The samples are prepared at a concentration of Q.i g of polymer in 50 l of solvent. The solvent used to prepare the samples contain 200 ppm ol the antioxidant buty!ated hydraxyto!uene {BHT}. Samples were prepared by agitating Sightly for 4 hours at 160°C. The injection volume used is 100 microliters and the flow rate is 10 ml/min. Calibration of the GPC column set is performed with twenty one narrow molecular weight distribution polystyrene standards purchased from Poiymer Laboratories, The polystyrene standard peak molecular wights are converted to polyethylene molecular weights using Equation 1A: Mpoiyetk ie - A * {^polystyrene) { QH 1A), where M is the molecular weight, A has a value of 0.431S, and B is equal to 1.0. A third order polynomial is determined to build the logarithmic molecular weight calibration as a function of e!ution volume. Polyethylene equivalent molecular weight calculations are performed using Viscotek TriSEC software Versio 3,0. The precision of the weight-averag molecular weight « is excellent at < 2.8 %.
'H-NMR - Ή-NMRspectm (500 MHz or 400 MHz) were obtained on a Varian VNMRS-500 or VNMRS-400 spectrometer, at 30°C, unless otherwise noted. The chemical shifts were referenced to
Experimental
The following examples illustrate the present invention but are not intended to limit the scope of the invention.
Procatalysis {P AT 1-4)
PCAT2
PCATI
PCAT3 PCAT4
Cocais/ysfy - 1) "Art Bor" stands for aninsum Borate tM¾ {H)Ph (CgFg} l " . 2} "Carb" 3} "Bis H borate" for
bis{h drogenated-tailowaikyi)methySammoniuni tetrakis{pentafuorap:henyi)borate [{C-^g. 22^37 - 5¾^^ e ^i * K^i¾^5¼3 Ranges in atoms subscripts depicts that the cation is a mixture of various chain lengths. 4) -'Carb-H" for [ e 2 N ' {H)Phf JHGB 1 1 H 1 1 †. 5} "Bis H CmW for [(C 18 . 22 H 37 .4 S } 2 N(Me)H] HCB 1 1 CI 1 1 " 8} "Bis H Cartx-Me* for {(C^Q^H^J.
Synthesis of fM&gifMP iHCBj Cljjf Card)
In A filied glovebox, I e 2 <H)Ph]CI {74.0 mg, 0.469 mmoi) and Na[HCB 1 1 C1 1 ]
(255.8 mg, 0.469 mrrio!) were combined, as solids, in a 50 mL culture tube, and
approximately 10 ml of CgHgF was added. The mixture was ieft to stir for 18 at room temperature (RT). The solution win white precipitate was filtered over a pad of Celite, into a 25 mL Schlenk flask, and the precipitate was washed with 3 x 2 mL of CgHgF. VolatS!es were removed from the filtrate yielding a white solid. The solid was collected, and rinsed with 3 x 2 mL of pantane. Solid was transferred to 10 ml Schlenk flask, and dried under vacuum for 2 hours at RT. 1 H MMR showed approximately 7% residual CgHgF (corrected MM
650.8341 g/moS). Yield: 243,4 mg, 0.3740 mmoi 80%. S H HMR f 500 MHz, {CD 2 CI 2 ): δ 7.94 {Si 1H, N~H), 7.63-7.66 (m, 3H, Ar-H), 7.55 (d, J = 8 Hz, 2H, Ar-H), 3.4? (s, SH, MegNH-Ph), 3.32 (S, 1 H, HCB 1 1 Ci 1 1 ).
CsjJHCB^H-j (347.2 mg, .28 mmol) was dissolved in approximately 5 ml. H2O at
80*C. A solution of £Me2N{H)Ph}Ci (138,4 mg, 1.26 mmol) in water was combined with ti
Cs[HB-| -j †J soiution, and a white precipitate was observed. The mixture was ieft to stir for two hours, then allowed to cool to RT, The white solid was collected on a g!ass frit, washed with 3 x 2 mL H 2 0, followed by 3 x 2 ml psntane. The solid was transferred info a 10 ml Sch!enk flask, and then dried under vacuum overnight at 40 * 0. Yleid: 182.7 mg, 0.689 mmol, 55%. ! H NMR, 500 MHz, {CD 2 C½): δ 8.22.(8, 1 H, N-H), 7,65-7.61 (m, 3H, Ar-H), 7.55
(d, J = 8 H2..2H, Ar-H), 3.41 (s, 6H, M¾NH-Ph), 2.50 (s, 1 H. HCB^H^ ), 2.26-1.19 (br m,
1 1 H, HCB^ H-| " | ). Synthesis OffiC 1 8„22 Η 37~45Ϊ 2 n ( MbW ^ hcb 11&1 jf i H Carb)
in a 50 mL Schienk flask, a solution of NafCHBnC!nj (32? mg, 0.600 mmol) in 10 mL fiuorobensene was added to a solution of {(C g_22^37- S½^^ fe ^^ m S * 0 , 600 mmol) in 10 ml fluorobenzene. Upon mixing, precipitate formed immediately, and the mixture was further stirred for 2 and filtered through a short pad of Celite. After removing the solvent of the filtrate, the oil was purified by passing the toluene soiution through a short pad of Silica gel to yield the title compound. Yield: 570 mg, 0,0538 mmci, 90%. l UMR (500 MHz, C&CN): S 6.78 (brs, 1H, NH), 3.95 (s, 1 H, CHGhiCfa), 3.02 (t, 4H, NCH2). 2.75 (s, 3H, NCH3), 1.64 (m, 4H, CH 2 )., 126-1 ,32 {m, 60H, CH 2 ), 0.88 (t, J - 6.9 Hz, 6H, CHa). 3 Cf H} UMR (126 MHz, CO3CN): δ 57.1 (s, alpha-CH., 2C), 47,3 (brs, CHS-nCb), 40.9 (s, - e), 32,6 (s, CH 2i 2C), 30,4-29.6(m, QH2, 24C), 26.8 (s, CH 2 , 2C), 24.4 s, CHa, 2C), 23.3 (s, CH2, 2C), 14.4 (s, terminal CH¾ 20). 18 MR (128 MHz, COgCN): δ -2.25 (br, 1 B, p-8), -9.72 (br, 58, o/m-B), -12.79 (br, SB, o/m-B).
Synthesis of JiC - f g . gg%/ -f 5) ^N{Me)H†*f HCB f jMe †f (Bis H Carfo~ffie}
To a 20 mt via! equipped with a magnetic stir bar was added G9jWCBiiMeit| «
2su!fo!ane (200 mg, 0,30 mmoS) arid 5 mL of a 4:1 P F:CHsCN mixture, resulting in a dear, ye!iowish solution. To this soiution was added i(C^g„22^37- 5½^^ e ^^ m 9< mmol) causing a white precipitate to form. The solution was allowed to stir for 2 hours and then was filtered through a plug of Celite. Th fiitrate was concentrated to a yellow oii which was brought up in ether and filtered through another plug of Celite. Th solution was again concentrated to a yellow oil and was dried under reduced pressure. The oil was washe with water (8x, 2 mL portions), triturated with toluene (4 ), and dried under reduced pressure at 50 * C to afford the title compound with 0,2 equiv, of sulfoSane remaining. Yield: 153 n g, 0.178 mmol, 60% yield. "B NMR (500 MHz, aeetone-ds): δ 3,45 (m t 4H » Chte), 3,17 (s, 3H, CHa), 1.91 :(m, 4H, GHa), 1.49-1,20 (m, 6.0H, GH 2 ), 1 ,10 (b , 1 H, carb C~H}, 0.88 (t, J - 6.9 Hz, 6H, CH 3 ), 0.15 (s t 1SH, B~CH 3 ) > -0.38 <s, 1SH, B~CH 3 ), -0,60 (s, 3H, B-CHg). <3 C{ H} N R (126 MHz, acetone-de): δ 61.4 (br s, carborane-C), 67,3 <s, aJpha-CHj. 2C), 40.9 (s, N™ Me), 33.0 (s, CHa, 2C), 32.0-28.8 <m, C¾, 24C), 27.6 Cs, gamma » CHs, 2C),.25.0 (s, beta- CM*.2C>, 23,7 (s. GH2, 2€), 14,8 (s, terminal CH¾, 2C), -0.27 - -4,02 (br m, 8™CH 3 , 11C). "B NMR (128 MHz, acetone-ds): 50.48 (br, IB, p-B), -7,70 (br, SB, o/m-B), -11.11 (br, SB, o/m-B).
Synthesis of iNa] + fHiC~C(H}CHs-CBriCin†
To a 50 ml Sc lenk flask was added iM^ HJ HCBuCk^ (500 mg, 0.86 mmol), 2.5 equiv NaH (51.5 mg, 2.15 mmol) and THF (20 mL), The resulting suspension was stirred at room temperature for 2 h until it stopped bubbling, Ail voiafiles were removed unde vacuum, and then THF {20 ml) and ally! bromide (89 μΐ, 124.6 mg, 1.03 mmol) were added. The suspension was further stirred at room temperature overnight. NaC! was removed by filtering the solution through a short pad of Ce!ste.
white solid after all volatiies were removed under vacuum. The residue was washed with cold pentane and dried under vacuum to afford the product. Yield: 427 mg, 0,73 mmol, 85% yield. H NMR (500 MHz, CD 3 CN): 66,10 (ddt, J * 17.2, 9.9, 7.4 Hz, 1 H), 5.13 (dq, J - 16.7, 14 Hz, H), 5,08 - 5.01 (dq, J = 16,7, 1.4 Bz, 1 H), 3.01 (q\ J = 7.3 Hz, 3H). NMR {128 MHz, Cf¾CN); δ -3-03, -10,10, -11.73. t3 C NMR (125 MHz, CDaCN): δ 137.5 (s, GHCHz), 116.5 (s, CHCH 2 ), 54.0 (brs, carborane-C), 29.4 (s, CH≥CHCH 2 ).
Sv7?fr?es*s o^
in a SO mL ScKenk flask, a solution of i a] H2C=C(H)CHs-CBiiCI-)¾r(300 mg, 0,513 mmol) in THF (10 mL) was added to a solution of (GsHi?) 2 N(Me)H|1C13- (165.3 mg, 0.564 mmol) in THF (10 mL). Upon mixing, precipitate formed immediately. The mixture was further stirred for 2 h, then filtered through a short pad of Celite, The filtrated was concentrated in vacuo, and the oil was purified by passing the toluene solution through a short pad of silica gel to remove excess amimurn chloride salts. Concentration of the filtrate in vacuo afforded(CgHi7)2 {Me)H *tH2CC<H)CH 2 eBtiC < ?] " as a viscous pale yellow oil. Yield: 360 mg, 0.44 mmol, 86% yield, 1 H NMR (500 MHz, CDC ): 6 6.16 (ddt, J = 17,2, 9.9, 7.4 Hz, 1 H), 5.20 (dq, J = 16.7, 14 Hz, 1H). 5.12 (dq, J = 16.7, 14 Hz, 1 H), 3.01 (d, J * 7,3 Hz, 3H), 3. 5 (vt, J * 7.5 Hz, 4H}, 3.08 (d, J « 7.4 Hz ( .2H), 2.97 {s; 3H), 1,80 (p, J = 8.0 Hz, 4H), 1.44 - 1.21 (m, 22H), 0.89 {!, J » 7,0 Hz, 3H). , B N R {128 MHz, CDG!s}: δ -3.53, -10.47, -11,75, 13 C NMR (12$ MHz, CD 3 CN): δ 137.6 (s, CHCH 2 , 1C), 116.5 (s, CHCH 2 , 1 C), 57 1 (s, aSpha-CH- ? , 2C), 54.0 (t , carborane-C, 1 C), 40.8 (s, N-Me, 1C), 32.3 (s, CH 2 , 2C), 29,6 (s, . .CH 2 , 2C), 29.5 (s, CHzCHGH ¾ 1C), 26.9 (s, CH 2 , 2C), 24.5 (s, CH 2 , 2C), 23.3 (s, CH 2 , 2C), 14.4 (s, terminal- e, 2C)
Representative Bin v!ene/l-Oetene Polymerization Procedure
The ethylene octene eopo!ymerizations were conducted m a .2 1 Parr batch reactor. This reactor was designed for ethylene octene eopolynierizations. The reactor was heated by an electrical heating mantle, and was cooled by an interna! serpentine cooling coil containing cooling water. Both the reactor and the heating/cooling system were controlled and moni-tored by a Camiie TG process computer. The bottom of the reactor was fitted with a . dump valve, which empties the reactor contents into a SS dump pot, which was preft!ied with a catalyst kill solution (typically 5 ml of an i RGAFOS 168 / I GANOX 1010 / toluene mixture). The dump pot was vented to a 30 gal . blow-down tank, with both the pot and th tank z purged. All ebernicais used for polymerization or catalyst make-up were run through purification columns, to remove any impurities that may affect polymerization. The 1 -octene, toluene and ISOPA E were passed through 2 columns, the first containing A2 alumina, the second containing QS reactant The ethylene was passed through 2 columns, the first containing A204 alumina and 4A mole sieves, the second containing GS reactant. The Ns, used for transfers, was passed through a single column containing A204 alumina, 4A mole sieves and QS reactant.
The reactor is loaded first from he shot tank that contains ISOPAR E and octene. The shot tank is filled to the load set-points b use of a lab scale which the tank is mounted on. After solvent addition, the reactor is heated up to the polymerization temperature set- point. The ethylene is added to the reactor when at reaction temperature to maintain reaction pressure set-point. Ethyiene addition amounts were monitored by a micro-motion flow meter. The catalyst and actiyator(s) were mixed with the appropriate amount of toluene t achieve a desired Molarity solution. The catalyst and activators) were handied in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. This was followed by 3 rinses of toluene, 5 mL each. Before ethylene addition, 10 pmoies of MMAO was added to the reactor through the catalyst shot tank. Catalyst and activator was added when reactor pressure set-point was achieved .
Immediately after the catalyst addition, the time of reaction was monitored. Usually within the first two minutes of successful cataiyst runs, an exotherm was observed, as well as decreasing reactor pressure. Ethylene was then added by the Camiie to maintain reaction pressure set-point in the reader. These polymerizations were run for 10 min., then the agitator was stopped, and the bottom dump valve opened to empty reactor contents into the dump pot. The dump pot contents were poured into trays placed in a la hood, where the solvent was evaporated otf overnight. The trays contai ing the remaining poiymer were then transferred to a vacuum oven, where they were heated up to 1 CTC, under vacuum, to remove any remaining solvent. After he trays cooled to ambient temperature, the polymers " were weighed for yield/efficiencies, and submitted for polymer tesiing. Results are shown in Tables 1-6,
Aniiiniurn earborane, [M&2N{H}P jfHCB, j ^ H^ j ], used as a cocatalyst in the above polymerization, was compared to conventional eoeataiysts, such as aniiinium tetrakis(penta- f!uorophenyijborate, [M^^W^HBCCe^s}^ an bis{hydrogenated-taiiovvaikyS}methyS- Four
different catalyst systems were studied at 140 S C and two catalyst systems at 190*0. it was discovered that ani inium earborane (Carb) coeaiaiysi led to very activ catalytic systems, with activities which were virtually the same as activators based on tetra-kls{pentaf!uoro- phenyi}borate. These results clearly demonstrate that carborane anions not only function weli as weakly coordinating , but also are highl stable at elevated temperatures.
The present invention may be embodied in other forms without departing from the Spirit and the essential attributes thereof, and, accordingly, reference Should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.
Table 1
Conditions: Temperature = 140°C, ISOPAR E = 605g, Octene = 300 g, Ethylene Pressure = 288 psi
Table 2
Conditions: Temperature = 190°C, ISOPAR E = 520g, Octene = 300 g, Ethylene Pressure = 400 psi
Table 4
Conditions: Temperature = 140°C, ISOPAR E = 605g, Octene = 300 g, Ethylene Pressure = 288 psi
Table 6
Table 7
Conditions: Temperature = 140°G, ISOPAR E = 605g, Octene = 300 g, Ethylene Pressure = 288 psi, MMAO = 0 μηηοΙ
Table 8
Conditions: Temperature = 140°C, ISOPAR E = 605g, Octene = 300 g, Ethylene Pressure = 288 psi, MMAO = 0 μπηο!
Table 9
Conditions: Temperature = 140°C, ISOPAR E = 605g, Octene = 300 g, Ethylene Pressure = 288 psi, MMAO = 0 μηιοΙ
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