CA2338526C - .alpha.-olefins and olefin polymers and processes therefor - Google Patents

Abstract

Disclosed heroin arc processes for polymerizing ethylene, acyclic olefins, and/or selected cyclic olefins, and optionally selected olefinic eaters a carboxylic acids, and other monomers. The polymerizations are catalysed by selected transition metal compounds, and sometimes other co-catalysts. Since some of the polymerizations exhibit some characteristics of living polymerizations, block copolymers can be readily made. Many of the polymers produced are often novel, particularly in regard to their microstructure, which gives some of them unusual properties. Numerous novel catalysts are disclosed, as well as some novel processes for making them. The polymers made are useful as elastomers, molding resins, in adhesives, etc. Also described herein is the synthesis of linear a.olefins by the oligomerization of ethylene using as a catalyst system a combination of a nickel compound having a selected .alpha.-diimine ligand and a selected Lewis or Bronsted acid, or by contacting selected $(a)diimine nickel complexes with ethylene.

Description

DEMANDES OU BREVETS VOLUMINEUX
LA PRESENTE PART1E DE CE7?E DEMANDE OU CE BREVET
COMPREND PLUS D'UN TOME.
CECI EST LE TOME ~ DE
NOTE: Pour les tomes additionels, veuiilez cantacter 1e Bureau canadien des brevets JUMBO APPLICAT'IONS/PATE111TS
THiS SECTION OF THE APPl..ICAT10N/PATENT CONTAINS MORE' THAN ONE VOLUME -f F
NOTE: For additional volumes-piease contact'the Canadian Patent Office .
a-OLEFINS AND OLEFIN POLYMERS AND PROCESSES THEREFOR

FIELD OF TFIE INVENTION
The invention concerns novel homo- and copolymers of ethylene and/or one or more acyclic olefins, and/or selected cyclic olefins, and optionally selected ester, carboxylic acid, or other functional group containing olefins as'comonomers; selected transition metal containing polymerization catalysts; and processes for making such polymers, intermediates for such catalysts, and new processes for making such catalysts. Also disclosed herein is a process for the production of linear alpha-olefins by contacting ethylene with a nickel compound of the formula [DAB] NiX= wherein DAB is a selected a-diimine and X is chlorine, bromine, iodine or alkyl, and a selected Lewis or Bronsted acid, or by contacting ethylene with other selected a-diimine nickel complexes - Homo- and copolymers of ethylene (E) and/or one or more acyclic olefins, and/or cyclic olefins, and/or substituted olefins, and optionally selected olefinic esters or carboxylic acids, and other types of monomers, are useful materials, being used as plastics for packaging materials, molded items, films, etc., and as elastomers for molded goods, belts of various types, in tires, adhesives, and for other uses. It is well AMENDED SHEEt CA 02338526 2001-03-O1 pC'T/LJS9610128'_ ~-ructure o= -hose vario~.:s .~:OCS~: -'e a-- _~':at -h°_ S.. -- _ C.~.lVmerS; a..~.d hence th°_.= prOpertleS a:.: LlSeS, are ..=c'_'_~.ly depende__~.t o~ the catalyst and soeci fic cc.~.ditions used durinc their synthesis. In addition to 1 ':,eSe faCtCrS, pro: eSScS _n Wi.~Ch theS= tV~-JeS O
~iy;~ers ca:: be made at .educed cost are also ir,~,oorta::t. There=ore, improved processes for maki:.c suc~ inew! polymers are of interest. ~_so disclosed .
~_-_~_- a=a uses for t'_he novel polymers.
u-p=ef_~s are commercial materials being v a s a f a l a s mo nome r s g ad a s c he m t c a t ____er~:=_d_ates. For a review o. a-olefi~s, --..-1ud=na E Elve=s, et al., Ed , ...___ ~.:ses and orecara=~ot:, see ___."~___.' s E.~.cyciop°_dia o' Indust-ial Ch°-~:ist''y, 5ti':
1~ _~., ._.. _._ , V~~Veriacsgesellschaft r;:.~.i:, wet~h°-i~, c- 1 . They are useful a= che:.~.ica_ _ . 236-25 ___t~--~~=::iates and they are often made by the c:".:==_za=ion of ethylene usin3 vario::s types cf ca=alvs~s. therefore catalysts which are capable c.
?0 _..rmi-_ a-olefins from ethylene are co~stantl.,r snug h~.
Si~~.,~ARv Or TiiF' TNVz'h'TZON
_..i= inver_tio:~ concerns a pciyolefir,, which ......ta_n_ abort 60 to about _50 branches per 1000 ~;__::v_~t:e Groups, and w'.~.ich co:.tains fo= every 1C0 __ _~a~ are methyl, about 30 to about °~~ e=W--__ ~__::c: -__ _._ h°a_~.c.:-__, about 4 :.o about 20 Y-opl., b=anche°, abcu= __ aDcut -~J buty'_ branches, about 3 to about __ amy_ a.~.d abort 30 to abo~.:~ 140 hexyi ~r .=nQ°=
..= a::ches .
3p ._.is invention also co:~cer__~.s a ce_yol a"_n w~:ich cc::ta_::s about 20 to about 150 branches per 1000 me_hv_e::e groups, and which contains for every 100 ~__nc .°. _h at a_~e met?:yl , about 4 to about 2G ethy, to Qbo;:t ' 2 ~=opyl branches, abo~,:= _ .._inch . , abou _t - _ 3j to about 12 butyl branches, about 1 to about 10 amvi branches, and 0 to about 20 hexyl or longer bra~.ches_ "_s~losed herein is a polym°_~, consisting eat L-:its arrived f nom the mono~~er s , e_=sew=_a__y o_ _ p _ .. mgt W 1 11 r ~iC~
....... ~ ....

ethylene and a compound cf the formula CH2=CH(CH~)mC02R1, wherein R1 is hydrogen, hydrocarbyl or substituted hydrocarbyi, and m is 0 or an integer from 1 to 16, and which contains about 0.01 to about 40 mole s percent of repeat units derived from said compound, and provided that said repeat units derived from said compound are in branches of the formula -CH(CHz)nCO~R', in abcut 30 to about 70 mole percent of said branches n is 5 or more, in about 0 to about 20 mole percent n is 4, in abcut 3 to~60 mole percent n is 1, 2 and 3, and in about 1 to about 60 mole percent n is 0.
This invention concerns a polymer of one or more alaha-of efir.s of the formula CH2=C~: (CH2i aH wherein a is an integer cf 2 or more, which contains the structure 1~ (XXV;

-CH-CH2-CH- (XXV) wherein R35 is an alkyl group and R36 is an alkyl group ?0 containing two or more carbon atoms, and provided that R35 is methyl in about 2 mole percent or more of the total amount of (XXV) in said polymer.
This invention also includes a polymer of one or more aloha-olefins of the formula CHZ=CH(CHZ)aH wherein ~ a is an integer of 2 or more, wherein said polymer contains methyl branches and said methyl branches comr~rise about 25 to about ?5 mole percent of the total branches.
This invention also concerns a polyethylene :0 containing the structure (XXVII) in an amount greater than can be accounted for by end groups, and preferably at least 0.5 or more of such branches per 1000 methylene groups than can be accounted for by end groups.
3;
rw wnT~T~ rTr ruCCT f01 II G ~f,1 WO 96!23010 PCT/US96/01282 -CH2-CH-CH2CH3 (XXVII) This invention also concerns a polypropylene containing one or both of the structures (XXVIII) and (XXIX) and in the case of (XXIX) in amounts greater than can be accounted for by end groups. Preferably at least 0.5 more of (XXIX) branches per 1000 methylene groups than can be accounted for by end groups, and/or at least 0.5 more of (XXVIII) per 1000 methylene groups are present in the polypropylene.

~CH\

-CH- (XXVIII) -CH2CH2 CH-CH3 (XXIX) l~ Also described herein is an ethylene homopolymer with a density of 0.86 g/ml or less.
Described herein is a process for the polymerization of olefins, comprising, contacting a transition metal complex of a bidentate ligand selected '_'0 from the group consisting of R4 ~ N
R$
(VIII) ..........~ ..~ mrT m n r nee t R4~=N~(CR3~2)n R2 45 N-~ R
cxxx>
Ras Ras R' ~ N
R31 a~N
~a~
(~IIII) R2o O ~-H
R2~ -N

O H
~23 R
(XXX11) with an olefin wherein:
said clefin is selected from the groin consisting of ethylene, an olefin of the formula R'~CH=CH: cr R' CH=CHR1', cyclobutene, cyclopentene, norbornene, or substituted norbornene;
said transition metal is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, FA, Co, Ni or Pd;
R' and RS are each independently hydrocarbyl or 1~ substituted hydrocarbyi, provided that the carbon atom bound tc the imino nitrogen atom has at least two carbon atoms bound to it;
R- and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 w w~~rr~ tTr n~ W rT ff~l 11 C ~7C\

taker_ together are hydrocarbylene substituted hydrocarbyiene to form a carbocyclic ring;
R4q is hydrocarbyl or substituted hydrocarbyl, and Rze is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R'~ taken together form a ring;
R45 is hydrocarbyl or substituted hydrocarbyl, and R'9 is hydrogen, substituted hydrocarbyl cr hydrocarbyl, or R~5 and R'~ taken together form a ring;
each RJ° is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R'° taken together form a ring;
R'~ and R'~ are independently hydrocarbyi or substituted hydrocarbyl;
R" and R" are each in independently hydrogen, 1~ hydrccarbyl cr substituted hydrocarbyl;
each R1 is independently hydrocarbyl or substituted hydrocarbyi provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
n is 2 or R1 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that:
said transition metal also has bonded to it a iigand that may be displace by said clefin o~ add tc said olefin;
when M is Pd, said bidentate ligand is (VIII;, (XXXII) or lXXIII);
;0 . when M is Pd a diene is not present; and when norbornene or substituted norbornene is used no other olefin is present.
Described herein is a process for the copolymerization of an olefin a:.d a fluorinated olefin, 3~ comprising, contacting a transit=on metal complex of a bidentate ligand selected from the group consisting of _-_-..-_ ~..~~ ,r,~ w r ncv _....... .. ~.....

WO 96!23010 PCT/US96/01282 ,N
Ra ~ N

!VIII;
with an olefin, and a fluorinated olefin wherein:
said olefin is selected from the group consisting of ethylene and an olefin of the formula R''CH=Ci:- or R' CH=CHR1 ~ ;
said transition metal is selected from the groin consisting of Ni and Pd;
said r,~ueri:~ated clef ir_ is of the formul a ~_C=Ci ; CH~ l ark=Win'' , a is gr. integer cf 2 to 20; RF is perfi~aoroalkyiene optionally containing one or more ether groups;
1~ Ry' is fluorine or a functional group;
R~ and R' are each independently hydrocarbyl or substituted hydrocarbyi, provided that the carbon atom bound to the imino nitrogen atom has at least two carbcn atoms bound to it;
~0 R~ and R~ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R' and R' taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring;
each ~.'~ is independently saturated hydrocarbyl;
and provided that said transition metal also has bonded to it a ligand that may be displaced by said olefir. or add to said olefin.
This invention also concerns a copolymer of an ,0 olefin of the formula R' CH=CHR'' and a fluorinated olefin of the formula H=C=CH(CH2)aRfR42, wherein:
each R1' is independently hydrogen or saturated hydrocarbyl;

nwnn~rT~eTr MJt'CT /DI II C ~~.'~

WO 96!23010 PCT/LTS96/01282 a is an, intea~r cf 2 to 20 ; :~f is perfluoroalkylene optionally containing one cr more ether groups; and R4z is fluorine or a functional group;
provided that when both of R'' are hydrogen and R9' is fluorine, RF is -(CFz)~- wherein b is 2 to 20 or perfluoroalkylene containing at least one ether group.
Described herein is a process for the polymerization. e~ olefins, comprising, co:~tacting, at a temperature of about -100°C to about +200'.
- a first compound W, which is a ne~.:tral Lewis acid capable cf abstracting either Q or S to form WQ
or WS , provided that the anicn formed is a weakly coordinating anion; or a cationic Lewis c= Bronsted 1~ acid whose ccunterion is a weakly coordir.,_--.ping anion;
a seccnd compound of the formula Rz R3 , N~ j Q)v M
R ~s (XI) ~0 and one or more monomers selected =nom the group consisting of ethylene, an olefin c. the formula R1 CH=CH, or R' CH=CHR'', cyclobutene, cyclcpentene, substituted norbernene, or norbornene;
?5 wherein:
M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd the m oxidation state;
y + z = m R' and Rr are each independently hydrocarbyl or 30 substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

_.._ __.~..r.. ..~ ~r.-T m » r nev ...Y .

WO 96123010 PCTlUS96/01282 R~ and R~' a=a each independently hydrogen, hydrccarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other clefinic bond er aromatic ring by a quaternary carbcn atom or at least two saturated carbon atoms;
Q is alkyl, :hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and provided that:
I~ when norbornene cr substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable ?0 of transferring a hydride or alkyl group to M.
This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about -100°C to about 1200°C, one or more monomers selected from the group consisting of '_'' ethylene, an olefin cf the formula R' CH=CH~ or R1~CH=CHR- , cyclobutene, cyclopentene, subst=ituted norbornene, and norbornene; with a compound of the formula _.._ __._. ~_ _. ._~ .." ,. ~ .,.., R3 ~ N\ /Ti R ~ N ./T~
\ ~Pd~ ~ NnZ

Ra R5 X_ R R5 X_ R2 OR$
R3 N O=C
M
R4 ~ Ni ~~CHR~6)n X_ (II) (III) (IV) or Rs ~ N~Pd~T2 R4 ~ N ~ X
R~
(VII) wherein:
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom ~~snc t,. the imino nitrogen atom has at least two carbo.~. atoms bound to it ;
R~ and R'~ are each independently hydrogen, 1> ~vdrocarbyl, substituted hydrocarbyl, or R' and R4 taker. Together are hydrocarbyiene or substituted ::vdrocwrbylene to form a ring;
T' is hydrogen, hydrocarbyl not containing ~=efi-'~ or acetylenic bonds, R15C(=O)- or R150C(=O)-, ?0 n is 2 or 3 ;
Z is a neutral Lewis base wherein the donating atom .s nitrogen, sulfur or oxygen, provided that it ~'~:e dc:~ating atom is ni trogen then the pKa of the conjugate acid of that compound is less than about 6;

X is a weakly cocrdinating anion;
R15 is hydrocarbyl not-containing olefinic or acetylenic bonds;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
M is Ni(II) or Pd(II);
each R16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms;
n is 1, 2, or 3;
RB is hydrocarbyi; and T~ is hydrogen, hydrocarbyl not containing Is olefinic or acetyienic bonds, hydrocarbyl subst,~tuted with keto or ester groups but not containing oiefinic or acetylenic bonds, R15C (=O) - or R150C (=O) - , and provided that:
when M is Pd a diene is not present; and ?0 when norbornene or substituted norbornene is used no other monomer is present.
This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about -100°C to about +200°C, one or more monomers selected from the group consisting of ethylene, an olefin of the formula R1'CH=CH, or R1'CH=CHR1', cyclobutene, cyclopentene, substituted norbornene, and norbornene; with a compound o. the formula ~..~.u~.~ rrr m ~rrT ~Dt 11 C ~G:\

RZo p~H
RZi -N, TZ
is ' R (CR3o2)~ Rzs PCi R4~=N' ?~l=~Ras R22 -N X
p H
~3 (Q)Yi (S)z R
(XVII) (XVIII) or R2o p~H
R2~ -N T~
~M~
R22 -N, . Z
p~H X
Rzs (X111) wherein:
R94 is h~~drocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R28 taken together form a ring;
R4' is hydrocarbyl or substituted hydrocarbyl, and R'~ is hydrogen, substituted hydrocarbv~1 or 10 :~:ydrocarby~;, or Rqs and R'9 taken cocrether form a ring;
each R'° is independently hydroge.~., substituted hydrocarbyl or hydrocarbyl, or two of R'~ taken together form a ring;
each R1' is independently hydrocarbyl cr l~ substituted hydrocarbyl provided that any clefinic bond in said olefir. is separated from any other olefinic bond or aromatic ring by a auaternary carbc: atom or at least two saturated carbon m oms;
R" and n'3 are independently hydrocarbyi or '_'0 substituted hydrocarbyl;
R" and R" are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
1 '_' T' is hydrogen, hydrocarbyl not coma=:.ing olefinic or acetylenic bonds, R15C(=0)- or R'-;".(=0)-;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;
and X is a weakly coordinating anion; ana provided that:
when. M is Pd or (XVIII ) is used a dime is not present ; and in (XVIi) M is not Pd.
This invention includes a process fc= the production of polyolefins, ccmprising contact=ng, at a temperature c~ about .00°C to about +200°C, c~:e cr more monomers selected from the group consist_ng cf ethylene, an olefin o~ the formula Rl~CH=CH2 cr R1~CH=CHR1~, 4-vinylcyclohexene, cyclobutene, cyclonentene, substituted norbornene, and norbornene;
with a compound of the formula Rzo ~~H
R2~ -N, Ti Pd~

~~-H

(XVIII) wherein:
R20 and R23 are independently hydroca~byl or substituted ~ydrocarbyl;
R" and Rz~ are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C (=O)- or R~50C(=O)-;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;
5 X is a weakly coordinating anion;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
each R'~ is independently hydrocarbyl or substituted hydrocarbyi provided that any olefinic bond 10 ~n said olefin i~ separated from any other olefinic bond cr aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
M is Ni(IT_) or Pd(II);
T2 is hydrogen, hydrocarbyl not containing Is olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C(=O)- or R150C(=0)-;
and provided that:
when M is Pd a diene is not present; and 20 when norbornene or substituted norbornene is used no other monomer is present.
Described herein is a process for the production for polyolefins, comprising contacting, at a temperature of about -100°C to about +200°C, a first compound W, which is a neutral Lewis aced cap_abie of abstracting either Q or S tc Fcrm WQ
or WS , provided that the anion formed is a weakly cocrd,_nating anion; or a cationic Lewis or Bronsced acid whose courterion is a weakly coordinating anion;
30 a second compound of the formula RZ8 /(CR3~2)n R29 1~1=~ R4s \M/
(Q)y~ ~ (S)z (XVII) 1~
__-_ _. .~~ .... n r nw and one or more monomers selected from the grou;. consisting of ethylene, an olefin of the formula R'~CH=CH, or R1'CH=CHR'', cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, or Ni, of oxidation. state m;
R~4 is hydrocarbyl or substituted.hydrocarbyl, and R'' is hydrogen, substituted hydrocarbyl cr hydrocarbyl , cr R4' and Rye taker. together form a r i.~.g;
R4' is hydrocarbyl or substituted hydrocarbyl, and R'~ is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R'S and R2~ taken together form a ring;
1' each R~' is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R3° taken together form a ring;
n is 2 or 3;
y and z are positive integers;
?0 y+z = m;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond cr aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, .._ bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and 30 provided that;
when norbornene or substituted norbornene is present, no other monomer is present.
Disclosed herein is a process for the production of polyolefins, comprisinc, contacting, at a temperature of about -100°C to about +200°C, one or more monomers selected from the croup consisting of ethylene, an olefin of the formula R1'CH=CH2 or R1 CH=CHR1', cyclobutene, cyclopentene, substituted 1;

norbornene, a~:a :.orbornene; optionally a so;:rce of R;
with a compound of the formula Rs I ~ N Rs N T
~Pd~ E T,/Pd\N
Ra ~ N I Ra Rs Rs X.
(v) wherein:
R' and :~~ are each independently hydrocarbyl or substituted hvdrocarbyl, provided that the carbon atom bound directlw ~.. the imino :_troge:, atem as at least twc carbon atoms bound to it;
R3 and ~.~' a=a each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene substituted hydrocarbylene 1~ to form a ring;
each t-~ is independently hydrocarby': or substituted hydrocarbyl provided that R-~ contains no olefinic bonds;
T1 is hydrogen, hydrocarbyl not containing oiefinic or acetvienic bonds, R15C (=O) - or R--rC (=O) - , .s R is hydrocarbyl not containi.~.g c~e~inic or acetylenic bonds;
E is halogen or -ORle.
R18 is hydrocarbyl not containing olefinic cr ~5 acetylenic bones; and X is a weakly coordinating anion;
provided :.hat, when norbornene or substituted norbcrnene is _present, no other monomer is present.
Described herein is a process for the 30 polymerization of olefins, comprising, contacting, at a temperature o~~abcut -100°C to about +200°C:
a first compound W, which is a neutral Lewis acid capable c~ abstracting either Q or S to form WQ

,~

WO 96123010 PC'f/US96/01282 or wS , provided t::at the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinatirc anion;
a second compound of the formula R3 ~ N\
~M~
R4 ~ N S

(I) and one or more monomers selected from the -,rout cc~sisting of ethylene, an olefin of the formula R' CH=CH-. or R'~CH=CHRi , 4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
IS M is Ni(II), Co(II), FeEII), or Pd(II);
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
'_0 R' and R~' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyi or R' and R4 taken together are hydrocarbylene or subst_tuted hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or '_'~ substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond cr aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or 30 bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and provided that;

_..___.~._~ .",..r.! mm r nc~

when norbornene or substituted norbornene ~s present, no other monomer is present;
when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each Independently chloride, bromide or iodide w is capable o' transferring a hydride or alkyl group to M.
Included herein is a polymerization process, comprising, contacting a compound of the formula gad (R'~CN) 4] X~ or a combination of Pd [0C (O) R;°] ; and HX; a ccmpo~~nd of the formula Ra~N
I

(VIII) 1~ and one or more monomers selected from the group consisting of ethylene. an olefin of the formula R' CH=CH2 or R1'CH=CHRj~', cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
R2 and RS are each independently hycirocarbyl or ?0 substituted hydrocarbyl, provided that the carbon atom bound ~o the imino nitrogen atom has at least two carbon atoms bound to it;
R' and R~ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that R1' contains no olefinic bonds;
30 R13 is hydrocarbyl;
. R'° is hydrocarbyl or substituted hydrocarbyl and X is a weakly coordinating anion;

...t _-_-..r _..~~ ~.,m r nc~

provided that, when norbornene cr substituted norbornene is present, no other monomer is present.
Also described herein is a polymerization process, comprising;
contacting Ni [0] , Rd[0] or Ni [I] compound containing a iigand which may be displaced by a ligand of the formula (VIII), (XXX), (XXXII) cr (XXIII);
a second compound of the formula R4 ~ N

(VIII) R (CR3~2)n R29 R°~=N~ Tl=~R4s (xxx) R48 R4s R-~ -N
R31 4~N
R ~47 (XXIII) 1~
or _.........~~. w, ~rrT W 11 t '1C\

R2o ~~H
R2 l -N

H
~23 R
(XXXII) an oxidizing agent;
a scurce of a relatively weakly coordinating anion;
~ and or.~ or more monomers selected from the group consisting of ethylene, an olefin of the formula _-,..__ R' C.=C:i~ or :~ ' :=Ci-iR-~, cycl we.~.tene, cycl cbutere, substitutea nerbornene, and norbornene;
wherei.~.:
R' and R' are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound tc the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R~ are each independently hydrogen, 1~ hydrocarbyl, substituted hydrocarbyl or R~ and R'' taken together are hydrocarbylene or substituted hydrccarbyiene to form a ring;
each R- is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond ~0 i.~. said olefin is separated from any other olefinic bond or aromatic ring by a auaternary carbon atom or at least two saturated carbon atoms;
R13 is hydrocarbyl;
R4' is hydrocarbyl or substituted hydrocarbyl, and R26 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R'~' and R28 taken together form a ring;
R°5 is hvdrocarbyl or substituted ~ydrocarbyl, and R's is hydrogen, substituted hydrocarbvi or hydrocarbyl, or R95 and R2s taken together ~~rm a ring;
?0 _..__.....~ ..~ ~~~ rw n r nee t , each R'° is independ~. . .1y hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R'° taken together form a ring;
R31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
R'6 and R" are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
IO R'e and R'9 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
R2° and R~' are independently hydrocarbyl or substituted hydrocarbyl;
n is 2 or 3;
I~ RZ' and R~~ are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and X is a weakly coordinating anion;
provided that;
when norbornene or substituted norbornene is 20 present, no other monomer is present;
when said Pd[O] compound is used, a diene is not present; and when said second compound is (XXX) only an Ni[0) or Ni (I] compound is used.
25 Described herein is a polymerization process, comprising, contacting an Ni[0] complex containing a ligand or ligands which may be displaced by (VIII), oxygen, an alkyl aluminum compound, and a compound of the formula R4 ~ N

(VIII) AMENDED SHEET

and one or more monomers selected f: m the~group consisting of ethylene, an olefin of the formula v 21a AMENOEO SHEET

PCTlLi S96/01:8=
WO 96/23010 ~ 02338526 2001-03-O1 .~'c' W=Cr= er R' C =CsR' , cycl epentene, cyc_cb~~=e.~.=, s::bstit;::.e ..~.orbornene, anQ nOrt70rnene; where_n:
z' and RS are eac ..ndepenaentl y cydrocarbvl c_ substitute3 hydrocarbyl , provided that t::e carbc:: atc.-..
J b0:: :O ~..~. t.~.°_ lTi.1 :O nitrOCen dtOLTl naS at ;east tw.~.
Oar.~.0:: a..W::a bOLi.':Cl t0 1t;
. . G.:.~r .... ~ ~ , hv_drccarbyi, .substituted hydrccarbyl or R1 and n' take:
_ --~t!-:e_ G=a '~ycrcca=bylene o. substituted ~'_.W_ccarb~~lene to form a rinJ; and each l s inaepena°_.ntly hydrocarbyl ,._ su~st_~::ted hydrocarbyl provided that any olefy..'_c b......
l:: said clefin is separate3 frcm a::y ether o_e=_.nic :,c~d cr aro;~at__ ring by a cuater::ary carbcr: a=cn c. a_ 1' _~c5~ tw0 SdtLlrated CarbO:: atOtlS;
orcwid=d t'r'.at, when ncrbornene o. substi=~.:=ed ncrbcr~ene is D=eser:t, nc otter monomer is prese::t.
A polymerization process, comprising, contacts::=
' ~ ~um cc;raou.~.3 or a C :.-.;00t4:..-.
OX'JQen a: a_~. a_kVl a111T~~_.. , _ 0 the fcrmu_a HX, a:.d a compound o' the formula _ Rs ~ z s R:
R I R:
/ /N R.
Ni COD N
O
~N~ \~~
Rr ( _ R' I
F
R' RS l' on~~
(7~J~?~III) IxxxxW rxxxxun Ra Rt Rs R3 R~ R~
N N N
/\
N.- ()_ N N N
Rs Is Ra I5 I: R~
R R
faxx\I~'1 or fxXxX~'1 and one o. mare monomers selected from the group consisti.~.c of ethylene, an olefin of the formula _ -, R' CH=CH, o_~ R''CH=CHR1', cycioperte.~.°_, cyclobute.~.~
rT~ and :_crbornene; where.:::
s....s_~tut_d ncrbo_.._ne, R2 and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R9 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; and each R1' is independently hydrocarbyl cr substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any cther olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
X is a weakly coordinating anion; and 1~ provided that, when norbornene or substituted norbornene is present, no other monomer is present.
Described herein is a polymerization process, comprising, contacting an Ni[O] complex containing a ligand or ligands which may be displaced by (VIII), HX
or a Bronsted acidic solid, and a compound of the formula Ra ~ N

(VIII?
,~
and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R1'CH=CHZ or R1'CH=CHR1', cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
Rz and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carboy. atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
' 1 ........~.~..~r ni ~rrT int It C ~Ct R3 and k' are each l ,.dependent-~y ~~et!~gen, hydrocarbyl, substituted hydrocarbyl or R' and R' taker_ together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other oiefinic bond or aromatic ring by a quaternary carbon atom or at 'east two saturated carbon atoms; and X is a weakly coordinating anion;
provided that, when norbornene or substituted norbornene is present, no other monomer is present Described herein is a process for the polymerization e~ olefins, comprising, contacting, at a temperature c'_ about -i00°C to about X200°C:
a first compound W, which is a neutral Lewis acid capable of abstracting either Q or S to form WQ-or WS , provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted ~0 acid whose counterion is a weakly coordinating anion;
a seccnd compound of the formula O~H
R2 l - ~N D
\ / A
M
R22 / N/ \S
LH
~R23 XIX
and ene c, more monomers selected from the group consisting of ethylene, an olefin of the formula R1'CH=CH, or R' CH=CHR1', cyclobutene, cyclopentene, substituted norbornene, or norbornene;
wherein:
30 M is Ni(II) or Pd(LI);
~ ~1 _ _ __ _-.-..~~ m rrr~ rnr 11 r ,1C1 . ..... ~ ....... ... , R2° and R'' are independently hydrocarbyl or substituted hydrocarbyl;
R21 and R2z are each in independently hydrogen, hydrocarbyl cr substituted hydrocarbyl;
each R1' is independently hydrocarbyl or subst_tuted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other oiefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
)p Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and provided that;
1, when norbornene or substituted norbornene is present, no other monomer is present;
when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable '?0 of transferring a hydride or alkyl group to M.
This invention also concerns a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200°C, a compound of the formula '_' S

R3 N NCRz' ~Pd~
R4 ~ nj ~ NCRz' ~5 2X
(XIV) 30 and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R1~CH=CHI or R1'CH=CHR'', cyclopentene, cyclobutene, substituted norbornene, and norborne.~.e; wherein:
___ _. .~~ .~~ n r nf!\

R' and R~ are each independently ny~~~:arbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken ~cgether are hydrocarbylene or substituted :~ydrocarbylene to form a ring;
each R' is independently hydrocarbyl cr substituted hydrccarbyl provided that R1' contains no olefinic bonds; and each R'' is independently hydrocarbyl;
each X is a weakly coordinating anion;
provided that, when norbornene or substituted 1~ ~orbornene is present, no other monomer is present.
This invention also concerns a process for the polymerization of olefins, comprising, contacting, at a ~emDerature of about -100°C to about +200°C:
a first compound W, which is a neutral Lewis ?0 acid capable of abstracting either Q or S~ to form WQ
cr WS , provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
a second compound of the formula R48 R4s R'~ N
R~ ~ ~I~
R4g K47 and one cr more monomers selected from the group consisting of ethylene, an olefin of the formula 30 R'~CH=CHz or R1'CH=CHR1', cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:
?6 R~~ and R4' are each independer.ziy hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R48 and R49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
each R31 is independently hydrocarbyl, substituted hydrocarbyl or hydrogen;
M is Ti, Zr, Co, V, Cr, a rare earth metal, Fe, Sc, Ni, or Pd of oxidation state m;
y and z are positive integers;
y+z = m;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond 1~ in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
Q is alkyl, hydride, chloride, iodide, or bromide;
S is alkyl, hydride, chloride, iodide, or bromide; and provided that;
when norbornene or substituted norbornene is present, no other monomer is present;
'_'S when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each independently chloride, bromide or iodide w is capable of transferring a hydride or alkyl group to M.
Disclosed herein is a compound of the formula Rs I
N\
a ~ N Pd Z
R

(II) '' 7 m ~w~rtr rfr nUf~T 1D111 C ~ .r.~

wherein:
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R° are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
10 T1 is hydrogen, hydrocarbyl not containing of efinic or acetylenic bonds, R15C (=O) - or R'SOC v=O) -;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the 1~ conjugate acid of that compound is less than about 6;
X is a weakly coordinating anion; and R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
provided that when. R3 and R4 taken together are ?0 hydrocarbylene to form a carbocyclic ring, Z is not an organic nitrile.
Described herein is a compound of the formula Rso ~s~
wherein:
RS° is substituted phenyl;
R51 is phenyl or substituted phenyl;
R' and R~ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R~ and Ra taken together are hydrocarbylene or substituted 30 hydrocarbylene to form a ring;
and provided that groups in the 2 and 5 positions of RS° have a difference in ES of about 0.60 or more.
Described herein is a compound of the formula ?8 _. ._ __._. ~_ ", ,..r.. ,." , WO 96123010 pCT/US96101282 Rs2 ,,. ~l / Q
i Ra ~ I~ ~ S
~s3 (XXXVI) wherein:
R5~ is substituted phenyl;
RS' is phenyl or substituted phenyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydroca~bylene to form a ring;
Q is alkyl, hydride, chloride, bromide or iodide;
S is alkyl, hydride, chloride, bromide or iodide;
1~ and provided that;
groups in the 2 and 6 positions of RS' have a difference in ES of 0.15 or more; and when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a ?0 hydride or alkyl group to Ni.
T'.:_s invention includes a compound of the formula R3 i N T~
Nib Ra N Z
Rs X-(III) wherein:
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom '9 w ~~w.wn~ r~ -t IrPT /DI II C

bound to the imino r_itrogen atom has at least two carbon atoms bound to it;
R3 and RS are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(=O)- or R150C(=O)-;
R15 is hydrocarbyl not containing an olefinic 10 cr acetylenic bond;
Z is a neutral Lewis acid wherein the donating atom is nitrogen, sulfur or oxygen, provided that, if the donating atom is nitrogen, then the pKa o~ the conjugate acid of that compound is less than about 6;
l~ and X is a weakly coordinating anion.
This invention also concerns a compound o~ the formula N~ IOC~
M
R4 ~Ni ~~CHR~6)n I

~u ( Iv) wherein:
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound tc it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' taken 30 together are hydrocarbylene or substituted hydrocarbylene to form a ring;
M is Ni(II) or Pd(II);

_ . ._ __._. ._~ ." ,~~r ..,. .. ~ nev WO 96/23010 PC'T/US96/01282 each R1~ is independently hydrogen or alkyl containing 1 to 10 carbon atoms;
n is 1, 2, or 3;
X is a weakly coordinating anion; and RB is hydrocarbyl.
Alsc disclosed herein is a compound of the formula R3 N T~ , . N Rs ~Pd~ E 1/Pd\ \
Ra N T N , Ra R5 Rs X_ (v) wherein:
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least l~ two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
''0 E is halogen or -OR1~;
R1g is hydrocarbyl not containing olefinic or acetylenic bonds;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15CI=O)- or R150C(=O)-;
'_~ R15 is hydrocarbyl not containing olefir_ic or acetylenic bonds; and X is a weakly coordinating anion.
Included herein is a compound of the formula [(r)4-1, 5-COD) PdTlZ]'X , wherein:
30 T1 is hydrocarbyl not containing olefinic or acetylenic bonds;
X is a weakly coordinating anion;
COD is 1,5-cyclooctadiene;
_.._ __._.._~ ., ,.r, ~r,m r nc~

Z is R-°CN; and R1° is hydrocarbyl not containing oiefinic or acetylenic bonds.
Also included herein is a compound of the formula R3 ~ N. ,P~
i~~~CHR»
R4 ' N R" HC X-(VI) wherein:
!~ is Ni(II) or Pd(T_I) ;
R~ and RS are each independently hydrocarbyl c.
substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
1~ R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R1' is independently hydrogen, alkyl or ?0 -(CHz)mCO,Rl;
T' is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or -CH2CH~CHzCG~RE;
P is a divalent group containing one or more repeat units derived from the polymerization of one or 25 more of ethylene, an olefin of the formula R'''CH=CH2 or R1'CH=CHR1', cyclobutene, cyclopentene, substituted norbornene, or norbornene and, when M is Pd(II), optionally one or more of: a compound of the formula CHz=CH(CH2?mC02R', CO, or a vinyl ketone;
30 Re is hydrocarbyl;
m is 0 or an integer from 1 to 16;
R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;

_ _ __ __-_ .r _. ._~ ,... .. . "", WO 96!23010 PCT/US96/01282 and X is a weakly coordinating anion;
provided that, when M is Ni(II), R11 is not -C02Re.
Also described herein is a compound of the formula R3 ~ N\ /T2 ~Pd~
R4 ~ N X

(VII) wherein:
R' and RS are each independently hydrocarb~~1 or substituted hydrocarbl~l, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon. atoms bound to it;
R? and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R~ taken 1~ together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic ?0 or acetvlenic bonds, R'SC(=O)- or R"OC(=O)-, R'S is hydrocarbyl not containing olefinic or acetyienic bonds; and X is a weakly coordinating anion.
Included herein is a process fcr the production of 35 polyoiefins, comprising, contacting, at a temperature of about -100°C to about +200°C, a compound of the formula R3 , N~ ,PT's iN\~CHR»
R4 N R~~HC X' (VI) >;
~......~w. r~r w ~rrT iDl II C ~R\

WO 96123010 PCTlUS96101282 and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R1~CH=CHI or R1'CH=CHR1', cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:
M is Ni(II) or Pd(II);
R2 and RS are each independently hydrocarbyl.or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted .
l~ ydrocarbylene to form a ring;
each R11 is independently hydrogen, alkyl or -(CH~)mC02R1;
T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or -CH~CH2CH2C02R8;
P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an olefin of the formula R1'CH=CH2 or R' CH=CHR1', cyclopentene, cyclobutene, substituted ...,rbornene, and norbornene, and, when M is Pd(II), ctionally one or more of: a compound of the formula CH==CH ( CH2 ) mC02R1, CO or a vinyl ketone ;
Ra is hydrocarbyl;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R1 is hydrogen, or hydrccarbyl or substituted hydrocarbyl containing 1 to -3~ 1 0 carbon atom ;
m is 0 or an integer of 1 to 16;
and X is a weakly coordinating anion;

~, mnT~r nr cucrT roi ii C ~R\

provided that:
when M is Pd a diene is not present;
when norbornene or substituted norbornene is present, no other monomer is present; and further provided that, when M is Ni(II), R11 is not -CORE .
Included herein is a process fer the production of polyolefins, comprising, contacting, at a temperature of about -100°C to about +200°C, a compound of the formula Rz R /N\ /Q~y ~
M-C-R"
~~
a N ~H-C-R"
R R5 PTs (XVI) (X )a I~ and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R1~CH=CH~ or R1'CH=CHR'', cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:
M is Zr, _ , Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation state m;
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
~0 each Rll is independently hydrogen, or alkyl, or both of R-1 take_~_ together are hydrocarbylene to form a carbocyclic ring;
3~
m rerTrrr rrc cuCCT /C!t II F ~Rl Tr is hydrogen., hydrocarbyl not coritainlng olefinic or acetylenic bonds, or -CHzCH2CH~COzR6;
P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an oleFin of the formula R1'CH=CH; or R1'CH=CHR1', cyciopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II), optionally one or more of: a compound of the formula l0 CH2=CH ( CHI ) mCO~R~ , CO, or a vinyl ketone ;
R~ is hydrocarbyl;
a is 1 or 2;
y + a + i = m;
each R' is independently hydrocarbyi or I~ substituted hycirocarby~ provided that any ciefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 20 10 carbon atoms;
m is 0 or an integer cf 1 to 16;
and X is a weakly coordinating anion;
provided that:
when norbornene or substituted norbornene is present, ..~.o other monomer is present;
when M is Pd a diene is not present; and further provided that, when M is Ni(II), R11 is not -CO,Re .
30 Also described herein is a compound of the formula R ~N\ %C)y I
M-C-R"
~~
H-C-R~ ~
R Rs PTs (XVI) (X )a _.._ __._. __ _. ._~ .~, " ~ .,~, wherein:
M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation state m;
R' and RS are each independently hydrocarbyi or subst_tuted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbo:. atoms bound to it;
R- and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbyiene or substituted hydrccarbylene to form a ring;
each R-' is independently hydrogen, c. alkyl, or both of R1' taken together are hydrocarbyiene to 1~ form G carbocyclic ring;
TJ is hydrogen, hydrocarbyl not containing olefir_ic cr acetylenic bonds, or -CH2CH~CH,CO_R~;
P is a divalent group containing one or more repeat units derived from the polymerization of one or ?0 monomers selected from the group consisting of ethylene, an olefin of the formula R1 'CH=CHI or R1~CH=CHR' , cyclopentene, cyclobutene, substituted norbcrnene, and norbornene, and optionally, when N! is Pd(II;, one or more of: a compound of the formula CH_=vF ! CH=! _.CO,R-, CO, or a vinyl ketone ;
is a monovalent anion;
R' is hydrocarbyl;
a is 1 or 2;
y + a + 1 = m;
30 each R1' is independently hydrocarbyi or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond cr aromatic ring by a quaternary carbon atom cr at least two saturated carbon atoms;
3~ R' is hydrogen, or hydrocarbyl or substituted hydrocarbyi containing 1 to 10 carbon atoms;
m is 0 or an integer of 1 to 16; and and X is a weakly coordinating anion;
., m _.._ __._. ~_ _. ....., ,.

and provided that when M is Pd a aiene is not present.
Described herein is a process, comprising, contacting, at a temperature of about -40°C to about +60°C, a compound of the formula [(r~4-1,5-COD)PdTlZ]'X
and a diimine of the formula R4 ~ N
Rs (VIIIi to prcduce a compound of the formula Rs I
N~ T~
Pd~
R4 ~ N Z
Rs X-(II) 1~
wherein:
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(=0)- or RlIOC(=O)-;
X is a weakly coordinating anion;
?0 COD is 1,5-cyclooctadiene;
Z is R1°CN;
R'° is hydrocarbyl not containing olefinic or acetylenic bonds;
R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and .. _-.-. .. .. ..r m n r nw WO 96/23010 ~ 02338526 2001-03-O1 R' and R4 are each independently ~yazctg~n, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.
Described herein is a process, comprising, contacting, at a temperature of about -80°C to about +2C°C, a compound of the formula (r)4-1,5-COD)PdMe2 and a diimine cf the formula Rs I
,N
Ra ~ N

(VIII) ~o produce a compound of the formula R' I
Me Pd \N/ ~ Me R
Rs (XXXXI) wherein:
COD is 1,5-cyclooctadiene;
R2 and RS are each independently hydrocarbyl or ?0 substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and R' and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' oaken together are hydrocarbylene or substituted hydrocarbylene to form a ring.
Also disclosed herein is a compound of the formula ..

e~meemtrr~ cuCCT lCil II C 9R1 WO 96/23010 PC"T/US96/01282 N NCR2' ~Pd~
R4 \ ~ 'NCR27 (XIV) wherein:
R' and RS are each independently hydrccarbyl or substituted hydrocarbyl, provided that the carbon atom bound tc the imino nitrogen atom has at least two carboy atom bcund to it;
R' and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and R' taker.
together are hydrocarbylene or substituted hydrocarbylene to form a ring;
1~ each R'' is hydrocarbyl; and each X is a weakly coordinating anion.
This invention includes a compound of tre formula R3 N '1'~
i~~CHR~4 Ra ~ N R~aHC~ X_ ?0 (IX) wher eir.
M is Ni(II) or Pd(II);
R' and R~ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
R' and R; are each independently hydrogen, hydrocarby , subst'_tuted hydrocarbyl or R3 and R4 taken _..___._..~~ .."~~ ~m » c nev WO 96/23010 ~ 02338526 2001-03-O1 p~/pg96/01282 together are hydrocarbylene cr substituted hydrocarbylene to form a ring;
each R14 is independently hydrogen, alkyl or - ( CHz ) ~CO~R1;
R' is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
T4 is alky 1 , -R6°C (O) ORg, R15 (C=O) - or R1~OC (=O) -R'S is hydrocarbyl not containing olefinic or acetylenic bonds;
R6° is aikylene not containing olefinic or acetyienic bends;
Re is hydrocarbyl;;
and X is a weakly coordinating anion;
1~ and provided that when R'y is - (CHz)mCO~R', or Ty is not alkyl, M is Pd(II).
Described herein is a homopolypropylene with a glass transition temperature of -30°C or less, and containing at least about 50 branches per 1000 methyiene groups.
This invention also concerns a homopolymer of cyclopentene having a degree of polymerization of about or more and an end of melting point of about 100°C
to about 320°C, provided that said homopolymer has less than 5 mole percent of enchained linear olefin containing pentylene '.:nits.
In addition, disclosed herein is a homopolymer or copolymer of cyclopentene that has an X-ray powder diffraction pattern that has reflections at :0 approximately 17.3°, 19.3°, 24.2°, and 40.7°
28.
Another novel polymer is a homopolymer of cyclopentene wherein at least 90 mole percent of enchained cyclopentylene units are 1,3-cyclopentylene units, and said homopolymer has an average degree of 3~ polymerization of 30 more.
Described herein is a homopolymer of cyclopentene wherein at least 90 mole percent of enchained cyclopentylene units are cis-1,3-cyclopentylene, and r.~ ~ecrT~ rrc cuccT raW ~ ~R~

said homopoiymer has an average degree c$' polymerization of about 10 or more.
Also described is a copolymer of cyclopentene and ethylene wherein at least 75 mole percent of enchained cyciopentylene units are 1,3-cyclopentyiene units.
This invention concerns a copolymer of cyciopentene and ethylene wherein there are at least 20 branches per 1000 methylene carbcn atoms.
Described herein is a copolymer of cyclopentene a::d ethylene wherein at least 50 mole percent of the repeat units are derived from cyclopentene.
Disclosed herein is a copolymer of cyclopentene and an a-olefin.
This invention also concerns a polymeriza'ion 1~ _=oces=, comprising, contacting an olefin of the ~errw.:la R1 CH=CH2 or R1'CH=CHR1', wherein each R' is independently hydrogen, hydrocarbyl, or substituted hydrccarbyl provided that any olefinic bond in said ciefin is separated from any other olefinic bond or ?0 aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms with a catalyst, wherein said catalyst:
contains a nickel or palladium atom in a positive oxidation state;
contains a neutral bidentate ligand coordinated ~o said nickel or palladium atom, and where,:n coordination to said nickel or palladium atom is t'.:rough two nitrogen atoms or a nitrogen atom and a p~:.osphorous atom; and 30 said neutral bidentate ligand, has an Ethylene ~xcaange Rate of less than 20,000 L-molls 1 when said catalvst contains a palladium atom, and less than 5.x,000 L-mol -s ' when said catalyst contains a nickel atom;
3~ and provided that when Pd is present a diene is not present.
4?
_.._ __....~~ ." ~~rT m n r nc~

Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200°C:
a first compound which is a salt of an alkali metal cation and a relatively noncocrdinating monoanion;
a second compound of the formula Rz R3 N T' ~P~
R4 ~ N~ ~S
k5 l0 (XX) and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R1~CH=CHz or R1'CH=CHR1', cyclobutene, cyclopentene, 1~ substituted norbornene, or norbornene;
wherein:
R2 and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two ?0 carbon atoms bound to it;
R3 and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that R1' contains no olefinic bond;
T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(=O)- or R150C(=O)-, 30 S is chloride, iodide, or bromide; and provided that, when norbornene or substituted norbornene is present, rio_other monomer is present.

m ~r,n~rt~ rrr nurcT tol 11 C ~t.'1 Described ~-:erein is a polyolefin, comprising, a polymer made by polymerizing one or more monomers of the formula H2C=CH(CH,)eG by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein:
each G is independently hydrogen or -CO2R1;
each a is independently 0 or an integer ef l to 20;
each R- -~.s independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that:
sa,~d polymer has at least 50 branches per 1000 methylene Groups;
in at least 50 mole percent of said monomers G
1~ is hvdroae~.; and except when no branches should be theoretica-;ly present, the number of branches per 1000 methyiene groups is 90% or less than the number of theoretical branches per 1000 methylene groups, or the number of 20 branches per 1000 methylene groups is 110% or more of theoretical branches per 1000 methylene groups, and when there should be no branches theoretically present, said polyolefin has 50 or more branches per 1000 methylene groups;
and provided that said polyoiefir. :~as at least two branches of different lengths ccntaini::c less t a:: _r~
6 carbon atoms each.
Also described herein is a polyolefi::, comprising, a polymer made by polymerizing one or more monomers c;
30 the formula HOC=CH(CH2)eG by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein:
each G is independently hydrogen cr -COZR';
each a is independently 0 or an integer of 1 to 35 20;
R' is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
and provided that:

_.._ __._..~~ ....~~ m n r nw said polymer has at least 50 branches per 1000 methylene groups;
in at least 50 mole percent of said monomers G
is hydrogen;
said polymer has at least 50 branches of the ~ormuia -(CH2)fG per 1000 methylene groups, wherei.~.
when G is the same as in a monomer and e~f, and/or for any single monomer of the formula HzC=CH(CH~ieG there.
are less than 90% of the number of theoretical branches per 1000 methylene groups, or more than 1100 of the theoretical branches per 1000 methylene groups of the formula -(CH2)fG and f=e, and wherein f is 0 or an integer c~ 1 or more;
and provided that said poiyolefin has at lease two i~ branches of different lengths containing less than 6 carbon atoms.
This invention concerns a process for the formation of linear a-olefins, comprising, contacting, at a temperature of about -100°C to about +200°C:
ethylene;
a first compound w, which is a neutral Lewis acid capable cf abstracting X to form WX , provided that the anion formed is a weakly coordinating anion, c. a cationic Lewis or Bronsted acid whose counterion is a '_'~ weakly coordinating anion; and a second compound of the formula ~Ni~
~S

(~5 (XXXI) wherein:
R' and RS are each independently hydrocarbyl or substit-.aed hydrocarbyl;
R' and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and Ry taken 4~
~..~..~.~ r~r m H~rT (D111 C ~r,~

together are hydrocarbylene or substituted hydrocarbylene to form a ring; and Q and S are each independently chlorine, bromine, iodine or alkyl; and wherein an a-olefin containing 4 to 40 carbon atoms is produced.
This invention also concerns a process for the formation of linear a-olefins, comprising, contacting, at a temperature of about -100°C to about +200°C:
ethylene and a compound of the formula Rz ~ +

R ~ N T' ~Nr Ra~N~ \Z X
~s (III) or N~Ni~U
(XXXIV) wherein:
R2 and R- are each independently hydrocarbyl or substituted hydrocarbyl;
R3 and R° are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T1 is hydrogen or n-alkyl containing up to 3B
carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6;
U is n-alkyl containing up to 38 carbon atoms;
and X is a noncoordinating anion;
and wherein an a-olefin containing 4 to 40 carbon atoms is produced.
Another novel process is a process for the formation of linear a-olefins, comprising, contacting, at a temperature of about -100°C to about +200°C:
ethylene;
and a Ni [ I I ] of Rs ~N
R4 ~ N

(VIII) 1~
R2 and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
'_0 R~ and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R' taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring and wherein an a-olefin containing 4 to 40 carbon '_'~ atoms is produced..
Also described herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about 0°C to about +200°C, a compound of the formula _.._.,~.~...~r r.,.rrT rein c ~Rv Rz ~M - ,~
~N/
R

XXXVII
and one or more monomers selected from the croup consisting of ethylene, an olefin of the Formula R1'CH=CH~ or R' CH=CHR1', cyclobutene, cyclcpentene, substituted norbornene, and norbornene, wherein:
M is Niil;i or Pd(IIi;
A is a ;~-ailyl or ;r-benzyl group;
10 R- and R- are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom acs at least two carbon atoms bound to it;
R' and R' are each independently hydrogen, 1~ hydrocarbyl, substituted hydrocarbyl or R~ and R° taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
each R'' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond ~0 in said olefin is separated from any ot'.~.er olefinic bond or aromatic ring by a quaternary carbon. atom en at least two saturated carbon atoms;
and X is a weakly coordinating anion;
and provided that:
when M is Pd a diene is not present; and when norbornene or substituted norbornene is present, no other monomer is present.
The invention also includes a compou.~.d of the f ormul a ......~~..r, r~r m ~rrT ant II C ~C\

R' R
N
M- .A
N
R<

XXXVII
wherein:
M is Ni(II) or Pd(II);
A is a ~-allyl or n-benzyl group;
R' and R'' are each independently hydrocarbyl cr substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbcn atoms bound to it;
RJ and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and R' taken together are hydrocarbylene or substituted hydrccarbylene to form a ring;
each R1' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond l~ in said olefin is separated from any other olefinic bona cr aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
and X is a weakly coordinating anion;
and provided that when M is Pd a diene is not '_'0 prese:.~.
';'his invention also includes a compound of the formula R' \ / N\ /
M
~N~ \Z X
R° I
Rsa (XXXViII) _.._ _-.-.r .......~ ,.,... r ncv wherein:
R3 and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
each R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional croup;
W is alkyiene cr substituted alkylene 1~ containing 2 or more carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is ?0 less than about 6, or an olefin of the formula R''CH=CHR1' ;
each R1' is independently hydrogen, saturated hydrocarbyl or substituted saturated hydrocarbyl; and X is a weakly coordinating anion;
?s and provided that when M is Ni, W is alkylene and each R1' is independently hydrogen or saturated hydrocarbyl.
This invention also includes a process for the production of a compound of the formula Rss Rss Rs5 R

~ \Z X
R' RS'' (XXX1/111) _ . __ ____..r .. .~~ m a r nI~\

comprising, heating a compound of the formula Rss Rss Rs~~ Rss R

\Z X
~5n (X~X~X) at a temperature of about -30°C to about +100° for a sufficient time to produce (XXXVIII), and wherein:
R- and Ry are each independently hydrogen, hvdrocarbvl, substituted hydrocarbyl or R' and R~ taken together are rydrocarbylene or substituted hydrocarbylene to form a ring;
RS'' is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;
each R~5 is independently hydrogen, IS hydrocarbyl, substituted hydrocarbyl, or a functional group;
R56 is alkyl containing 2 to 30 carbon atoms;
is is alkyl;
W is alkylene containing 2 to 30 carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6; and X is a weakly coordinating anion.
This invention also concerns a process for the polymerization of olefins, comprising, contacting a compound of the. formula 51 ..
_ _ . ._~ ._... . .,."

WO 96/23010 PC'TIUS96/01282 Rss Rss R"
Rs R3 ~ ~n~
\ / N\
M
wN \Z X.
R' Rsa (XXXViII) and ore or more monomers selected from the group consisting of ethylene, an olefin of the formula .,- CH=CH2 or R1'CH=CHR1', cyclobutene, cyclopentene, substituted norbcrnene, and norbornene, wherein:
R- and R' are each independently hydrogen, vdrocarby-~, substituted hydrocarbyl or R' and R' taken together are hydrocarbylene or substituted 10 ydrocarbylene to form a ring;
R54 is hydrocarbyl or substituted hydrocarbyi, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to 1t;
1~ each R~5 is independently hydrogen, '.~:vdrocarb}'1, substituted hydrocarbyl, or a functional Jroup;
w is alkviene or substituted alkvlene ....::tai::in g 2 cr more carbon atoms;
'_'0 Z is a neutral Lewis base wherein the donatincr atom is nitrogen, sulfur, or oxygen, provided that ..
t::e donating atom is nitrogen then the pKa of the ccn~ugate acid of that compound (measured in water? is less than about 6, or an olefin of the formula ..- CH=CHR1' ;
each R1' is independently hydrogen, saturated ~v~rocarbyl or substituted saturated hydrocarbyl; and X is a weakly coordinating anion;
and provided that:
30 when M is Ni, w is alkylene and each R1~ is _:dependently hydrogen or saturated hydrocarbyl;

pCT/US961OI282 WO 96/23010 ~ 02338526 2001-03-O1 and when norbornene or substituted norbornene is present, no other monomer is present.
This invention also concerns a homopoiypropylene containing about 10 to about 700 8+ methyiene groups ~ per 1000 total methylene groups in said homopolypropylene.
Described herein is a homopolypropylene wherein the ratio of 8+:~ methylene groups is about 0.5 to about 7.
Also included herein is a homopolypropylene in whicr. about 30 to about 85 mole percent of the monomer units are enchained in an c.~,l fashion.
nRTATT ~ OT Tug' IhTVENTION
Herein. certain terms are used to define certain 1~ chemical groups or compounds. These terms are define d below.
~ A "hydrocarbyl group" is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein.
contain. 1 to about 30 carbon atoms.
~ By "not containing olefinic or acetylenic bonds" is meant the grouping does not contain olefinic carbon-carbon double bonds (but aromatic rings are not excluded) and carbon-carbon triple bonds.
'_'~ ~ By "substituted hydrocarbyl" herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted" are heteroaromatic rings.
3j ~ By an alkyl aluminum compound is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide, ~3 ~i ~oc~Ti tTC cNFFT lRl II F 26) oxygen, and halogen may also be bound to aluminum atoms in the compound.
~ By "hydrocarbylene" herein is meant a divalent group containing only carbon and hydrogen.
Typical hydrocarbylene groups are -(CHz)4-, -CH2CH ( CH~CH3 ) CH2CH,- and \ \
/ /
(An) If not otherwise stated, it is preferred that hydrocarbylene groups herein contain 1 to about 30 carbon atoms.
~ By "substituted hydrocarbylene" herein is 1~ meant a hydrocarbylene group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. if not ?0 otherwise stated, it is preferred that substituted hydrocarbylene groups herein contain 1 to about 30 carboy. atoms. Included within the meaning of "substituted" are heteroaromatic rings.
~ Bv substituted norbornene is meanta norbornene whicr. is substituted with one cr more groups whit:. does not interfere substantially with the polymerization. It is preferred that subsrituent groins (if they contain carbon atoms) contain 1 to 30 carbon atoms. Examples of substituted norbornenes are ~0 ethylidene norbornene and methylene norbornene.
~ By "saturated hydrocarbyl" is meant a univalent group containing only carbon and hydrogen which contains no unsaturation, such as oiefinic, acetylenic, or aromatic groups. Examples of such ~? groins include alkyl and cycloalkyl. If rot otherwise ;4 w vw~~eT~ >n !~t 1t'1-T ID111 C nG'\

stated, it is preferred that saturated hydrocarby-_ groups herein contain 1 to about 30 carbon atoms.
~ By "neutral Lewis base" is meant a compound, which is not an ion, which can act as a Lewis base.
Examples of such compounds include ethers, amines, sulfides, and organic nitrites.
~ By "cationic Lewis acid" is meant a cation which oan act as a Lewis acid. Examples of such cations are sodium and silver ca n ons.
~ By "a-olefin" is meant a compound or the form'~1 a C::,=CHR19, wherein R'9 is n-alkyl or branched alkyl, N=e~erably n-alkyl.
~ By "linear a-olefin" is meant a compound cf the formula CH;=CHRIS, wherein R19 is n-alkyl. It is 1~ preferred ti:at t::e linear a-olefin have 4 to ~~ carbcr.
atoms.
~ By a "saturated carbon atom" is meant a carbon atom which is bonded to other atoms by single bonds or.~~y. Not included in saturated carbon atoms are ?0 carbon atoms which are part of aromatic rings.
~ By a quaternary carbon atom is meant a saturated carbon atom which is not bound to anv hydrogen atoms. A preferred quaternary carbon atom, is bound to four other carbon atoms.
'-' ~ By an olefinic bond is meant a carbon-carbon.
doub_e bc.~.d, but does not '_~clude bonds ~.. aro",at;c rings.
~ By a rare earth metal is meant one of lant hanur;~, cerium, praeseodymium, neodymium, 30 promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium c.
lutetium.
':his invention concerns processes for making polymers, comprising, contacting one or more selected 3~ olefins en cycloolefins, and optionally an ester or carboxylic acid of the formula CHz=CH(CH2)mCO:RI, and other selected monomers, with a transition metal containing catalyst (and possibly other catalyst m ~e~TiTmc cuccT lL7111 C 9R1 components). Such catalysts are, for instance, various complexes of a diimine with these metals. By a "polymerization process herein (and the polymers made therein)" is meant a process which produces a polymer s with a degree of polymerization (DP) cf about 20 or more, preferably about 40 or more [except where otherwise noted, as in P in compound (VI)] By "DP" is meant the average number of repeat (monomer) units ir.
the polymer.
One ef these catalysts may generally be written as Rz R3 , N~ ,Q
M
W
Ra N S

(I) l~ wherein: M is Ni(II), Co(II), Fe(II) or Pd(II); R' and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R4 are each independently hydrogen, '_'0 hydrocarbyl, substituted hydrocarbyl or R' and R' taken together are hydrocarbylene or substituted ::ydrocarbylene tc form a ring; Q is alkyl, hydride, chlcride, iodide, or bromide; and S is alkyl, hydride, chloride, iodide, or bromide. Preferably M is Ni(II) or Pd(II) .
In a preferred form of (l), R3 and R4 are each independently hydrogen or hydrocarbyl. If Q and/or S
.s alkyl, it is preferred that the alkyl contains I to 4 carbon atoms, and more preferably is methyl.
,0 Another useful catalyst is ~6 .., ~.,r~~~,Tr cucrT ~a1 n F ~R1 Rz T~
~Pd~
Ra N Z
Rs X-(II) wherein: R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it: R' and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R~ and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R'SC(=O)- or R150C(=O)-; Z
is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that, if the 1~ donating atom is nitrogen, then the pKa of the conjugate acid of that compound is less than about 6; X
is a weakly coordinating anion; and R15 is hydrocarbyl not containing olefinic or acetylenic bonds.
In one preferred form of (II), R' and R9 are each ?0 independently hydrogen or hydrocarbyl. In a more preferred form of (II), T' is alkyl, and T' is especially preferably methyl. It is preferred that Z
is R6~O or R'CN, wherein each R6 is independently hydrocarbyl and R is hydrocarbyl. It is preferred that R6 and R' are alkyl, and it is more preferred that they are methyl or ethyl. It is preferred that X is BAF, SbF6 , PFD or BF9 .
Another useful catalyst is m ~en~~ tTe euLtT !0111 C ~R1 N\ Ti Nib R4 ~ N Z

(III) wherein: R~ and RS are each independently hydrocarbyl s or substituted hydrocarbyl, provided that t~e carbon atom bound to the imino nitrogen atom has at '.east two carbcn atoms bound to it; R~ and R~ are each independently hydrogen, hydrocarbyl, cr substituted hydrocarbyiene, or R3 and R4 taken together a=a 10 hydrocarbyiene or substituted hydrocarbylene ~~. fo=m a ring; T' is hydrogen, hydrocarbyl not contai~~.ng olefinic or acetyienic bonds, R15C(=O)- or R'-OC(=O)-, Z
is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the 1~ donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6; X is a weakly coordinating anion; and R15 is hydrocarbyl not containing olefinic or acetylenic bonds.
In one preferred form of (III), R' and :~' are each ~'0 independently hydrogen, hydrocarbyl. In a mc=a pre_erred form of (III) T' is alkyl, and T' .s especially preferably methyl. It is preferred that Z
is R~,O or R Cn, wherein each R6 is independe_~.~ 1y hydrocarbyl and R'' is hydrocarbyi. It is preferred that R6 and R are alkyl, and it is especially preferred.
that they are methyl or ethyl. It is preferred that X
is BAF- , SbF~- , PF6- or BF9- .
Relatively weakly coordinating anions are known tc the artisan. Such anions are often bulky anions, 30 particularly those that may delocalize their negative charge. Suitable weakly coordinating anions in this Application i::clude (Ph)4B (Ph = phenyl), tetrakis[3,5-bis(trifluoromethyl)phenyl]bora~e (hereir_ ~8 _ _-.-..__ .. .~~ m w r nev WO 96/23010 PC'T/US96/01281 abbre~~iated BAF) , PF6 , 3F4 , SbFE , trifluoromethanesulfonate, p-toluenesulfonate, (RfS02) 2N-, and (C6F5) 4B~ . Preferred weakly coordinating anions include BAF , PF6 , BF4 , and SbF6 .
Also useful as a polymerization catalyst is a compound of the formula N~ ,O=C - -M
N~ ~(CHR~6)n R I X_ Rs (IV) wherein: R2 and RS are each independently hydrocarbyi or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R° are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and R° taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; M is Ni(II) or Pd(II); each R16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms; n is '?0 1, 2, or 3; X is a weakly coordinating anion; and RB is hydrocarbyl.
It is preferred that n is 3, and all of R16 are hydrogen. Tt is also preferred that RB is alkyl or substituted alkyl, especially preferred that it is alkyl, and more preferred that Re is methyl.
Another useful catalyst is Rs I i I R3.
~Nv ~T ,N~
~Pd E 1/Pd\
T
R4 Rs Rs Ra X_ (v) ~9 w m~~rm rTN HL)t_'~T /D111 C ~~'.~

WO 96!23010 PCTNS96/01282 wherein: R~ and RS are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and Ry are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R9 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T1 is hydrogen, hydrocarbyl not containing w clefinic or acetylenic bonds, R15C(=O?- or R1'OC(=O)-;
:~'S is hydrocarbyl not containing olefinic or acetylenic bonds; E is halogen or -OR'e; R18 is hydrocarbyl not containing olefinic or acetylenic bonds; and X is a weakly coordinating anion. It is 1~ preferred that T~ is alkyl containing 1 to 4 carboy. -atoms, and more preferred that it is methyl. In other preferred compounds (v), R3 and R4 are methyl or hydrogen and R2 and RS are 2,6-diisopropylphenyl and X
is BAF. It is also preferred that E is chlorine.
20 Another useful catalyst is a compound of the formula N Pd T
Ra ~ Ni vX
I
Rs (VII?
wherein: R2 and RS are each independently hydrocarbyl or substituted hydrocarbyl , provided that the carbon atom bound to the imino nitrogen atom has at least twc 30 carbon atoms bound to it; R3 and R° are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R9 taken together are hydrocarbylene or substituted hydrocarbylene to form a "
_.._..~.~, .~.. ..~ ~~rT m n c nc~

ring; T' is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing oiefinic or acetylenic bonds, R15C (=O) - or R150C (=O) -; R'S is ~ hydrocarbyl not containing olefinic cr acetylenic bonds; and X is a weakly coordinating anion. In a more preferred form of (VII), T2 is alkyl containing 1 to 4 carbon atoms and T' is especially preferably methyl.
It is preferred that X is perfluoroalkylsulfonate, especially trifluoromethanesulfonate (triflate). If X
is an extremely weakly coordinating anion. such as BAF, (VII) may not form. Thus it may be said that ;ViI) forms usually with weakly, but perhaps not extremely weakly, coordinating anions.
l~ Ir. al-; compcunds, intermediates, catalysts, processes, etc. in which they appear ;.. is preferred that R' and RS are each independently hydrocarbyl, and in one form it is especially preferred that R' and RS
are both 2,6-diisopropylphenyl, particularly when R3 ?0 and R4 are each independently hydrogen or methyl. It is also preferred that R and R are each independently hydrogen, hydrocarbyl or taken together hydrocarbylene to form a carbocyclic ring.
Compounds of the formula (I) wherein M is Pd, Q is alkyl and S is halogen may be made by the reaction of the c..rrespon :lag 1, S-cycloectadiene (COD) P~ cc-~piex wit'.: the appropriate diimine. When M is Ni, '_) can be made by the displacement of a another ligand, such as a dialkylether or a polyether such as 1,2-~0 dimethoxyethane, by an appropriate diimine.
Catalysts of formula (II), wherein X is BAF , :nay be made by reacting a compound of formula (I) wherein Q
is alkyl and S is halogen, with about one eauivalent of a.~. alkal_ metal salt, particularly the sodium sale, of 3~ HBAF, in the Dresence of a coordinating ligand, particularly a nitrite such as acetonitrile. When X
is an anion. such as BAF , SbF6~ or BF4 the same rm mnTiTmTr cu«T lDl II C ~7R1 starting palladiu;r, compound can be reacted with the silver salt AgX.
However, sometimes the reaction of a diimine with a 1,5-COD Pd complex as described above to make ~ compounds of formula (II) may be slow and/or give poor conversions, thereby rendering it difficult to make the starting material for (II) using the method described in the preceding paragraph. For instance when:
R'=RS=Ph-CH- and R'=Ry=H; R'=RS=Ph- and R3=R4=Ph; R'=RS=2-10 t-butylphenyi and R'=R~'=CH3; R2=RS=a-naphthyl and R'=R'=CHI ; and R'=R~=2-phenylphenyl and R3=R°=CH, difficulty may be encountered in making a compound of formula (_I).
In these ~r.stances it has been found more Is convenient to prepare (~I) by reacting [(r~'-1,5-COD) PdT'Z)'X , wherein T- and X are as defined above and Z is an organic nitrite ligand, preferably in an organic nitrite solvent, with a diimine of the formula Rs t ,N
Ra ~ N

?0 (VII) By a "nitrite solvent" is meant a solvent that is at least 20 volume percent nitrite compound. The ?~ product o. this reaction is (II), in which the Z ligand is the nitrite used in the synthesis. ~n a preferred synthesis, T' is methyl and the r.itrile used is the same as in the starting palladium compound, and is more preferably acetonitrile. The process is carried out in 30 solution, preferably when the nitrite is substantially all of the solvent, at a temperature of about -40°C to about +60°C, preferably about 0°C to about 30°C. It is 6'_' _..~~~.~...~~ m ~rrT rnt tt C nC\

preferred that the reactants be used in substantially equimolar quantities.
The compound [ (r)4-1, 5-COD) PdTlZ]'X , wherein T' is alkyl, Z is an organic nitrite and X is a weakly ~ coordinating anion may be made by the reaction of [(r~'-1,5-COD)PdTlA, wherein A is C1, Br or I and T1 is alkyl with the silver salt of X~, AgX, or if X is BAF with an alka'_i metal salt of HBAF, in the presence of an organic nitriie, which of course will become the ligand Tj. In a preferred process A is C1, T1 is alkyl, more pre_erGbiy methyl, and the organic nitrite is a~z alkyl nitrite, more preferably acetonitrile. The starting mate=fiats are preferably present in approximately equ_~:clar amounts, except for the nitrite which is 1~ preset= preferably in excess. The solvent is pre:=rably a non-coordinating solvent such as a halcoarbon. Methylene chloride is useful as such a solvent. she process preferably is carried out at a temperature of about -40°C to about +50°C. It is ?Q preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen.
ComDOUnds of formula (II) [or (III) when the metal is r..cke 1 ] car. also be made by the reaction of R3~-,-N T' i , v Ra~N T
i ~5 (X) 30 wit:. a source of the conjugate acid of the anion X, the acid HX or its equivalent (such as a trityl salt) in the presence of a solvent which is a weakly coord'_nating ligand such as a dialkyl ether or an alkyl ~~ ~nnm,~~ rrr rucLT rDl 11 C ~R1 nitrite. It is preferred to carry out this reaction at about -80°C to about 30°C.
Compounds of formula (XXXXI) can be made by a process, comprising, contacting, at a temperature of about -80°C to about +20°C, a compound of the formula rl'-1, 5-COD) PdMe2 and a diimine of the formula Rz R4 ~ N

(VIII) wherein: COD is 1,5-cyclooctadiene; R' and R' are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the 1~ imino nitrogen atom has at least two carbon atoms bound to it; and R3 and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R~ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.,_It is preferred that ?0 the temperature is about -50°C to about +10°C. It is also preferred that the two starting materials be used in approximately equimolar quantities, and/or that the reaction be carried out in solution. It is preferred that R-' and RS are both 2-t-butylphenyl or 2,5-di-t-butylphenyl and that R3 and Rq taken together are A.n, or R' and R5 are both hydrogen or methyl.
ComDOUnds of formula (IV) can be made by several routes. In one method a compound of formula (II) is reacted with an acrylate ester of the formula 30 CHZ=CHCO~R1 wherein R1 is as defined above. This reaction is carried out in a non-coordinating solvent such as methylene chloride, preferably using a greater than 1 to 50 fold excess of the acrylate ester. In a 6~
_.._ __._.... .,. ,~..T m, n r ncv preferred reaction, Q is methyl, and R- is alkyl containing 1 to 4 carbon atoms, more preferably methyl.
The crocess is carried out at a temperature of about -100°C to about +100°C, preferably about 0°C to about 50°C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen Alternatively, (IV) may be prepared by reacting (I), wherein Q is alkyl and S is C1, Br or I with a source of an appropriate weakly coordinating anion such as AgX or an alkali metal salt of BAF and an acrylate ester (formula as immediately above) in a single step.
l~ Approximately eauimolar auantities of (I) and the weakly coordinating anion source are preferred, but the acrylate ester may be present in greater than 1 to 50 fold excess. In a preferred reaction, Q is methyl, and R' is alkyl containing 1 to 4 carbon atoms, more preferably methyl. The process is preferably carried out at a temperature of about -100°C to about +100°C, preferably about 0°C to about 50°C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification e( the ingredients and keeping the process mass under an inert gas such as nitrogen.
In another variation of the preparation of (IV) from (.) the source of the weakly coordinating anion is a compound which itself does not contain an anion, ~ut which can combine with S [of (I)] to form such a weakly coordinating anion. Thus in this type of process by "source of weakly coordinating anion" is meant a compound which itself contains the anion which will become X , or a compound which during the process can 3~ combine with other process ingredients to form such an anion.
Catalysts of formula (V), wherein X~ is BAF , may be made by reacting a compound of formula (I) wherein Q
6~
__.__._~ ...~~ ..,. n r nr\

WO 96!23010 PCT/US96/01282 is alkyl and S is halogen, with about one-rd~~~ or an equivalent of an alkali metal salt, particularly the sodium salt, of HBAF. Alternatively, (V) containing other anions may be prepared by reacting (I), wherein Q
is alkyl and S is C1, Br or I with one-half equivalent of a source of an appropriate weakly coordinating anion such as AgX.
Some of the nickel and palladium compounds described above are useful in processes for 10 polymerizing various olefins, and optionally also copolymeri~~rg olefinic esters, carboxylic acids, or other functional olefins, with these olefins. When (I) is used as a catalyst, a neutral Lewis acid or a cationic Lewis or Bronsted acid whose counterion is a 1~ weakly coordinating anion is also present as part of the catalyst system (sometimes called a "first compound" in the claims;. By a "neutral Lewis acid" is meant a compound which is a Lewis acid capable for abstracting Q or S from (I) to form a weakly ?0 coordination anion. The neutral Lewis acid is originally uncharged (;.e., not ionic). Suitable neutral Lewis acids include SbFS, Ar3B (wherein Ar is aryl), and BF~. By a cationic Lewis acid is meant a cation with a positive charge such as Ag', _. , and Na' .
In those instances in which (I) (and sim,~lar catalysts whic:. require the presence of a ne~.:tral Lewis acid or a cationic Lewis or Bronsted acid), does not contain ar: alkyl or hydride group already bonded to the metal (;.e., neither Q or S is alkyl or hydride), the 30 neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the metal, ;.e., causes an alkyl group or hydride to become bonded to t::e metal atom.
A preferred neutral Lewis acid, which can alkylate 3~ the metal, is a selected alkyl aluminum compound, such as R9~A1 , zy,AlC1 , R9A1C1 2 , and "R9A10"
(alkylaluTinoxanes), wherein R9 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms.

Suitable alkyl aluminum compounds include methylaluminoxane !which is an oligomer with the general formula [MeAlO) n) , (CzHs) 2A1C1, C,H~A1C1~, and [ ( CH3 ) zCHCHz ) 3A1 .
Metal hydrides such as NaBH4 may be used to bond hydride groups to the metal M.
The first compound and (I) are contacted, usually in the liquid phase, and in the presence of the olefin, and/or 4-vinylcyclohexene, cyclopentene, cyclobutene, substituted norbornene, or norbornene. The liquid phase may include a compound added just as a solvent and/or may include the monomerls) itself. The molar ratio of first compound:nickel or palladium ccmplex is about 5 to about 1000, preferably about 10 tc about 1~ 100. The temperature at which the polymerizatio.~. is carried out is about -100°C to about +200°C, preferably about -20°C to about +80°C. The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa, or more, being a ?0 suitable range. The pressure may affect the microstructure of the polyolefin produced (see below).
When using (I) as a catalyst, it is preferred that R3 and R4 are hydrogen, methyl, or taken together are \ \
/ /
?5 (An) It is also preferred that both RZ and RS are 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,6-30 diethylphenyl, 4-methylphenyl, phenyl, 2,4,6-trimethylphenyl, and 2-t-butylphenyl. When M is NilII), it is preferred that Q and S are each independently chloride or bromide, while when M is Pd(II) it is preferred that Q is methyl, chloride, or _.
~5 bromide, and S is chloride, bromide or methyl. In __ _.._~ ._... .. ,.,., addition, the specific combinations of groups in't~:e catalysts listed in Table I are especially preferred.
Table I
R' R' R' RS Q S M

2,6-i-PrPh H H 2,6-i-PrPh Me C1 Pd 2,6-i-PrPh Me Me 2,6-i-PrPh Me Cl Pd 2,6-i-PrPh An An 2,6-i-PrPh Me C1 Pd 2,6-MePh H H 2,6-MePh Me Cl Pd 4-MePh H H 4-MePh Me C1 Pd 4-MePh Me Me 4-MePh Me C1 Pd 2,6-i-PrPh Me Me 2,6-i-PrPh Me Me Pd ~,o-i-PrPh H H 2,6-i-PrPh Me Me Pd 2,6-MePh H H 2,6-MePh Me Me Pd 2,6-i-PrPh H H 2,6-i-PrPh Br Br Ni 2,6-i-PrPh Me Me 2,6-i-PrPh Br Br Ni 2,6-MePh H H 2,6-MePh Br Br Ni Ph Me Me Ph Me Cl Pd 2,6-EtPh Me Me 2,6-EtPh Me C1 Pd 2,4,6-MePh Me Me 2,4,6-MePh Me C1 Pd 2,6-MePh Me Me 2,6-MePh Br Br Ni 2,6-i-PrPh An An 2,6-i-PrPh Br Br Ni 2,6-MePh An An 2,6-MePh Br Br 1i 2-t-BuPh An An 2-t-BuPh Br Br Ni 2,5-t-BuPh An An 2,5-t-BuPh Br Br Ni ~-i-Pr-6-MePh An An 2-i-Pr-6-MePh Br Br Ni -i-Pr-6-MePh Me Me 2-i-Pr-6-MePh Br Br Ni ~,6-t-BuPh H H 2,6-t-BuPh Br Br Ni 2,6-t-BuPh Me Me 2,6-t-BuPh Br Br Ni 2,6-t-BuPh An An 2,6-t-BuPh Br Br Ni 2-t-BuPh Me Me 2-t-BuPh Br Br Ni Note - In Tables and II, and elsewhere herein, I

t'_:e following convention and abbreviations ed.
are us For R2 and R5, when a ring is .
substituted phenyl present, the a mountof ubstitution is by the s indicated l0 ~~.:mber of numbers indica ting positions pheny_ on the _. __ _. .___ ,...

ring, so that, for example, 2,6-i-PrPh is 2,6-diisopropylphenyl. The following abbreviations are used: i-Pr = isopropyl; Me = methyl; Et = ethyl; t-Bu =
t-butyl; Ph = phenyl; Np = naphthyl; An = 1,8-naphthylylene (a divalent radical used for both R3 and Rq, wherein R3 and R9 taken together form a ring, which is part cf an acenaphthylene group); OTf = triflate;
and BAF = tetrakis[3,5-bis(trifluoromethyl)phenyiJborate.
Preferred olefins in the polymerization are one or more of ethylene, propylene, 1-butene, 2-butene, 1-hexene 1-octene, 1-pentene, 1-tetradecene, norbornene, and cvclonentene, with ethylene, propylene and 1~ cyclopentene being more preferred. Ethylene (alone as a homopolymer) is especially preferred.
The polymerizations with (I) may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, monomer(s), and ?0 polymer may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene arci benzene.
Whether such a liquid is used, and which and how much liquid is used, may affect the product obtained.
It may affect the yield, microstructure, molecular weight, etc., of the polymer obtained.
30 Compounds of formulas (XI), (XIII), (XV) and (XIX) may also be used as catalysts for the polymerization of the same monomers as compounds of formula (I). The polymerization conditions are the same fcr (XI), (XIII), (XV) and (XIX) as for (I), and the same Lewis 35 and Bronsted acids are used as co-catalysts. Preferred groupings R2, R', R', and RS (when present) in (XI) and (XIII) are the same as in (I), both in a polymerization process and as compounds in their own right.

...........err r",rrT ,ni ~~ r ~1C\

' CA 02338526 2001-03-O1 Preferred (XI) compounds have the metals Sc(III), Zr(IV), Ni(II), Ni(I), Pd(II), Fe(II), and Co(II).
When M is Zr, Ti, Fe, and Sc it is preferred that all of Q and S are chlorine or bromine more preferably chlorine. When M is Ni or Co it is preferred that all of Q and S are chlorine, bromine or iodine, more preferably bromine.
In (XVII) preferred metals are Ni(II) and Ti(IV).
It is preferred that all of Q and S are halogen. It is also preferred that all of RZB, R29, and R3° are hydrogen, and/or that both R44 and R45 are 2,4,6-trimethyiphenyl or 9-anthracenyl.
In (XV) it is preferred that both of R~' are hydrogen.
In (XIII), (XXIII) and (XXXII) (as polymerization catalysts and as novel compounds) it is preferred that all of R'°, R'1, R'2 and R~3 are methyl. It is also preferred that T1 and T' are methyl. For (XIII), when M is Ni(I) or (II), it is preferred that both Q and S
?0 are bromine, while when M is Pd it is preferred that Q
is methyl and S is chlorine.
Compounds (II), (IV) or (VII) will each also cause the polymerization of one or more of an olefin, and/or a selected cyclic olefin such as cyclobutene, '?~ cvclo~entene or norbornene, and, when it is a Pd(II) complex, optionally copolymerize ar_ ester or carboxylic acid of the formula CHI=CH(CH2)mC02R1, wherein m is 0 or an integer of 1 to 16 and R1 is hydrogen or hydrocarbyl or substituted hydrocarbyl, by themselves (without 30 cocatalysts). However, (III) often cannot be used when the ester is present. When norbornene or substituted norbornene is present no other monomer should be present.
Other monomers which may be used with compounds 35 (II), (IV) or (VII) (when it is a Pd(II) complex) to form copolymers with olefins and selected cycloolefins are carbon monoxide (CO), and vinyl ketones of the general formula HOC=CHC (O) RCS, wherein R~5 is alkyl _.....,~.~, ...~ m ~r~ m n c nc~

WO 96!23010 PCT/US96/01282 containing 1 to 20 carbon atoms, and it is preferred that R25 is methyl. In the case of the vinyl ketones, the same compositional limits on the polymers produced apply as for the carboxylic acids and esters described s as comonomers in the immediately preceding paragraph.
CO forms alternating copolymers with the various olefins and cycloolefins which may be polymerized with compounds (II), (IV) or (VII). The polymerization to form the alternating copolymers is done with both CO
and the olefin simultaneously in the process mixture, and available to the catalyst. It is also possible to form block copolymers containing the alternating CO/(cyclo)olefin copolymers and other blocks containing just that olefin or other olefins or mixtures thereof.
is This may be done simply by sequentially exposing compounds (II), (IV) or (VII), and their subsequent living polymers, to the appropriate monomer cr mixture of monomers to form the desired blocks. Copolymers of CO, a (cyclo)olefin and a saturated carboxylic acid or ester ef the formula CHz=CH(CHZ)mCOzRl, wherein m is 0 or an integer of 1 to 15 and R1 is hydrogen or hydrocarbyl or substituted hydrocarbyl, may also be made by simultaneously exposing the polymerization catalyst or living polymer to these 3 types of ''s monomers .
The polymerizations may be carried out with (II), (III), (IV) or (VII), and other catalyst molecules or COmbiiiatlOnS, initially in the solid state [assuming (IIi, (III) (IV) or (VII) is a solid] or in solution.
The olefin and/or cycloolefin may be in the gas or licruid state (including gas dissolved in a solvent). A
liquid, which may or may not be a solvent for any or all of the reactants and/or products.may also be.
present. Suitable liquids include alkanes, 3~ cycloalkanes, halogenated alkanes and cycloalkanes, ethers, water, and alcohols, except that when (III) is used, hydrocarbons should preferably be used as solvents. Specific useful solvents include methylene __ _..___ ._... . ".., chloride, hexane, CO2, chloroform, perfiuoro-(n-butyltetrahydrofuran) (herein sometimes called FC-75), toluene, dichlorobenzene, 2-ethylhexanol, and benzene.
It is particularly noteworthy that one of the liquids which can be used in this polymerization process with (II), (III), (IV) or (VII) is water, see for instance Examples 213-216. Not only can water be present but the polymerization "medium" may be largely water, and various types of surfactants may be employed 10 so that ar_ emulsion polymerization may be done, along with a suspension polymerization when surfactants are not employed.
Preferred olefins and cycloolefins in the oolvmerization using (II), (III) or (IV) are one or l~ more ef ethylene, propylene, 1-butene, 1-hexene, i-octene, 1-butene, cyclopentene, 1-tetradecene, and norbornene; and ethylene, propylene and cyciopentene are more preferred. Ethylene alone is especially preferred.
20 Olefinic esters or carboxylic acids of the formula CHZ=CH ( CH2 ) mCO2R1, wherein R' is hydrogen, hydrocarbyl , or substituted hydrocarbyl, and m is 0 or an integer of 1 to 16. It is preferred if R' hydrocarbyl or substituted hydrocarbyl and it is more preferred if it is alkyl ccntaining 1 to 10 carbon atoms, or glycidyl.
It is also preferred if m is 0 and/or R' is alkyd containing 1 to 10 carbon atoms. It is preferred to make copolymers containing up to about 60 mole percent, preferably up to about 20 mole percent of repeat uni:.a 30 derived from the olefinic ester or carboxylic acid.
Total repeat unit units in the polymer herein refer not only to those in the main chain from each monomer unit, but those in branches or side chains as well.
When using (II), (III), (IV) or (VII) as a 3~ catalyst it is.preferred that R' and R4 are hydrogen, methyl, or taken together are WO 96/23010 PC?/US96/01282 \ \
/ /
(An) It is also preferred that both R~ and RS are 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 4-methylphenyl, phenyl, 2,6-diethylphenyl, 2,4,6-trimethylphenyl and 2-t-butylphenyl. When (II) is used, it is preferred that T1 is methyl, R~ is methyl or ethyl and R is methyl.
When (III) is used it is preferred that T1 is methyl and said Lewis base is 8620, wherein R6 is methyl or ethyl. When (IV) is used it is preferred that R~ is methyl, n is 3 and R1E is hydrogen. In addition i:.
Table II are listed all particularly preferred combinations as catalysts for (II), (III), (IV) and 1~ (VII) .

_.._.,_._.._.. ." ,.rte ,." .. ~ ~r~~

i Table II
Com- R' R3 R' R' T'/T2/ Z M X
pound Re Type (II 2,6-i- Me Me 2,6-i- Me OEt, ?d BAF
) PrPh PrPh (II) 2,6-i- H H 2,6-i- Me OEt, ad BAF

PrPh PrPh (III) i- Me Me 2,6-i- Me OEt~ Ni BAF
2,6- _ PrPh PrPh (III) i- H H 2,6-i- Me OEt, ~i BAF
2,6- _ Pr Ph PrPh (II 2,6- H H 2,6-MePh Me OEt~ .d BAF
) Meph (II 2,6- Me Me 2,6-MePh Me OEt, ?d BAF
?

MePh (II) 2,6-i- Me Me 2,6-i- Me OEt2 Pd SbFS

PrPh PrPh (II) 2,6-i- Me Me 2,6-i- Me OEt~ Pd BF4 PrPh PrPh (II) 2,6-i- Me Me 2,6-i- Me OEt~ Pd PF6 PrPh PrPh (II) 2,6-i- H H 2,6-i- Me OEt_ Pd SbF

prph PrPh (II ~,4,e- Me Me 2,4,6- Me OEt, ?d SbF
i MePh MePh (II) 2,6-_ An An 2,6-i- Me OEt, Pd SbFE
-PrPh PrPh (II) 2,6-i- Me Me 2,6-i- Me NCMe Pd SbFS

PrPh PrPh (II) Ph Me Me Ph Me NCMe Pd SbF6 (II) 2,6- Me Me 2,6-EtPh Me NCMe Pd BAF

EtPh (II) 2,6- Me Me 2,6-EtPh Me NCMe Pd SbFE

EtPh (II) 2-t- Me Me 2-t-BuPh Me NCMe Pd SbF6 .

BuPh _ _ __ _-.-..~ .. .....~ ..,. " r nev (II) 1-Np Me Me 1-Np Me NCMe Pd SbF6 (Ii) Ph2CH H H Ph2CH Me NCMe Pd SbF6 (II) 2-PhPh Me Me 2-PhPh Me NCMe Pd SbF6 (II) Ph a a Ph Me NCMe Pd BAF
(IV) 2,6-i- Me Me 2,6-i- Me b Pd SbF6 PrPh PrPh (IV) 2,6-i- Me Me 2,6-i- Me b Pd BAF
PrPh PrPh (IVi 2,6-i- H H 2,6-i- Me b Pd SbFE
PrPh PrPh (IV) 2,6-i- Me Me 2,6-i- Me b Pd B(C6 PrPh PrPh FS) ,C . .

(II) Ph Me Me Ph Me NCMe Pd SbF
(VI.2,6-~ Me Me 2,6-i- Me - Pd OTf PrPh PrPh (II) Ph Ph Ph Ph Me NCMe Pd BAF
( I I ) Ph2CH H H PhzCH Me NCMe Pd SbFs a This group is -CMe2CHzCMe~
b This group is - (CHz) 3COZMe 4dhen using (II), (III), (IV) or (VII) the temperature at which the polymerization is carried out is about -100°C to about +200°C, preferably about 0°C to about X50°C, more preferably about 25°C to about 100°C.
The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. The pressure can affect the microstructure of the polyolefin produced (see below).
Catalysts of the formulas (II), (III), (IV) and (VII) may also be supported on a solid catalyst (as opposed to just being added as a solid or in solution), 1~ for instance on silica gel (see Example 98). By sup>rerted is meant that the catalyst may simply be carried physically on the surface of the solid support, may be adsorbed, or carried by the support by other means.

nme~~n~rTG CUCCT lCtl l) C ~Rl When using (XXX) as a ligand or in any process or reaction herein it is preferred that n is 2, all of R'', R'e and R'9 are hydrogen, and both of R44 and R45 are 9-anthracenyl.
Another polymerization process comprises contacting a compound of the formula [Pd (R13CN) 4] XZ or a combination of Pd[OC(O)R4°]z and HX, with a compound of the formula Rs N
R4 \ N

(VIII) and one or more monomers selected from the croup consisting of ethylene, an olefin of the formula I~ R''CH=CHI or R1'CH=CHR1', cyciopentene, cyclobutene, substituted norbornene and norbornene, wherein: R' and RS are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound '_'0 tc it; R3 and R'' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R- and R' taken together are hydrocarbyiene or substituted hydrocarbylene to form a carbocyclic ring; each R- is independently hydrocarbyl or substituted hydrocarbyl provided that R1' contains no olefinic bonds; R4° is hydrocarbyl or substituted hydrocarbyl; and X is a weakly coordinating anion; provided that when norbornene or substituted norbornene is present no other monomer is present.
30 It is believed that in this process a catalyst similar to (II) may be initially generated, and this then causes the polymerization. Therefore, ail cf the conditions, monomers (including clefinic esters and m m~r~mTT' PlIrLT /D111 C ~~.' carboxylic acids), etc., which are appl,lcable to the process using (II) as a polymerization catalyst are applicable to this process. All preferred items are also the same, including appropriate groups such as R2, R?, R4, R5, and combinations thereof . This process however should be run so that all of the ingredients car contact each other, preferably in a single phase.
Initially at least, it is preferred that this is done in solution. The molar ratio of (VIII) to palladium compound used is-not critical, but for most economical use of the compounds, a moderate excess, about 25 to 1000 excess, of (VIII) is preferably used.
As mentioned above, it is believed that in the polymerization using (VIII ) and [Pd (R"C:~T) 4] X~ or a is Pd[I; carboxylate a catalyst similar to (II) is formed. Other combinations of starting materials that can combine into catalysts similar to (l/), (III), (IV) and (VII) often also cause similar polymerizations, see for instance Examples 238 and 239.
?0 Also combinations of a-diimines or other diimino ligands described herein with: a nickel [~] or nickel [I] compound, oxygen, an alkyl aluminum compound and an olefin; a nickel [0] or nickel [I] compound, an acid such as HX and an olefin; or an a-diimine Ni[0) or nickel [I) complex, oxygen, an alkyl aluminum compound and ar, olefin. T:.us active catalysts prom a-diimines and other bidentate imino compounds can be formed beforehand or in the same "pot" (in situi in which the polymerization takes place. In all of the 30 polymerizations in which the catalysts are fcrmed in situ, preferred groups on the a-diimines are the same as for the preformed catalysts.
In general Ni[C], Ni[I]' or Ni(II) compounds may be used as precursors to active catalyst species. They 3~ must have ligands which can be displaced by the appropriate bidentate nitrogen ligand, or must already contain such a bidentate ligand already bound to the nickel atom. Ligands which may be displaced include /" m,nwr~ tTr nut~T' fDl II C ~R\

WO 96!23010 PCTlUS96/01282 1,5-cyclooctadiene and tris(o-tolyl)phosphite, which may be present in Ni[0] compounds, or dibenzylideneacetone, as in the useful Pd[0] precursor tris(dibenzylideneacetone)dipalladium[0]. These lower valence nickel compounds are believed to be converted into active Ni(II] catalytic species. As such they must also be contacted (react with) with an oxidizing agent and a source of a weakly coordinating anion (X~).
Oxidizing agents include oxygen, HX (wherein X is a 10 weakly coordinating anion), and other well known oxidizing agents. Sources of X include HX, alkylaluminum compounds, alkali metal and silver salts of X . As can be seen above, some compounds such as HX
may act as both an oxidizing agent and a source of X . , l~ Compounds containing other lower valent metals may be converted into active catalyst species by similar methods.
When contacted with an alkyl aluminum compound or HX useful Ni[0] compounds include R3 N Ra I R
/ '' ~N~ R' NI COD N
R \~ R ~N/ , \N/Ni - ~ O

s R 5 0~1e (X~i~I I I) l xxxxtn txxxxun R' R~ Rs Rs R~ Rv N N N
/ ~ \
N~- O:
\N~ \N~ N/
Ra Is Ra Is 12 R3 txxx~ctvt or txxxxv>
Various types of Ni(0] compounds are known in the literature. Below are listed references for the types 25 shown immediately above.

~..~..~.~..~r~ m ~rrT mm C nC\

~ (XXXIII) G. van Koten, et al., Ate.
Organometal. Chem., vol. 21, p. 151-239 (1982).
~ (XXXXII) W. Honrath, et al., Angew. Chem.
Int. Ed. Engl., vol. 29, p. 298-300 (1990).
~ (XXXXIV) H. tom Dieck, et al., Z.
Natruforsch., vol. 366, p. 823-832 (1981); and M.
Svoboda, et al., J. Organometal. Chem., vol. 191, p.
321-328 (1980).
~ (XXXXV) G. van Koten, et al., Adv.
Organcmetal. Chem., vol. 21, p. 151-239 (1982).
~n polymerizations using lXIV), the same preferred monomers and groups (such as R', R~, R4, RS and X) as are preferred for the polymerization using (II) are used and preferred. Likewise, the conditions used and .
I~ preferred for polymerizations with (XIV) are similar tc those used and preferred for (II), except that higher olefin pressures (when the olefin is a gas) are preferred. Preferred pressures are about 2.0 to about MPa. (XIV) may be prepared by the reaction of one 20 mcle of [Pd lRi3CN) 4] X2 with one mole of (VII I ) in aceto:~itrile or nitromethane.
~lovel compound (XIV) is used as an olefin.
polymerization catalyst. In preferred forms o' (XIV), the preferred groups R', R3, R", R~ and X are the same as are preferred for compound (II).
A:~.other type of compound whic h is an clefin polymerization catalyst are n-allyl and n-benzyl compounds of the formula R~
R
N
M- A
N
R' ~ ?C
Rs XXXVII
wherein M is Ni~(II) or Pd(II); R' and RS are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen m....n~,~tr~r I~uCL'1' IDI II C ~Rl atom has at least two carbon atoms bound to i~; R- ana R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R~' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; X is a weakly coordinating anion; and A is a n-allyi or n-benzyl group. By a n-allyl group is meant a monoanionic with 3 adjacent sp2 carbon atoms bound to a metal center in an r~3 fashion. The three spz carbon atoms may be substituted with other hydrocarbyl groups cr functional groups. Typical n-allyl groups include ~ co,R
CO,R
Ph ~ CI
wherein R is hydrocarbyl. By a n-benzyl group is meant is n-allyl ligand in which two of the sp2 carbon atoms are part of an aromatic ring. Typical Z-benzyl groups include F
F
F
?0 F.
n-Benzyl compounds usually initiate polymerization of the olefins fairly readily even at room temperature, but n-allyl compounds may not necessarily do so.
....~.nT.~ n~r twccT ~Dt 11 C ~R\

Initiation of ~-ally! compounds can be improved by using cne cr more of the following methods:
~ Using a higher temperature such as about 80°C.
~ Decreasing the bulk of the a-diimine ligand, such as Rz and R' being 2,6-dimethylphenyl instead of 2,6-diisoprcpyiphenyl.
~ baking the n-ally! ligand more bulky, such as using rather than the simple n-ally! group itself.
~ Having a Lewis acid present wl-.ile using a functional z-ally! or r-benzyl group. Relatively weak I~ Lewis acids such a triphenylborane, tris(pentafluorophenyl)borane, and tris(3,5-trifluoromethylphenyl)borane, are preferred. Suitable functional groups include chloro and ester. "Solid"
acids such as montmorillonite may also be used.
When using (XXXVII) as a polymerization catalyst, it is preferred that ethylene and/or a linear a-olefin is the monomer, or cyclopentene, more preferred if the monomer is ethylene and/or propylene, and ethylene is especially preferred. A preferred temperature for the polymerization process using (XXXVII) is about +20°C to about 100°C. It is also preferred that the partial pressure due to ethylene or propylene monomer is at least about 600 kPa.It is also noted that (XXXVII) is a novel compound, and preferred items for (XXXVII) for the polymerization process are also preferred for the compound itself.
Another catalyst for the polymerization of olefins is a compound of the formula e~ ~eeTt~ rt'e cu~CT IG! 11 F 9R1 Rss Rss R55 Rs R3 ~ W
~N\
M
N~ \Z X
R< I
R~
(XXXVIII) and one or more monomers selected from the. group consisting cf ethylene, an olefin of the formula R1'CH=CH- or R1'CH=CriRi', cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherei:: R3 and R4 are each independent_y hydrogen., hydrocarbyl, substituted hydrocarbyl or R- .
and R' take.~. together are hydrocarbylene or substituted hydrocarbyiene to form a ring; R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R55 is independently hydrogen, i:ydrocarbyl, substituted hydrocarbyl, or a functional group; W is alkylene cr substituted alkylene 1~ containing 2 or more carbon atoms; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that i~ the donating atom is nitrogen then the oKa of the conjugate acid of that compound (measured ;:~ water) is less than about 6, cr an clefin ?0 of the ~orc~,ula R1'CH=CHR1'; each R'' is independently alkyl cr substituted alkyl; and X is a weakly coordinating anion. It is preferred that l:: compound (XXXV==; that: RS° is phenyl or substituted Cheryl, and preferred substituents are alkyl groups; each RSS is '_'~ independently hydrogen or alkyl containing 1 to 10 carbon atoms; W contains 2 carbon atoms between the phenyl ri:.Q and metal atom it is bonded to or W is a divalent =~lymeric group derived from the polymerization of R1'CH=CHR'', and it is especially 30 preferred that it is -CH (CHI ) CHz- or -C (CH~ ) zCH2- , and Z
is a dialkwi ether or an olefin of the formula 8'' _..__.....~~ ~. .~~T .m n r nc~

~:- CH=CHR1'; and combinations thereof . W is a.-. alkylene croup in which each of the two free valencies are to different carbon atoms of the alkylene group.
When W is a divalent group formed by the pclymerization of R''CH=CHR'', and Z is Rl'CH=CHR1', the compound (XXXVIII) is believed to be a living ended polymer. That end of W bound to the phenyl ring actually is the original fragment from R56 from which the "bridge" w originally formed, and the remaining part of w is formed from the olefin (s) R1 ~CH=CHR1'. In a sense this compound is similar in function to compound (VI).
By substituted phenyl in (XXXVIII) and (XXXIX) is meant the phenyl ring can be substituted wit'.~_ any I~ grouping which does not interfere with the co;~pound's stability or any of the reactions the compounc undergoes. Preferred substituents in substituted phenyl are alkyl groups, preferably containing 1 to 10 carbon atoms.
~0 Preferred monomers for this polymerization are ethylene and linear a-olefins, or cyclopentene, particularly propylene, and ethylene and propylene or both are more preferred, and ethylene is especially preferred.
s Tt is noted that (XXXVII=) is a novel cc~~:pound, and preferred compounds and groupings are tire same as in the polymerization process.
Compound (XXXVIII) can be made by heating compound (XXXIX), Rss Rss R55 R< I ~ R
R' /Tr M
X-R~
15.
(XXX~X) ~..~.....~ ~r m rrrT Ifl1 it C ~R\

wherein: R' and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R' taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; R54 is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a _unctional group; R56 is alkyl containing 2 to 30 10 carboy. atoms; T' is alkyl; Z is a neutral Lewis base wherein. the donating atom is nitrogen, sulfur, or oxyge_~., provided that if the donating atom is nitrogen t:~en t:-~e pKa cf the conjugate acid of that compound ;measured in water) is less than about 6; and X is a l~ weakiv coordinating anio.~.. ?referred groups are the same as those ~n (XXXVIII). In addition it is creferred that TS contain 1 to 10 carbon atoms, and more preferred that it is methyl. A preferred temperature fey the conversion of (XXXIX) to (XXXVIII) ?0 v_s about -30°C to about 50°C. Typically the reaction takes about ~0 min. to about 5 days, the higher the temperature, the faster the reaction. Another factor which affects the reaction rate is the nature of Z.
The weaker the Lewis basicity of Z, the faster the desired reaction will be.
~nThen (II) , (III) , (IV) , (V) , (VII) , (VIII) or a combination of compounds that will generate similar co~pounds, (subject to the conditions described above) s used in tre polymerization of olefins, cyclclefins, 0 a:.d o:tionally olefinic esters or carboxylic acids, polymer having what is believed to be similar to a "living end" is formed. This molecule is that from e.:zic:. the polymer crows to its eventual molecular weight. This compound may have the structure 3~

........W T~ tTr NurCT rDI II C'C.\

WO 96/23010 PC'T/US96I01282 ~M~
~CHR»
Ra ~N R~iHCi~ X_ ~5 (VI) wherein : M is Ni ( I I ) or Pd ( I I ) ; R2 and R' are hydrocarbyl cr substituted hydrocarbyl, ~rovided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R3 and R~' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and R' take_~. together are hydrccarbyier.e o= subst,~tuted hydrccarbv;e~e tc fcrm a ring; each R" is independently hydrogen, alkyl or -(CHz)mC02R1; _ is hydrogen, hydrocarbyl got containing olefinic or acetylenic bonds, R'S(C=O)-, R1'0(C=O)-, or -CHzCH2CH~C02Re; R'S is hydrocarbyl not containing 1~ olefinic or acetylenic unsaturation; P is a divalent group containing one or more repeat units derived from the polymerization of one or more of ethylene, ar_ olefin of the formula R''CH=CHz or R1'CH=CHR'~, cyclobutene, cyclopentene, substituted ncrbornene, or ~'0 norbornene and, when M is Pd(IT_), optionally one cr more compounds of the formula CH~=CH ( CH~ ) ~CO~R' ; R~ is hydrocarbyl; each Rl' is independently hydrocarbyl or substituted hydrocarbyl provided that anv olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; m is 0 or an integer from 1 to 16; R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; and X is a weakly coordinating anion; and that 30 when M is Ni ( II ) , R11 is not -COzRe and when M is Pd a diene is not present. By an "olefinic ester or carboxylic acid" is meant a compound of the formula 8~
~..~.,~.~..~. .,~ ~re~r ,nt n a ~c~

WO 96/23010 PCTlUS96/01282 CH2=C~-i ( CHI ) mCO~R- , where in m and R1 are as def fined immediately above.
This molecule will react with additional monomer (olefin., cyclic olefin, olefinic ester or olefinic carboxylic acid) to cause further polymerization. In other words, the additional monomer will be added to P, extending the length c~ the polymer chain. Thus P may be of any size, from one "repeat unit" to many repeat units, and when the polymerization is over Gad P is 10 removed from M, as by hydrolysis, P is essentially the polymer product o~ the polymerization. Polymerizations with (Vi), that v~s contact of additional monomer with this r~.oiecule takes peace under the same conditions as described above for the polymerization process using 1~ (II), ._II), (IV), (V), (VII) or (VIII), or combinations of compounds that will generate similar molecules, and where apprcpriate preferred ccnditions and structures are the same.
The Group T' in (VI) was originally the group T1 in (II) or (III), or the group which included R8 in (IV). ;t in essence will normally be one of the end groins of the eventual polymer product. The oiefinic grou5 which is coordinated to M, R"CH=CHR11 is normally one of the monomers, olefin, cyclic olefin, or, if Pd(I-' is M, an olefinic ester or carboxylic acid. If more than one cf these monomers is present _.. the reac~icn, it may be any one of them. It is preferred that "_' is alkyl and especially preferred that __ is methyl, and it is also preferred that R11 is hydroger_ 30 or n-alkyl. It is also preferred that M is Pd(II).
Another "form" for the living end is (XVI).

R N (Q)r H
-R~
err,( ,,H_~_R, (XVI) ~h )a __._..~ .,. ...~ ,." a r nee This type of compound is sometimes referred to as a compound in the "agostic state". In fact both (VI) and (XVI) may coexist together in the same polymerization, both types cf compound representing living ends. It is believed that (XVI)-type compounds are particularly favored when the end of the growing polymer chain bound to the transition metal is derived from a cyclic olefin.
such as cyclopentene. Expressed in terms of the structure of (XVI) this is when both of R11 are ::vdrocarbylene to form a carbocyclic ring, and it is -=eferred that this be a five-membered carbocyclic ring.
l~ ~cr both the polymerization process using (XVI) and the structure of (XVI) itself, the same conditions a:.d groups as are used and preferred for (VI) are also used and preferred for (XVI), with the exception that for R'1 it is preferred in (XVI) that both of R11 are ?0 ~ydrocarbylene to form a carbocyclic ring.
This invention also concerns a compound of the formula R3~N, i~~~CHR~a Ra N RiaHC X' (IX) when ein : M is Ni ( Ih) or Pd ( II ) ; RZ and RS are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen 30 atom has at least two carbon atoms bound to it; R3 and R' are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R' and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ~~ ww~rw r~r Al IPrT /R11) C'C:~

WO 96!23010 PCTNS96/01282 ring; each R14 is independently hydrogen, alkyl or [when M is Pd(II) ] - (CH~),~C02R1; R' is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; T4 is alkyl, -R6°C (O) ORe, R15 (C=O) - or R150C(=O)-; R15 is hydrocarbyl not containing olefinic or acetylenic bonds; R6° is alkylene not containing olefinic or acetylenic bonds; Re is hydrocarbyl; and X
is a weakly coordinating anion.
(IX) may also be used to polymerize olefins, l0 cyclic olefins, and optionally olefinic esters and carboxylic acids. The same conditions (except as noted below) apply to the polymerizations using (IX) as they do for (VI). It is preferred that M is Pd(II) and T~
is methyl.
1~ A compound of formula (V) may also be used as a catalyst for the pclymerization of olefins, cyclic olefins, and optionally olefinic esters and/or carboxylic acids. In this process (V) is contacted with one or more of the essential monomers. Optionally 20 a source of a relatively weakly coordinating anion may also be present. Such a source could be an alkali metal salt of BAF or AgX (wherein X is the anion), etc.
Preferably about 1 mole of the source of X, such as AgX, will be added per mole of (V). This will usually ''~ be done in the liquid phase, preferably in which (V) and the source of the anion are at least partially soluble. The conditions of this polymerization are otherwise the same as described above for (II), (III), (IV) and (VII), including the preferred conditions and 30 ingredients.
In polymerizations using (XX) as the catalyst, a first compound which is a source of a relatively noncoordinating monoanion is present. Such a source can be an alkali metal or silver salt of the monoanion.
3~

_ _ __ _~~ .r _. .

_ R3 N T' ~Pc~
~S
R4 ~ N
~5 (XX) It is preferred that the alkali metal cation is sodium or potassium. It is preferred that the monoanion is SbF6 , BAF, PFE , or BF9 , and more preferred that it is BAF. It is preferred that '.' is methyl and/or S is chlorine. All other preferred groups and conditions for these polymerizations are the same as for polymerizations with (i1).
In aii of the above poiymerizations, and the catalysts for making them i~ is preferred that R2 and R5, if present, are 2,6-diisopropylphenyl and R3 and R4 are hydrogen or methyl. When cyclopentene is l~ polymerized, is preferred that R~ and RS (if present) are 2,6-dimethylphenyl or 2,4,6-trimethylphenyl and that R3 and R~' taken together are An. R', R', Rq and R
and other groups herein may also be substituted hydrocarbyl. As previously defined, the substituent ?0 groups in substituted hydrocarbyl groups (there may be one or more substituent groups) should not substantially interfere witr. the polymerization or other reactions that the compound is undergoing.
Whether a particular group will interfere can first be 2~ judged from the artisans general knowledge and the particular polymerization or other reaction that is involved. For instance, in polymerizations where an alkyl aluminum compound is used may not be compatible with the presence of groups containing an active 30 (relatively acidic) hydrogen atom, such as hydroxyl or carboxyl because of the known reaction of alkyl aluminum compounds with such active hydrogen containing groups (but such polymerizations may be possible if _..___.~....~ "",.,.T m n c nay enough "extra" alkyl aluminum compound is added to react with these groups). However, in very similar polymerizations where alkyl aluminum compounds are not present, these groups containing active hydrogen may be ~ present. Indeed many of the polymerization processes described herein are remarkably tolerant to the presence of various functional groups. Probably the most important considerations as to the operability of compounds containing any particular functional group l0 are the effect of the group on the coordination of the metal atom ('_~ present), and side reaction of the group with other process ingredients (such as noted above).
Therefore c~ course, the further away from the metal atom the f~.:nctional group is, the less likely « is to l~ influence, say, a polymerization. If there is doubt as to whether a particular functional group, in a particular position, will affect a reaction, simple minimal experimentation will provide the requisite answer. Functional groups which may be present in R', ?0 Ri, R~', R', and other similar radicals herein include hydroxy, halo (fluoro, chloro, bromo and iodo), ether, ester, dialkylamino, carboxy, oxo (keto and aldehyo), nitre, amide, thioether, and imino. Preferred functional groups are hydroxy, halo, ether and '_'J dialkvlamino.
hlso ~_. ail of the polymerizations, the (cyclo)olefi:~ may be substituted hydrocarbyl. Suitable substituents include ether, keto, aldehyde, ester, carboxylic acid.
30 Tn ail of the above polymerizations, with the exce~tio:~s noted below, the following monomer(s), to produce the corresponding homo- or copolymers, are preferred to be used: ethylene; propylene; ethylene and propylene; ethylene and an a-olefin; an a-olefin;
3~ ethylene and an alkyl acrylate, especially methyl acrylate; ethylene and acrylic acid; ethylene and carboy. monoxide; ethylene, and carbon monoxide and an acryiate ester or acrylic acid, especially methyl _ _ __ _-.-. .~~ .., ,~.-~ ..~., .. r nc~

acryiate; propylene and alkyl acrylate, especially meth~~1 acrylate; cyciopentene; cyclopentene and ethylene; cyclopentene and propylene. Monomers which contain a carbonyl group, including esters, carboxylic ~ acids, carbon monoxide, vinyl ketones, etc., can be polymerized with Pd(II) containing catalysts herein, with the exception of those that require the presence of a neutral or cationic Lewis acid or cationic Bronsted acid, which is usually called the "first 10 compou:~d" in claims describing such polymerization processes.
Another useful "monomer" for these polymerization.
processes is a C4 refinery catalytic cracker stream, which will often contain a mixture of n-butane, Is isobutane, isobutene, 1-butene, 2-butenes and small amounts of butadiene. This type of stream is referred to herein as a "crude butenes stream". This stream may act as both the monomer source and "solvent" for the polymerization. It is preferred that the '0 concentration of 1- and 2-butenes in the stream be as high as possible, since these are the preferred compounds to be polymerized. The butadiene content should be minimized because it may be a polymerization catalyst poison. The isobutene may have been '_'~ oreviouslv removed for other uses. After being used in the pciymerization (during which much or most cf the ;
butene would have been polymerized), the butenes stream can b~ returned to the refinery for further processing.
In many cf the these polymerizations certain 30 general trends may be noted, although for all of these trends there are exceptions. These trends (and exceptions) can be gleaned from the Examples.
Pressure of the monomers (especially gaseous monomers such as ethylene) has an effect on the 3~ polvmerizations in many instances. Higher pressure often affects the polymer microstructure by reducing branching, especially in ethylene containing polymers.
This effect is more pronounced for Ni catalysts than Pd wwww~rm r~ NI IrTT Inl II

CatalySLS. Under certain cord=tlCr_S higher preS5ure5 also seem to give higher productivities and higher molecular weight. When an acrylate is present anc a Pd catalyst is used, increasing pressure seems to decrease the acrylate content in the resulting copolymer.
Temperature also affects these poiymerizations.
Higher temperature usually increases branching with hTi catalysts, but often has little suet. effect using Pd catalysts. With Ni catalysts, higher temperatures appear to often decrease molecular weight. With P
catalysts, when acrylates are present, increasing temperature usually increases the acrylate conte:-=t o~
the polymer, but also often decreases the proauct_vity anc molecular weight of the polymer.
1~ Anions surprisingly also often affect moiecu_ar weight cf the polymer former. More highly coordinatinc anions often give lower molecular weight polymers.
Althougr. all of the anions useful herein are relatively weakly coordinating, some are more strongly ?0 coordinating than others. The coordinating ability of suc:~ ar_ions is known and has been d=scussed ir. the literature, see for instance w. Beck., et al., Chem.
Rev., vcl. 88 p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942 (1993), both of which may be referred to. The results found here.: in which the molecular weight of the pclyr:er produced is related to the coordinating ability c. the anior. used, ~s in line with the coordinating abil_ties of these anions as described in Beck (p. 1411) and .0 Strauss (p. 932, Table II).
In addition to the "traditional" weakly coordinating anions cited in the paragraph immed_ately above, heterogeneous anions may also be employed. =n these cases, the trse nature of the counterion is poorly defined cr unknown. Included in this arou~ are MA~~, MMAO and related aiuminoxanes which do not form true solutions. The resulting counterions are though to bear anionic aluminate moieties related to those 9?

~_tc1:: t~°_ Ja~aC~,..t:: _:.~..',1~'~=atS_v a:rOt'e. -,~._1,~~~:e~~C
a::ic::IC r"a=e;=a_s ssch as Nafion''M polyfluorosulfonic aC~~~ Ca:l =L:.'.,~.t_J.~a a5 Il0~-CC:7ZC3..~.at.ll:.'t.
C.~.l::at°.Ø~.5. 1r aC1'Z1.'.1C.~., a WIC? W levy O~ 1'leLe=OC1°_IleJl:S l:lv~~~3~1C
?aate~lci5 Ca : C$ ma~:5 LO I;:. :: L1C.~. aS .'.J.~.-.'.JO. :..'.a.'.. :~
COL.~.te~10::5. =Xa.'.:D_°S w01:~:~ i:lClude a~:l.~..l:la5, Si13Ca5.
s_1_ca/alu-~.._s, _,._d=?=it=_=_, c_ay=, °'~ _ ate= may oLhexs Lt:~_zea as tra3=t=oaai supports ~e~ Z'_=die=
r ~ -.
i\otta O~S_1:. ~~IV.T,?=IZat=O:: CaLalyStS. ~:~':e5e a~e 10 a°ae_a=iv r.a___'_a_s w!:?c:.aye Lewis c_ _=o.~.st=d ac_dlt:'. .:'_cs;:=__~e area is usually cesi=e~ an::
OiteLheS? T~ate=lc_S w111 aye bee.~. o.'.tl4aLe : tG~OIlC::
some heac_ _ . ,.cess . Leat'_:~g may re:~ov? axcess 5::==c:.~ w ~_- a.'..~_ ~.... gc ,°_ S~==aCc ...__.__ _.,...., _=OI:Si°_..., .°4:15 WDC. :~i6te=1a15 wCICa=° ::...
a=:lva :Z L::e r~?e r~~ c_~=.~. be maa~ active ~~ s_==a~_ L~eatm~~t. r,~.= 1=:Sta:lC°, a SLl~iaC°r'1\'.,~.=av°_J S1_lCc, Z~a.~. OXid° C. Ca=DC.~. Call D°_ tZeaLe.~'. w1L11 a:1 C~Ca:OaIL:.°,._....~.. :.~..'.:~0;:.~.d ..~. D~OVlde Lr:e =o~~~,l~e.,~:
?0 _unctioralitv.
The cata_vsts cescr_bed here.~. ca.-. be here=oa° ize_..=ou=~ a va=iety ct mea~s. T_he ° :°_~J~°::°C::S d::~C.'.5 ~aa L::°_ ~a~a~~a-.'.:'?~'C~aL°.1' a.~~CVe wil_ a'.i se=ve :o ~eLeroae::=ze the cata_ys:.s.
rata' yStS C_.. a_s0 ~° he=e=O~e.~.:zea y eXCs2: _ t~:°_m tC
S;iWc:~ v:::c::=_t_°S C~ $ ~.O~O:.':e~ tC e:lCa.',5::..8~~
_.'.°_.'.: :i. a polvmer2c na_e=ial through which additio:.a_ mc.~.ome-s wi'_ di:fuse. :~nothe_~ method is to sD:av-d=v the catalyst wit:: its s;:i:.abie non-coordinati.-.g cc;:nter-err.
C:lt C a DCiV,::°_'... S:::JDJ~ t . ::ete~oaeneC::S v'°~5~:
:a5 O.
the Cata:~'S: 2;e Da-:lCLlla~~v 115eful i0: :uIlZi::g gaS-phase no:~yme=Izaticns. The catalyst Is s;:'_tably ___...°_.~. GEC __C: °__S°_.~. C:: t~°_ S;:=~aCe C_ ...'.°_ Ca=a~VS=
S;ly _ ~ w CC.'...=__ r.~:e ~1°_Gs C., t:.Olytl~=1ZG.._C::.
~'s!:°.~.
applied :.c ~'_u-_o:,ze~-bed oolymezizations, :.he heterogeneous s;:ppc: is p:ovide a coavenie: ~ mea.~.s o' catalvs= irt:cd'.:ctio:~.
9~

Another item may effect the ircorporat_ wr.~ of colG_-monomers such as acrylic esters in olefin copolymers.
It has been found that catalysts containing less bulky a-diimines incorporate more of the polar monomer into the polymer (one obtains a polymer with a higher percentage o~ polar monomer) than a catalyst cor.tainir~=
a more bulky a-diimine, particularly when ethylene is the olefin comonomer. For instance, in an a-diimine c-_' formula (VIII), if Rz and RS are 2,6-dimethylphenyl instead of 2,6-diisopropylphenyl, more. acrylic monomer will be incorporated into the polymer. However, another common, effect of using a less bulky catalyst is to produce a polymer with lower molecular weight.
Therefore one may have to make a compromise between.
1~ polar monomer content in the polymer and polymer molecular weight.
When an olefinic carboxylic acid is polymerized into the polymer, the polymer will of course contain carboxyl groups. Similarly in an ester containing polymer, some or all of the ester groups may be hydrolyzed to carboxyl groups (and vice versa). The carboxyl groups may be partially or completely converted into salts such as metallic salts. Such polymeric salts are termed ionomers. Ionomers are 2~ useful in adhesives, as ionomeric elastomers, and as molding resins. Salts may be made with ions of metals such as Na, K, Zn, Mg, A1, etc. The polymeric salts may be made by methods known to the artisan, for instance reaction of the carboxylic acid containing polymers with various compounds of the metals such as bases (hydroxides, carbonates, etc.) or other AMENDED SHEET

compounds, such as acetylacetonates. Novel polymers that contain carboxylic acid groups herein, also form novel ionomers when the carboxylic acid groups are partially or fully converted to carboxylate salts.
When copolymers of an olefinic carboxylic acid or olefinic ester and selected olefins are made, they may be crosslinked by various methods known in the art, depending on the specific monomers used to make the polymer. For instance, carboxyl or ester containing polymers may be crosslinked by reaction with diamines to form bisamides. Certain functional groups which may be present on the polymer may be induced to react to crosslink the pclymer. For instance epoxy groups (which may be present as glycidyl esters) may be I~ crosslinked by reaction of the epoxy groups, see for instance Example 135.
It has also been found that certain fluorinated olefins, some of them containing other functional aroups may be polymerized by nickel and palladium catalysts. Note that these fluorinated olefins are included within the definition of H2C=CHR1', wherein R1' can be considered to be substituted hydrocarbyl, the substitution being fluorine and possibly other substituents. Olefins which may be polymerized include ;,C=CH (CH2) aRfR42 wherein a is an integer of 2 to 20, Ra is perfluoroalkylene optionally containing one or more ether groups, and R'~ is fluorine or a functional group. Suitable functional groups include hydrogen, chlorine, bromine or iodine, ester, sulfonic acid (-S03H), and sulfonyl halide. Preferred groups for R4' include fluorine, ester, sulfonic acid, and sulfonyl fluoride. A sulfonic acid croup containing monomer does not have to be polymerized directly. It is preferably made by hydrolysis of a sulfonyl halide 3~ group already present in an already made polymer. It is preferred that the perfluoroalkylene group contain 2 to 20 carbon atoms and preferred perfluoroalkylene groups are -(CF2)b- wherein b is 2 to 20, and -9~
_.._ __._.._~ .. .~~ m n r nr~~

WO 96!23010 PCT/US96/01282 (CFA) dOCF2CF2- wherein d is 2 to 20. A preferred olefinic comonomer is ethylene or a linear a-olefin, and ethylene is especially preferred. Polymerizations may be carried out with many of the catalysts=described herein, see Examples 284 to 293.
As described herein, the resulting fluorinated polymers often don't contain the expected amount of branching, and/or the lengths of the branches present are not those expected for a simple vinyl polymerization.
The resulting polymers may be useful for compatibilizing fluorinated and nonfluorinated poivmers, for changing the surface characteristics of fluorinated or nonfluorinated polymers (by being mixed 1~ with themi, as melding resins, etc. Those polymers containing functional groups may be useful where those functional groups may react or be catalysts. For instance, if a polymer is made with a sulfonyl fluoride group (R4~ is sulfonyl fluoride) that group may be 20 hydrolyzed to a sulfonic acid, which being highly fluorinated is well known to be a very strong acid.
Thus the polymer may be used as an acid catalyst, for example for the polymerization of cyclic ethers such as tetrahydrofuran.
_r. this use it has been found that this polymer is more effective than a completely fluorinated sulfonic acid containing polymer. For such uses the sulfor.ic acid content need not be high, say only 1 to 20 mole percent, preferably about 2 to 10 mole percent of the 30 repeat units in the polymer having sulfonic acid groups. The polymer may be crosslinked, in which case it may be soluble in the medium (for instance tetrahydrofuran), or it may be crosslinked so it swollen but not dissolved by the medium, Or it may be 35 coated onto a substrate and optionally chemically attached and/or crosslinked, so it may easily be separated from the other process ingredients.

pCT/US96/Oi282 One of the monomers that may be polymerized by the above catalysts is ethylene (E), either by itself to form a homopolymer, or with a-olefins and/or olefinic esters or carboxylic acids. The structure of the polymer may be unique in terms of several measurable properties.
These polymers, and others herein, can have unique structures in terms of the branching in the polymer..
Branching may be determined by NMR spectroscopy (see the Examp~~es for details), and this analysis can determine the total number of branches, and to some extent the length of the branches. Herein the amount of branching is expressed as the number of branches per 1000 of the total methylene (-CHI-) groups in the 1~ polymer, wish one exception. Methylene groups that are in an ester grouping, i.e. -C02$, are not counted as part of the 1000 methylenes. These methylene groups include those in the main chain and in the branches.
These polymers, which are E homopolymers, have a brancr.
content of about 80 to about 150 branches per 1000 methylene groups, preferably about 100 to about 130 branches per 1000 methylene groups. These branches do not include polymer end groups. In addition the distribution of the sizes (lengths) of the branches is uniaue. Cf the above total branches, For every 100 that are methyl, about 30 to about 90 are e~hy-, about 4 to about 20 are propyl, about 15 to about 50 butyl, about 3 to about 15 are amyl, and about 30 to about 140 are hexyl or longer, and it is preferred that for every 100 that are methyl, about 50 to about 75 are ethyl, about 5 to about 15 are propyl, about 24 to about 40 are butyl, about 5 to 10 are amyl, and about 65 to about 120 are hexyl or larger. These E homopolymers are often amorphous, althoug:-~ in some there may be a 3~ small amount o~ crystallinity.
Another polyolefin, which is an E homopolymer that can be made by these catalysts has about 20 to about 150 branches per 1000 methylene groups, and, per 100 .-_ _..... ...,w r ~W

methyl groups, about 4 to about 20 ethyl groups, about 1 to about 12 propyl groups, about 1 to about 12 butyl group, about 1 to about 10 amyl groups, and ~ to about 20 hexyl or larger groups. Preferably this polymer has about 40 to about 100 methyl groups per 1000 methylene groups, and per 100 methyl groups, about 6 to about 15 ethyl groups, about 2 to about 10 propyl groins, about 2 to about 10 butyl groups, about 2 to about 8 amyl groups, and about 2 to about 15 hexyl or lara~r groups.
Many of the~polyolefins herein, including homopolyethylenes, may be crosslinked by various methods known in the art, for instance by the use of peroxide or other radical generating species ~,~hich can crosslink these polymers. Such crosslinked polymers 1~ are novel when the uncrosslinked polymers from which they are derived are novel, because for the most part the structural features) of the uncrosslinked polymers which make them novel will be carried over into the crosslinked forms.
?0 In addition, some of the E homopolymers have an exceptionally low density, less than about 0.86 g/mL, preferably about 0.85 g/mL or less, measured at 25°C.
This density is based on solid polymer.
Homopelymers of polypropylene (F) can also have unusual structures. Similar effects have bee.~. observed with otn~r a-olefins (e.g. 1-hexene). A "normal" P
homopolvmer will have one methyl group for each methylene croup (or 1000 methyl groups per 1000 methylene groups), since the normal repeat u::it is -30 CH(CH;)CH~-. However, using a catalyst of fe=mula (I) in whic?: M is Ni(II) in combination with an alkyl aluminum compound it is possible to produce a P
homopolymer with about 400 to about 600 methyl groups per 1000 methylene groups, preferably about 450 to 3~ about 550 methyl groups per 1000 methylene groups.
Similar effects have been observed with other a-olefins (e. g. 1-hexene).

_.._......~ ... ,~~~ ."m r nr~

T_n the polymerization processes described herein olefinic esters and/or carboxylic acids may also be present, and of course become part of the copolymer formed. These esters may be copolymerized with one or more of E and one or more a-olefins. When copolymerized with E alone polymers with unique structures may be formed.
In many such E/olefinic ester and/or carboxylic acid copolymers the overall branching level and the distribution of branches of various sizes are unusual.
In addition, where and how the esters or carboxylic acids occur in the polymer is also unusual. A
relatively high proportion of the repeat units derived from the olefinic esters are at the ends of branches.
1~ In such copclymers, it is preferred that the repeat units derived from the olefinic esters and carboxylic acids are about 0.1 to 40 mole percent of the total repeat units, more preferably about 1 to about 20 mole percent. In a preferred ester, m is 0 and R1 is hydrocarbyl or substituted hydrocarbyl. It is preferred that R1 is alkyl containing 1 to 20 carbon atoms, more preferred that it contains 1 to 4 carbon atoms, and especially preferred that R1 is methyl.
One such preferred dipolymer has about 60 to 100 methyl Groups (excluding methyl groups which are esters) per 1000 methylene groups in the polymer, and contains, per 100 methyl branches, about 45 to about 65 ethyl branches, about 1 to about 3 propyl branches, about 3 to about 10 butyl branches, about 1 to about 3 amyl branches, and about 15 to about 25 hexyl or longer branches. In addition, the ester and carboxylic acid containing repeat units are often distributed mostly at the ends of the branches as follows. If the branches, and the carbon atom to which they are attached to the main chain, are of the formula -CH (CHz) ~COZRl, wherein the CH is part of the main chain, then in some of these polymers about 40 to about 50 mole percent of ester groups are found in branches where n is 5 or more, ~..~~~..~...r.. ... ~nrT ini n r net about 10 to about 20 mole percent when n is 4, about 20 to 30 mole percent when n is 1, 2 and 3 and about 5 to about 15 mole percent when n is 0. When n is 0, an acrylate ester has polymerized "normally" as part of ~ the main chain, with the repeat unit -CHz-CHCO~R1-.
These branched polymers which contain olefin and olefinic ester monomer units, particularly copolymers of ethylene and methyl acrylate and/or other acrylic esters are particularly useful as viscosity modifiers for lubricating oils, particularly automotive lubricating oils.
Under certain polymerization. conditions, some of the polymerization catalysts described herein produce polymers whose structure is unusual, especially l~ considering from what compounds (monomers) the polymers were made, and the fact that polymerization catalysts used herein are so-called transition metal coordination catalysts (more than one compound may be involved in the catalyst system, one of which must include a transition metal). Some of these polymers were described in a somewhat different way above, and they may be described as "polyolefins" even though they may contain other monomer units which are not olefins (e.g., olefinic esters). In the polymerization of an ~~ unsaturated compound of the formula H,C=CH(CH2)eG, wherein a is 0 or an integer of 1 or more, and G is -hydrogen or -C02R1, the usual ("normal") polymeric repeat unit obtained would be -CH2-CH[(CH2)eG]-, wherein.
the branch has the formula -(CH2)~G. However, with soanz of the instant catalysts a polymeric unit may be -CH~-CH [ ( CHZ ) fG] - , wherein f ~ a , and f is 0 or an integer of Z or more. If f<e, the "extra" methylene groups may be part of the main polymer chain. If f>e (parts cf) additional monomer molecules may be incorporated into 3~ that branch. I~ other words, the structure of any polymeric unit.may be irregular and different for monomer molecules incorporated into the polymer, and the structure of such a polymeric unit obtained could _. ._ __.~ .__ ." '~~ .n' n r nee WO 96/23010 ~ 02338526 2001-03-O1 pCTNS96101282 be rationalized as the result of "migration c_ the active polymerizing site" up and down the polymer chain, although this may not be the actual mechanism.
This is highly unusual, particularly for ~ pcivmerizations employing transition metal coordination catalysts.
For "normal" polymerizations, wherein the polymeric unit -CHI-CH[(CH2)eG]- is obtained, the theoretical amount of branching, as measured by the number of branches per 1000 methylene (-CHI-) groups can be calculated as follows which defines terms "theoretical branches" or "theoretical branching"
herein:
1 ~ Thecrec_:a: branches = 1000~Tetal mole fraction of a-olef_a /(=(2~mole fraction e=011?(-(mole fraction u-olefin~er);
In this eauation, an a-olefin is any olefinic compound H~C=CH(CHz)eG wherein e~0. Ethylene or an acrylic '_'0 compound are the cases wherein e=0. Thus to calculate the number of theoretical branches in a polymer made from 50 mole percent ethylene (e=0), 30 mole percent propylene (e=1) and 20 mole percent methyl 5-heptenoate (e=4) would be as follows:

Theoret:cai cranches ~ '~00~C ° ~ 238 (branchesil0-_~ethyienes n (2~0.:)I~Ii0.30~11~t0.I0~411~
The "1000 methylenes" include all of the methylene ~0 groups in the polymer, including methylene groups i.~.
the branches.
For some of the polymerizations described herein, the actual amount of branching present in the polymer is considerably greater than cr less than the above theoretical branching calculations would indicate. For instance, when an ethylene homopolymer is made, there should be no branches, yet there are often many such branches. When an a-olefin is polymerized, the .......,~.~,.~r m~rcT rDI(( C'7R1 branching level may be much lower or higher than the theoretical branching level. It is preferred that the actual branching level is at 90% or less of the theoretical branching level, more preferably about SOo ~ or less of the theoretical branching level, or 1100 or more cf the theoretical branching level, more preferably about 1200 or more of the theoretical branching level. The polymer should also have at least about SO branches per 1000 methylene units, preferably 10 about 75 branches per 1000 methylene units, and more preferably about 100 branches per 1000 methylene amts.
In cases where there are "0" branches theoretically present, as ir_ ethylene homopolymers or copolymers with acrylics, excess branches as a percentage cannot be l~ calculated. In that instance if the polymer has .0 or more, preferably 75 or more branches per 1C00 methylene groups, it has excess branches (i.e. in branches in which f>0) .
These polymers also have "at least two branches of '_0 different lengths containing less than 6 carbon atoms each." By this is meant that branches of at least two different lengths (i.e. number of carbon atoms?, and containing less than 6 carbon atoms, a=a present ~_. the polymer. For instance the polymer may contain ethyl and butyl branches, or methyl and amyl branches.
As will be understood from the above discuss=o~, the lengths of the branches ("f") do not necessarily correspond to the original sizes of the monomers used ("e"). Indeed branch lengths are often present which ~0 do net correspond to the sizes of any of the monomers used and/or a branch length may be present "in excess".
By "in excess" is meant there are more branches c. a particular length present than there were monome r which corresponded to that branch length in the polymer. For instance, in the copolymerization of 75 mole percent ethylene and 25 mole percent 1-butene it would be expected that there would be 125 ethyl .
branches per 1000 methylene carbon atoms. If there 10'_ _..___._... .,..~~ m m ~ nee WO 96!23010 ~ 02338526 2001-03-O1 pC'1'/US96/01282 were mcre ethyl branches than that , the~~bbd~ be- i:~r excess compared to the theoretical branchinc. There may also be a deficit of specific length branches. If there were less than 125 ethyl branches per 1000 methylene groups in this polymer there would be a deficit. Preferred polymers have 90% or less or 1100 or more of the theoretical amount of any branch length present in the polymer, and it is especially preferred if these branches are about 80% or less or about 120%
or more of the theoretical amount of any branch length.
In the case cf the 75 mole percent ethylene/25 mole percent 1-butene polymer, the 90o would be about 113 eti~.vl branches er less, while the 1100 would be about 138 ethyl branches or more. Such polymers may also or l~ exclusively ccntain at least 50 branches per 1000 methylene atoms with. lengths which should not theoretically (as described above) be present at all.
These polymers also have "at least two branches of different lengths containing less than 6 carbon atoms ?0 each." Bv this is meant that branches of at least two different lengths (i.e. number of carbon atoms), and containing less than 6 carbon atoms, are present in the polymer. For instance the polymer may contain ethyl and butyl branches, or methyl and amyl branches.
Some of the polymers produced herein are novel because cf unusual structural features. Normally, l:
polymers of alpha-olefins of the formula CHI=CH(CH2)aH
wherein a is an integer of 2 or more made by coordination polymerization, the most abundant, and 30 often the only, branches present in such pciymers have the structure -(CH2)aH. Some of the polymers produced herein are novel because methyl branches comprise about 25% tc about 75% of the total branches in the polymer.
Such polymers are described i.~. Examples 139, 162, 173 3~ and 243-245. Some of the polymers produced herein are novel because in addition to having a high percentage (25-750) of methyl branches (of the total branches present), they also contain linear branches of the nr mnTtTi tTe cutGT ~O~ 11 C ~Rl structure -(CH2)nH wherein n is an integer ef six or greater. Such polymers are described in Examples 139, 173 and 243-245. Some of the polymers produced herein are novel because in addition to having a high percentage (25-75%) of methyl branches (of the total branches present), they also contain the structure (XXVI), preferably in amounts greater than can be accounted for by end groups, and more preferably greater than 0.5 (XXVI) groups per thousand methyl groins in the polymer greater than can be acccunted for by end groups.

-CH2-CH-(CH2)aH (XXVI) 1~ Normally, homo- and copolymers of one er more alpha-olefins of the formula CH2=CH(CH2)aH wherein a is an integer of 2 or more contain as part of the polymer backbone the structure (XXV) -CH-CHZ-CH- (XXV) whereon R35 and R36 are alkyl groups. In most such polymers of alpha-olefins of this formula (especially those produced by coordination-type polymerizations), boti,. of R35 and R36 are - (CH2) aH. However , l:: certain of these polymers described herein, about 2 mole percent or more, preferably about 5 mole percent or more and more preferably about 50 mole percent or more of the total amount of (XXV) in said polymer consists 30 of the structure where one of R35 and R36 is a methyl group and the other is an alkyl group containing two or more carbon atoms. Furthermore, in certain of these polymers described herein, structure (XXV) may occur in side chains as well as in the polymer backbone.
3~ Structure (XXV) can be detected by '-3C NMR. The signal m fr,nTe~ tTe eutLT !O1 II C ~R1 WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96/01282 _.._ the carbon atom of the methylene group between the two methine carbons in (XXV) usually occurs in the 13C
NvR at 41.9 to 44.0 ppm when one of R35 and R36 is a ~ethyl group and the other is an alkyl group containing two or more carbon atoms, while when both R35 and R3s contain 2 or more carbon atoms, the signal for the --~ethyiene carbon atom occurs at 39.5 to 41.9 ppm.
~ntegratior. provides the relative amounts of these _~ructures present in. the polymer. If there are 10 _nterferir_g signals from other carbon atoms in these regions, they must be subtracted from the total ==~tecrals to give correct values for structure (XXV).
Normally, homo- and copoivrners of one or more ,_iDha-olefins of the formula CHI=CH(CH2)aH wherein a is l~ ~.. _~teaer of 2 or more (especially those made by coerination polymerization) contain as part of the aolvmer backbone structure (XXIV) wherein n is 0, 1, or 2. When n is 0, this structure is termed "head to hea~" polymerization. When n is 1, this structure is ?0 termed "head to tail" polymerization. When n is 2, ,.his structure is termed "tail to tail" polymerization..
/r. most such polymers of alpha-olefins of this formula especially those produced by coordination-type coivmerizations), both of R3~ and R38 are -(CH2)aH.
'_'~ ..owever some of the polymers of alpha-olefins of this _ormu_a described herein are novel in that they also contain structure (XXIV) wherein n = a, R3~ is a methyl ~ro;:~, and R3g is an alkyl group with 2 or more carbon atcms.
~0 I I
-C H-(C H2)n-C H-(XXN) Normally polyethylene made by coordination Dcivmerization has a linear backbone with either no 10~
m ~nrT~T~ rte cuCCT !0I i1 C ~Rl branching, or small amounts of linear branches. Some of the polyethylenes described herein are unusual in that they contain structure (XXVII) which has a methine carbon that is not part of the main polymer backbone.

-CH2-CH-CH2CH3 (XXVII) Normally, polypropylene made by coordination polymerization has methyl branches and few if any 10 branches of other sizes. Some of the polypropylenes described herein are unusual in that they contain one or both of the structures (XXVIII) and (XXIX).

NCH' -CH- (XXVIII) I
-CH2CH2 CH-CH3 (XXIX) As the artisan understands, in coordination polymerization alpha-o~efins of the formula CH2=CH(CH2)aH may insert into the growing polymer chain '_'0 in a 1,2 or 2,1 manner. Normally these insertion steps lead to 1,2- enchainment or 2,1-enchainment of the monomer. Both of these fundamental steps form a -(CH2)aH branch. However, with some catalysts herein, some of the initial product of 1,2 insertion can rearrange by migration of the coordinated metal atom to the end of the last inserted monomer before inserticn of additional monomer occurs. This results in omega,2-enchainment and the formation of a methyl branch.

_.._..~.....~r r.~ ~~rT ~n~ t~ c ~fa~

1.2 insertion polymer-M + CH z=CH(CH z)aH
M
CHz CH3 t CH rearrangement ~CH\
polymer ~ ~ (CHz)aH ~ polymer (CHz)eM
1,2-enchainment ~o.2-enchainment -(CHz)aH branch -CH, branch It is also known that with certain other catalysts, some of the initial product o~ 2,1 insertion can rearrange in a similar manner by migration cf the coordinated metal atom to the end of the last inserted monomer. T':is results in omega, 1-enchainme.~.t and no branch is formed.
2.1 insertion polymer-M + CHz=CH(CHz)aH
M
t polymer~CH2 CH\(CHz)aH rearrangements of mer~CHz P Y ,CHz~
(CHz)aM
2.1-enchainment r~,.1-enchamment 1 ~ -(CHz)aH branch no branch Of the four types of alpha-olefin enchainment, omega,l-enchainment is unique in that it does not generate a branch. In a polymer made from an alpha-1~ olefin of the formula CH2=CH(CHz)aH, the total number of branches per 1000 methylene groups (S' can be expressed as:
B = (1000) (1-X~,,1)/[!1-X~,,1)a + Xw,l(a + 2)]
where X«,1 is the fraction of omega,l-enchainment 20 Solving this expression for Xw,l gives:
X~,1 = (1000 - aB)/(1000 + 2B) This equation provides a means of calculating the fraction of omega,l-enchainment in a polymer of a.
linear alpha-olefin from the total branching B. Total ~5 branching can be measured by 1H NMR or i'C NMR.
Similar equations can be written for branched alpha-_.._ _-.-... ...... .... w r nw olefins. For example, the eq~aticn f.or 4-methyl-pentene is:
Xw,l = (2D00 - 2B)/(1000 + 2B) Most polymers of alpha-olefins made by other coordination polymerization methods have less thar_ 50 omega,l-enchainment. Some of the alpha-olefin polymers described herein have unusually large amounts (say >5%) of omega,i-enchainment. In essence this is similar to stating t~:at a polymer made from an a-olefin has much less t)-:ar. the "expected" amount of branching. Although many of the polymerizations described herein give substantiGl amounts of w,1- and other unusual forms of enchainme::t cf olefinic monomers, it has surprisingly been fcu~d that "unsymmetrical" a-diimine ligands of l~ formula sVIII) give especially high amounts of ca,l-enchainment. In particular when R~ and R~ are phenyl, and one cr both of these is substituted in such a way as different sized groups are present in the 2 and 6 position cf the phenyl ring(s), c~,l-enchainment is ~0 enhances. For instance, if one or both of R2 and R
are 2-t-butylphenyl, this enchainment is enhanced. T_n this context when R' and/or RS are "substituted" phenyl the substitution may be not only in the 2 and/or 6 positions, but on any other position in the phenyl =ins. _.._ instance, 2,5-di-t-butylphenyl, and 2-t-butyl-~,5-dichiorophenyl would be included in substituted phenyl.
'I!-:= steric effect of various groupings has been quantified by a parameter called ES, see R. w. Taft, Jr., ~. Am. Chem. Soc., vol. 74, p. 3120-3128, and M.S.
Newma~, Steric Effects in Organic Chemistry, John Wiley & Sons, New York, 1956, p. 598-603. For the purposes herei_~., the ES values are those fcr o-substituted benzoates described in these publications. If the 3~ value fcr ES for any particular group is not known, it can be determined by methods described in these publica~ic.~.s. For the purposes herein, the value of hvdroQer is defined to be the same as for methyl. It __ _.._~ ,_... . .,.., WO 96123010 ~ 02338526 2001-03-O1 p~~g96/01282 is preferred that difference in ES, when R" a:-:~
preferably also RS) is phenyl, between the groups substituted in the 2 and 6 positions of the phenyl ring is at least 0.15, more preferably at least about 0.20, and especially preferably about 0.6 or more. These phenyl groups may be unsubstituted or substituted in any other manner in the 3, 4 or S positions.
These differences in ES are preferred in a diimine such as (VIII), and in any of the polymerization processes herein wherein a metal complex containing an a-diimine ligand is used or formed. The synthesis and use of such a-diimines is illustrated in Examples 454-463.
Because of the relatively large amounts of w,1-l~ enchainment that may be obtained using some c~ the poivmerization catalysts reported herein novel polymers can be made. Among these homopolypropylene (PP). In some of the PP's made herein the structure ?0 CaHCH2CHZCdHp(CbH2)nCdH2CH2CHpCaH
may be found. In this structure each C° is a methine carbon atom that is a branch point, while each Cb is a methylene group that is more than 3 carbon atoms removed from any branch point (Ca). Herein methylere groups of the type -CbH2- are termed 8+ (or delta+) methylene groups. Methylene groups of the type -C°H--, which are exactly the third carbon atom from a branch point, are termed y (gamma) methylene groups. The NMR
.0 signal for the S+ methylene groups occurs at about 29.75 ppm, while the NMR signal for the y methylene groups appears at about 30.15 ppm. Ratios of these types of methylene groups to each other and the total number of methylene groups in the PP is done by the usual NMR integration techniques.

~..~..~.....~~ w irrT mm r ~C\

It is preferred that PP's made herein have about 25 to about 300 8+ methylene groups per 1000 methylene groups (total) in the PP.
It is also preferred that the ratio of b+:y methylene groups in the PP be 0.7 to about 2Ø
The above ratios involving $+ and r methylene groups in PP are of course due to the fact that high relatively high w,1 enchainment can be obtained. It is preferred that about 30 to 60 mole percent_of the 10 monomer units in PP be enchained in an w,1 fashion.
Using the above equation, the percent w,1 enchainment for polypropylene can be calculated as:
o w,1 = (100)(1000-B)/(1000+2B) wherein B is the total branching (number of methyl 1~ groups) per 1000 methyler_e groups in the polymer.
Homo- or copolymers of one or more linear a-olefins containing 3 to a carbon atoms may also have 8+
carbon atoms in them, preferably at least about 1 or more S+ carbon atoms per 1000 methylene groups.
?0 The above polymerization processes can of course be used to make relatively random copolymers (except for certain CO copolymers) of various possible monomers. However, some of them can also be used to make block polymers. A block polymer is conventionally defined as a polymer comprising molecules in which there is a linear arrangement of blocks, a block being a portion of a polymer molecule which the monomeric units have at least one constitutional or configurational feature absent from adjacent portions .0 (definition from H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, Vol. 2, John Wiiey &
Sons, New York, 1985, p. 324). Herein in a block copolymer, the constitutional difference is a difference in monomer units used to make that block, while in a block homopolymer the same monomers) are used but the repeat units making up different blocks are different structure and/or ratios of types of structures.

______.-..~...~~~~ m.w r nc\

WO 96123010 ~ 02338526 2001-03-O1 PCT/US96/01282 Since it is believed that many of the polymerization processes herein have characteristics that often resemble those of living polymerizations, making block polymers may be relatively easy. One method is to simply allow monomers) that are being polymerized to be depleted to a low level, and then adding different monomers) or the same combination of monomers in different ratios. This process r-~ay be repeated to obtain polymers with many blocks.
Lower temperatures, say about less than 0°C, preferably about -10° to about -30°, tends to enhance the iivingness of the polymerizations. Linder these conditions narrow molecular weight distrib;:tion pclymers may be obtained (see Examples 35%-3E9 and 1~ 37~,', and block copolymers may also be made ,Example 370) .
As pointed out above, certain polymerization conditions, such as pressure, affect the microstructure of many polymers. The microstructure in turn affects ?0 many polymer properties, such as crystallization.
Thus, by changing polymerization conditions, such as the pressure, one can change the microstructure of the part cf the polymer made under those ccnditions. This of course leads to a block polymer, a polymer have defined portions having structures differe.~.t rrom other defined pcrtions. This may be done with mcre than one monomer to obtain a block copolymer, or may be done with a single monomer or single mixture of monomers to obtain a block homopolymer. For instance, in the ~0 polymerizaticn of ethylene, high pressure sometimes leads to crystalline polymers, while lower pressures give amorphous polymers. Changing the pressure repeatedly could lead to an ethylene homopelymer containing blocks of amorphous polyethylene and blocks 3~ of crystalline polyethylene. If the blocks were of the correct size, and there were enough of them, a thermoplastic elastomeric homopolyethylene could be n~ m~TlTt tTt- CLJ~LT IDI 11 C 9R\

produced. Similar polymers could possibly be made trom other monomer(s), such as propylene.
Homopolymers of a-olefins such as propylene, that is polymers which were made from a monomer that consisted essentially of a single monomer such as propylene, which are made herein, sometimes exhibit unusual properties compared to their "normal"
homopciymers. For instance, such a homopolypropylene usuai'_y would have about 1000 methyl groups per 1000 10 metl:viene groups. Polypropylenes made herein typically have about half that many methyl groups, and in addition have some longer chain branches. Other a-olefins often. give polymers whose microstructure is analogous to these polypropylenes when the above 1~ catalysts are used for the polymerization.
These polypropylenes often exhibit exceptionally low glass transition temperatures (Tg's). "Normal"
polypropylene has a Tg of about -17°C, but the polypropylenes herein have a Tg of -30°C or less, ''D preferably about -35°C or less, and more preferably about -~0°C or less. These Tg's are measured by Differential Scanning Calorimetry at a heating rate of 10°C/min, and the Tg is taken as the midpoint of the transition. These polypropylenes preferably have at least ~~ branches (methyl groups) per 1000 carbon atom, more preferably at least about 100 branches per 1000 methylene groups.
rreviously, when cyclopentene was coordination polymerized to higher molecular weights, the resulting ~0 polymer was essentially intractable because of its very hig'.~. milting point, greatly above 300°C. Using the catalysts here to homopolymerize cyclopentene results in a polymer that is tractable, i.e., may be reformed, as by melt forming. Such polymers have an end of 3~ melti:~g point of about 320°C or less, preferably about 300°C or less, or a melting point of about 275°C or less, preferably about 250°C or less. The melting poi:.t is determined by Differential Scanning Il?
_.._ __._..-_ ...~~.~ ,r.", r nev WO 96123010 ~ 02338526 2001-03-O1 PCT/US96101282 Calorimetry at a heating rate of 15°C/min, and taking the maximum of the melting endotherm as the melting point. However these polymers tend to have relatively diffuse melting points, so it is preferred to measure the "melting point" by the end of melting point. The method is the same, except the end of melting is taken as the end (high temperature end) of the melting endotherm which is taken as the point at whic:~ the DSC
signal returns to the original (extrapola.ted) baseline.
Such polymers have an average degree of polymerization ;average number of cyclopentene repeat units per polymer chain) of about 10 or more, preferably about 3C
or more, and more preferably about 50 or more.
In these polymers, enchainment of the cyclopenLene I~ =epeat units is usually as cis-1,3-pentylene units, i::
contrast to many prior art cyclopentenes which were enchained as 1,2-cyclopentylene units. It is preferred that about 90 mole percent or more, more preferably about 95 mole percent or more of the enchained ?0 cyclopentene units be enchained as 1,3-cyclopentylene units, which are preferably cis-1,3-cyclopentylene units.
The X-ray powder diffraction pattern of the instant poly(cyclopentenes) is also unique. To produce cyclopentene polymer samples of uniform thickness fer X-ray measurements, powder samples were compressed incc disks approximately 1 mm thick and 32 mm in diamete_.
X-ray powder diffraction patterns of the samples were collected over the range 10-50° 28. The diffraction 30 data were collected using an automated Philips 8-8 diffractometer (Philips X'pert System) operating in the symmetrical transmission mode iNi-filtered CuKa radiation, equipped with a diffracted beam collimator (Philips Thin Film Collimator system), Xe filled 3~ proportional detector, fixed step mode (0.05°/step), 12.5 sec./step, 1/4° divergence slit). Reflection positions were identified using the peak finding routine in the APD suite of programs provided with the ci iac~n tTF ~NFFT rRl ii E 2s1 X'pert System. The X-ray powder diffraction pattern had reflections at approximately 17.3°, 19.3°, 24.2°, and 40.7° 28, which correspond to d-spacings of approximately 0.512, 0.460, 0.368 and 0.222 nm, respectively. These polymers have a monoclinic unit cell of the approximate dimensions: a=0.561 nm; b=0.607 nm; c=7.37 nm; and g=123.2°.
Copolymers of cyclopentene and various other olefins may also be made. For instance a copolymer of ethylene and cyclopentene may also be made. In such a copolymer -~t is preferred that at least 50 mole percent, more preferably at least about 70 mole percent, of the repeat units are derived from cyciopentene. As also noted above, many of the .
1~ polymerization. systems described herein produce polyethylenes that have considerable branching in them.
Likewise the ethylene units which are copolymerized with the cyclopentene herein may also be branched, so it is preferred that there be at least 20 branches per 1000 methylene carbon atoms in such copolymers. In this instance, the "methylene carbon atoms" referred to in the previous sentence do not include methylene grouDS in the cyclopentene rings. Rather it includes methylene groups only derived from ethylene or other olefin, but not cyciopentene.
Another copolymer that may be prepared is one from cyclopentene and an a-olefin., more preferably a linear a-olefin. It is preferred in such copolymers that repeat units derived from cyclopentene are 50 mole percent or more ef the repeat units. As mentioned above, a-olefins may be enchained in a 1,w fashion, and it is preferred that at least 10 mole percent of the repeat units derived from the a-olefin be enchained in such a fashion.. Ethylene may also be copolyinerized 3~ with the cyclopentene and a-olefin.
Poly(cyclopentene) and copolymers of cyclopentene, especially those that are (semi)crystalline, may be used as molding and extrusion. resins. They may contain e~~ ieeTtTt fTC cuCCT (R111 F'761 WO 96123010 cA 02338526 2001-03-O1 pC'f/~TS96/01282 various materials normally found in resins, such as fillers, reinforcing agents, antioxidants, antiozonants, pigments, tougheners, compatibilizers, dyes, flame retardant, and the like. These polymers may also be drawn cr melt spun into fibers. Suitable tougheners and compatibilizers include polycyclopentene resin which has been grafted with malefic anhydride, an grafted EFDM rubber, a grafted EP rubber, a functionalized styrene/butadiene rubber, or other rubber w:~:ich i:as been modified to selectively bond to components c~ the two phases.
~n all ef the above homo- and copolymers of cyclo~entene, where appropriate, any of the preferred state may be ccmbined any other preferred state(s).
l~ The homo- and copo~iymers of cyclopentene described above may used or made into certain forms as described below:
1. The cyclopentene polymers described above may be part of a polymer blend. That is they may be mixed in any proportion with one or more other polymers which may be thermoplastics and/or elastomers.
Suitable polymers for blends are listed below in the listing for blends of other polymers described herein.
One preferred type of polymer which may be blended is a '_'~ toughening agent or compatibilizer, which .s often elastomeric and/or contains functional groups which may help compatibilize the mixture, such as epoxy or carboxyl.
2. T_he polycyclopentenes described herein are :0 useful i.~. a nonwoven fabric comprising fibrillated three-dimensional network fibers prepared by using of a polycyclopentene resin as the principal component. It can b~ made by flash-spinning a homogeneous solution contain i ng a polycyclopente.~.e . The results.~.t nonwoven 3~ fabric is excellent fir. heat resistance, dimensional stability and solvent resistance.
3. A shaped part of any of the cyc'~opentene containing resins. This part may be formed by II~
w wnT~Tt rrr PtJ>~CT !DI II C 7C,\

WO 96123010 PCTlUS96101282 injection molding, extrusion, and thermoform=ng.
Exemplary uses include molded part for automotive use, medical treatment container, microwave-range container, food package container such as hot packing cc_~.tainer, oven container, retort container, etc., and heat-resisting transparent container such as heat-resisting bottle.
4. A sheet or film of any of the cyciopentene containing resins. This sheet or film may be clear and 10 may be used for optical purposes (i.e. breakage resistant glazing). The sheet or film may be oriented or unoriented. Orientation may be carried opt by any of the known methods such a uniaxial or biaxial drawing. The sheet or film may be stampable or l~ thermoformable.
5. The polycyclopentene resins are useful i:~
nonwoven fabrics or microfibers which are produced by melt-blowing a material containing as a main component a polycyclopentene. A melt-blowing process for ?0 producing a fabric or fiber comprises supplying a polycyclopentene in a molten form from at least one orifice of a nozzle into a gas stream which attenuates the molten polymer into microfibers. The nonwoven fabrics are excellent in heat-resistant and chemical resistant characteristics, and are suitable =cr use as medical fabrics, industrial filters, battery separators and so forth. The microfibers are particularly useful in the field of high temperature filtration, coalescing and insulation.
30 6. A laminate in which one or more of the layers comprises a cyclopentene resin. The laminate may also contain adhesives, and other polymers in some or all of the layers, or other materials such as paper, metal foil, etc. Some or all of the layers, may be 3~ oriented in the same or different directions. The laminate as a whole may also be oriented. Such materials are useful for containers, or other uses ..
where barrier properties are required.

_.._~ ,_... . .,.., WO 96/23010 ~ 02338526 2001-03-O1 7. A fiber of a cyclopentene polymer. This fiber may be undrawn or drawn to further orient it. It is useful for apparel and in industrial application where heat resistance and/or chemical resistance are important.
8. A foam or foamed object of a cyclopentene polymer. The foam may be formed in any conve.~.tional manner such as by using blowing agents.
9. The cyclopentene resins may be.microporous membranes. They may be used in process wherein semi-permeable membranes are normally used.
Ir. addition, the cyclopentene resins may be treated or mixed with other materials to improve certain properties, as follows:
1~ 1. They may further be irradiated wits electron rays. This often improves heat resistance and/or chemical resistance, and is relatively inexpensive.
Thus the molding is useful as a material required to have high heat resistance, such as a structural '?0 material, a food container material, a food wrapping material or an electric or electronic part material, particularly as an electric or electronic part material, because it is excellent in soldering resistance.
2. Parts with a crystallinity of at least 200 may be obtained by subjecting cyclopentene peiymers having an end of melting point between 240 and 300°C to neat treatment (annealing) at a temperature o~ 120°C to just below the melting point of the polymer. Preferred ~0 conditions are a temperature of 150 to 280°C. for a period of time of 20 seconds to 90 minutes, preferably to give a cyclopentene polymer which has a heat deformation temperature of from 200 to 260°C. These parts have good physical properties such as heat resistance and chemical resistance, and thus are useful for, for example, general construction materials, electric or electronic devices, and car parts.

........gym rrr rv ~rr~r rm 11 C ~R1 3. Cyclopentene resins may be nucleated to promote crystallization during processing. An example would be a poiycyclopentene resin composition containing as main components (A) 100 parts by weight of a poiycyclopentene and (B) 0.01 to 25 parts by weight ~~ one or more nucleating agents selected from the group consisting of (1) metal salts of organic acids, (2i inorganic compounds, (3) organophosphorus compounds, and/or (4) metal salts of ionic hydrocarbon 10 copolymer. Suitable nucleating agents may be sodium methyienebis(2,4-di-tertbutylphenyl) acid phosphate, sodium bis(4-tent-butylphenyl) phosphate, aluminum p-(tert-butyl) benzoate, talc, mica, or related species.
These could be used in a process for producing 1~ polycyciooentene resin moldings by molding the above polycyclooentene resin composition at a temperature above their melting point.
4. Flame retardants and flame retardant combinations may be added to a cyclopentene polymer.
?0 Suitable flame retardants include a halogen-based or phosphorus-based flame retardant, antimony trioxide, antimony pentoxide, sodium antimonate, metallic antimony, antimony trichloride, antimony pentachloride, antimony trisulfide, antimony pentasulfide, zinc borate, barium metaborate or zirconium oxide. Thev may be used in conventional amounts.
S. Antioxidants may be used ir. conventiona-~
amounts to improve the stability of the cyclopentene polymers. For instance 0.005 to 30 parts by weight, 30 per 100 parts by weight of the cyclopentene polymer, of an antioxidant selected from the group consisting of a phosphorous containing antioxidant, a phenolic antioxidant or a combination thereof. The phosphorous containing antioxidant may be a monophosphite or diphosphite or,mixture thereof and the phenolic antioxidant may be a dialkyl phenol, trialkyl phenol, diphenylmonoalkoxylphenol, a tetraalkyl phenol, or a mixture thereof. A sulfur-containing antioxidant may ~..~~~.~...~ r...rrr m m r nev WO 96/23010 ~ 02338526 2001-03-O1 pCTIUS96/01282 also be used alone or ir. combination with o~~-antioxidants.

6. Various fillers or reinforcers, such as particulate or fibrous materials, may be added to improve various physical properties.

7. "Special" physical properties cGn be obtained by the use of specific types of materials.
Electrically conductive materials such as fi=a metallic wires or graphite may be used to render the polymer electrically conductive. The temperature coefficient of expansion may be regulated by the use of appropriate fillers, and it may be possible to even obtain materials with positive coefficients of expa.~.sion.
Such materials are particularly useful ir_ e--ectricai 1~ and electronic parts.
e. The polymer may be crosslinked by irradiation or chemically as by using peroxides, optionally in the presence of suitable coagents.
Suitable peroxides include benzoyl peroxide, lauroyl '°0 peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butylperoxybenzoate, tent-butylcumyl peroxide, tert-butylhydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,1-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylpercxy)-3,3,5- trimethyicyclohexane, ~-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butyiperoxy)butane and tert-butylperoxybenzene.
When polymerizing cyclopentene, it has been found 30 that some cf the impurities that may be found in cyclopentene poison or otherwise interfere with the pclymerizations described herein. Compounds such as 1,3-pentadiene (which can be removed by passage through 5A molecular sieves), cyclopentadiene (which can be 3~ removed by distillation from Na), and methylenecyclobutane (which can be removed by distillation from polyphosphoric acid), may interfere e~ mcT~Ti tT~ cN~FT (RI1LE 261 WO 96!23010 PCT/US96/01282 with the polymerization, and their level should be kept as low as practically possible.
The above polymers (in general) are useful in many applications. Crystalline high molecular weight polymers are useful as molding resins, and for films for use in packaging. Amorphous resins are usefu_ as elastomers, and may be crosslinked by known methods, such as by using free radicals. When such amorphous resins contain repeat units derived from polar monomers 10 they are oil resistant. Lower molecular weight polymers are useful as oils, such as in polymer processing aids. When they contain polar groups, particularly carboxyl groups, they are useful in adhesives.
I~ In many of the above polymerizations, the transition metal compounds employed as (part of the) catalysts contains) (a) metal atoms) in a positive oxidation state. In addition, these complexes may have a square planar configuration about the metal, and the 20 metal, particularly nickel or palladium, may have a de electronic configuration. Thus some of these catalysts may be said to have a metal atom which is cationic and has a de-square planar configuration.
In addition these catalysts may have a bidentate '_'~ licrand wherein coordination to the transition metal i=
through two different nitrogen atoms or through a nitrogen atom and a phosphorus atom, these nitrogen and phosphorus atoms being part of the bidentate iigand.
It is believed that some of these compounds herein are 30 effective polymerization catalysts at least partly because the bidentate ligands have sufficient steric bulk or. both sides of the coordination plane (of the square planar complex). Some of the Examples herein with the various catalysts of this type illustrate the 3~ degree of steric bulk which may be needed for such catalysts. If such a complex contains a bidentate ligand which has the appropriate steric bulk, it is ... r.,r.~rTr rTr c~uccT r0111 C ~R1 WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96101282 wolieved that it produces polyethylene with a de~rt'ee ~t ~olymerization of at least about 10 or more.
It is also believed that the polymerization catalysts herein are effective because unpolymerized olefir_ic monomer can only slowly displace from the complex a cocrdirlated olefin which may be formed by ~3-hydride elimination from the growing polymer chain which is attached to the transition metal. The ..isplacement can occur by associative exchange.
___creasing the steric bulk of the ligand slows the rate .... associative exchange and allows polymer chain =owth. A auar.titative measure of the steric bulk of _~:e biaentate ~~aand can be obtained by measuring at -_'.°C the rate of exchange of free ethylene with l~ ~:~mpiexed ethylene in a complex of formula (XI) as shown -gin equation 1 using standard 1H NMR techniques, which is called herein the Ethylene Exchange Rate ,EER). The neutral bidentate ligand is represented by ~'i~ where Y is either N or P. The EER is measured in ?0 _his system. In this measurement system the metal is always Pd, the results being applicable to other metals as noted below. Herein it is preferred for catalysts to contain bidentate ligands for which the second order rate constant for Ethylene Exchange Rate is about '_'~ 20,000 L-mol-ls-1 or less when the metal used in the -olymerization catalyst is palladium, more preferably about 20,000 L-mcl-ZS-1 or less, and more preferably about 5,000 L-moi 's 1 or less. When the metal in the _olymerization catalyst is nickel, the second order 30 .ate constant (for the ligand in EER measurement' is about 50,000 L-mol is 1, more preferably about 25,000 L-moi ls~l or less, and especially preferably about 10,000 _.
.-mol is or less. Herein the EER is measured usi:~~ the ....mpounc (XI) in a procedure !including temperature' cescribed in Examples 21-23.
1 '_' 1 m m~~rt~ tTC cuCCT f C71 It F ~Rl _.
X CH3 ~' , k X' ~CH3 - ~ N Pd~ ~ ~ -N~ ~ II ~ II
(XI) X=N or P
In these polymerizations it is preferred if the bidentate ligand is an a-diimine. T_t is also preferred l f the olefin has the formula R1'CH=CH~, wherein R1' is hydrogen or n-alkyl.
In general for the polymers described herein, blends may be prepared with other polymers, and such other polymers may be elastomers, thermoplastics or thermosets. By elastomers are generally meant polymers 10 whose Tg (glass transition temperature) and Tm (melting ., poin t ) , __ prose=.t , are below amble.~.t temperature, usually considered to be about 20"C. Thermoplastics are those polymers whose Tg and/or Tm are at or above ambient temperature. Blends can be made by any of the 1~ common techniques known to the artisan, such as solution blending, or melt blending in a suitable apparatus such as a single or twin-screw extruder.
Specific uses for the polymers of this application in the blends or as blends are listed below.
'_'0 Blends may be made with almost any kind of elastomer, such as EP, EPDM, SBR, natural rubber, polyisoprene, poiybutadiene, neoprene, butyl rubber, styrene-butadiene block copolymers, segmented polyester-polyethe~ copolymers, elastomeric polyurethanes, chlorinated or chlorosulfonated polyethylene, (per)fluorinated elastomers such as copolymers of vinylidene fluoride, hexafluoropropylene and optionally tetrafluoroethylene, copolymers of tetrafluoroethylene and perfluoro(methyl vinyl ether), 30 and ccpolymers of tetrafluoroethylene and propylene.
Suitable thermoplastics which are useful for blending with the polymers described herein include:
polyesters such as polyethylene terephthalate), poly(butylene terephthalate), and polyethylene m iee~T~Tt tT~ cuCtT IRI I1 F ~Rl WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96101282 adipate); polyamides such as nylon-6, nylon-b,~, nylon-12, nylon-12,12, nylon-11, and a copolymer of hexamethylene diamine, adipic acid and terephthalic acid; fluorinated polymers such as copolymers of ethylene and vinylidene fluoride, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and a perfluoro(alkyl vinyl ether) such as perfluoro(propyl vinyl ether), and polyvinyl fluoride); other halogenated polymers such a polyvinyl chloride) and poly(vinylidene chloride) and its copolymers; polyolefins such as polyethylene, polypropylene and polystyrene, and copolymers thereof;
(meth)acrylic polymers such a poly(methyl methacrylate) and copolymers thereof; copolymers of olefins such as Is ethylene with various (meth) acrylic monomers such as alkyl acrylates, (meth)acrylic acid and ionomers thereof, and glycidyl (meth)acrylate); aromatic polyesters such as the copolymer of Bisphenol A and terephthalic and/or isophthalic acid; and liquid crystalline polymers such as aromatic polyesters or aromatic polyester-amides).
Suitable thermosets for blending with the polymers described herein include epoxy resins, phenol-formaldehyde resins, melamine resins, and unsaturated polyester resins (sometimes called thermoset polyesters). Blending with thermoset polymers will often be done before the thermoset is crosslinked, using standard techniques.
The polymers described herein may also be blended with uncrosslinked polymers which are not usually considered thermoplastics for various reasons, for instance their viscosity is too high and/or their melting point is so high the polymer decomposes below the melting temperature. Such polymers include 3~ poiy(tetrafluoroethylene), aramids such as poly(p phenylene terephthalate) and poly(m-phenyiene isophthalate), liquid crystalline polymer such as ..

ei~oeTt~tTC cuCFT IAI II F 9f1 pcly(be.~_zcxazo~es), and non-melt processible Do~y~~~Ces whi.c:. are of ten aromatic polyimides .
A~i o~ the polymers disclosed herein may be mixed wit:: various additives normally added to eiastomers a.-.d thermoplastics [see EPSE (below), vol. 14, p. 327-41G].
Fcr i_-:star~ce reinforcing, non-reinforcing and conductive Fillers, such as carbon black, glass fiber, minera=s such as clay, mica and talc, glass spheres, bar=u,~.: sulfate, zinc oxide, carbon fiber , ana aramid 10 _=ber c_ f_brids, may be used. Antioxidants, antiozcna:.ts, pigments, dyes, delusterants, compounds to ~roTcte crosslinking may be added. Plasticizers suc:: G_= vGrioLs hydrocarbon oils may also be used.
Tie =oilc>wing listing is of some uses fcr 1~ ~olvc_e__:_s, whic:~ are made from linear oief~~s and d:, .not _._clud= polar monomers such as acrylates, which are disclosed herein. In some cases a reference .s giver.
whit:: c~scusses such uses for polymers in general. All of the=e references may be referred to.
?0 For ~~~ r_ierences, "'J" refers to W. Gerhartz, et ate., Ed., ;:1'_mann's Encyc~~.opedia cf Industrial Chemistry, 5th E~. ~';.H V~rlagsgesellschaft mBH, Weinheim, fer w):ic t:~.e volume arid page number are given, "ECT3"
refe_s ~.. the H. F. Mark, et al., Ed., Kirk-Cthmer '_'~ ~nc~.~~~~~edia ef Chemical Technology, 4th Ed. , John tile.- ~ Sc:a, New York, "~CT4" refers to the J. _ Krosc'.~.witc, et a.., Ed., Kirk-Othmer Encyclopedia of CheT.ica:: Technciogy, 4th Ed., John Wiley & Sons, New York, for which the volume and page number are given, 30 _.'rpc'='" _e=ers to H., F. Mark, et al . , Ed. , Enc~-ciopedia cf :ciymer Science and Technology, 1st Ed., John Wiley & Sor_s, few York, for which the volume and page number are give~, "EPSE" refers to H. F. Mark, et a.., Ed., ~.ncyc_cpedia of Polymer Science and Engineering, 2nd 3~ Ed. , Jc:~_~. k'iley & Sons, New York, for which volume and page numbers are given, and "PM" refers to J. A.
Arydsc::, e~., Plastics Materials, 5 Ed., Butterworth-:~ei:~e~~a::_-., Oxford, UK, 1989, and the page is given. In WO 96/23010 cA 02338526 2001-03-O1 pCT/US96101282 these uses, a polyethylene, polypropylene and a copolymer of ethylene and propylene are preferred.
1. Tackifiers for low strength adhesives (U, vol. Al, p. 235-236) are a use for these polymers.
Elastomeric and/or relatively low molecular weight polymers are preferred.
2. An cil additive for smoke suppression in single-stroke gasoline engines is another use.
Elastomeric polymers are preferred.
3. The polymers are useful as base resins for hct melt adhes-.'rves (U, vol. A1, p. 233-234), pressure sensitive adhesives (U, vol. A1, p. 235-236) or solvent applied adhesives. Thermoplastics are preferred for hot melt adhesives. The poivmers may also be used in a 1~ carpet installation adhesive.
4. Lubricating oil additives as Viscosity Index Improvers for multigrade engine oil (ECT3, Vol 14, p.
495-496) are another use. Branched polymers are preferred. Ethylene copolymer with acrylates or other ?0 polar monomers will also function as Viscosity Index Improvers for multigrade engine oil with the additional advantage of providing some dispersancy.5. Polymer for coatings and/or penetrants for the protection of various porous items such as lumber and masonry, particularly out-of-doors. The polymer may be in a suspension or emulsion, or may be dissolved ~.. a solvent.
6. Base polymer for caulking of various kinds is another use. An elastomer is preferred. Lower .0 molecular weight polymers are often used.
7. The polymers may be grafted with various compounds particularly those that result in functional groups such as epoxy, carboxylic anhydride (for instance as with a free radically polymerized reaction with malefic anhydride) or carboxylic acid (EPSE, vol.
12, p. 445). Such functionaiized polymers are particularly useful as tougheners for various thermoplastics and thermosets when blended. When the 1_>
m toeTtTt tTt= cNCCT IRI II F X61 polymers are elastomers, the functional groups whicr_ are grafted onto them may be used as curesites to crosslink the polymers. Malefic anhydride-grafted randomly-branched polyolefins are useful as tougheners for a wide range of materials (nylon, PPO, PPO/styrene alloys, PET, PBT, POM, etc.); as tie layers in multilayer constructs such as packaging barrier films;
as hot melt, moisture-curable, and coextrudable adhesives; or as polymeric plasticizers. The malefic 10 andhydryde-grafted materials may be post reacted with, for example; amines, to form other functional materials. Reaction with aminopropyl trimethoxysilane would allow for moisture-curable materials. Reactions with di- and tri-amines would allow for viscosity l~ modifications.

8. The polymers, particularly elastomers, may be used for modifying asphalt, to improve the physical properties of the asphalt and/or extend the life of asphalt paving.
~0 9. The polymers may be used as base resins for chlorination or chlorosulfonation for making the corresponding chlorinated cr chlorosulfonated elastomers. The unchlorinated polymers need not be elastomers themselves.
10. wire insulation and jacketing may be made from ar.y of the pclyolefins (see EPSE, vol. 17, _. 828-842). ~n the case of elastomers it may be preferable to crosslink the polymer after the insulation or jacketing is formed, for example by free radicals.
.i0 11. The polymers, particularly the elastomers, may be used as tougheners for other polyolefins such as polypropylene and polyethylene.
12. The base for synthetic lubricants (motor oils) may be the highly bunched polyolefins described 3~ herein (ECT3, vol. 14, p. 496-501).
13. The branched pclyolefins herein can be used as drip suppressants when added to other polymers.
1?6 .......a,~W 1Tr f'uCCT rD111 C ~R1 WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96/01282 14. The branched pciyolefins herein. are especially useful in blown film applications because of their particular rheologicai properties (EPEE, vol. 7, p. 88-106). It is preferred that these polymers have some crystallinity.
15. The polymer described herein can be used to blend with wax fcr candles, where they woula provide smoke suppression and/or drip control.
16. The polymers, especially the.branched polymers, are useful as base resins for carpet backing, especially for autcmobile carpeting.
17. The polymers, especially those which are relatively flexible, are useful as capliner resins for carbonated and noncarbonated beverages.
I~ 18. The polymers, especially those having a relatively low melting point, are useful as thermal transfer imaging resins (fcr instance for imaging tee-shirts or signs).
19. The polymers may be used for extrusion or ?0 coextrusion coatings onto plastics, metals, textiles or paper webs.
20. The polymers may be used as a laminating adhesive for glass.
21. The polymers are useful as for blown or cast films or as sheet (see EPSE, vol. 7 p. 68-106;
ECT4, vol. '~1, p. 843-856; PM, p. 252 and p. 432ff).
The films may be single layer or multilayer, the multilayer films may include other polymers, adhesives, etc. For packaging the films may be stretch-wrap, 30 shrink-wrap or cling wrap. The films are useful form many applications such as packaging foods, geomembranes and pond liners. It is preferred that these polymers have some crystallinity.
G2. The polymers may be used to form flexible 3~ or rigid foamed objects, such as cores for various sports items such as surf boards and liners for protective headgear. Structural foams may also be made. T_t is preferred that the polymers have some 1?7 et ieeTm wr cuCCT IG1 LI F ~Rl WO 96/23010 PC'T/L1S96/01282 crystallinity. The pciymer of the foams may be crosslinked.
23. In powdered form the polymers may be used to coat objects by using plasma, flame spray or ~ fluidized bed techniaues.
24. Extruded films may be formed from these polymers, and these films may be treated, for example drawn. Such extruded films are useful for packaging of various scrts.
10 25. The polymers, especially those that are elastemeric, may be used in various types of hoses, such as automotive heater hose.
26. The polymers, especially those that are branched, are useful as pour point depressants for 1~ =uels and cils.
27. These polymers may be flash spun to nonwoven fabrics, particularly if they are crystalline (see EPSE vol. 10, p. 202-253) They may also be used to form spunbonded polyolefins (EPSE, vol. 6, p. 756-20 760). These fabrics are suitable as house wrap and geotextiles.
28. The highly branched, low viscosity polyolefins would be good as base resins for master-batching of pigments, fillers, flame-retardants, and ?~ related additives for polyolefins. 29. The polymers may be grafted with a compound containing ethylenic unsaturation and a functional group such as a carboxyl group or a derivative of a carboxyl group, such as ester, carboxylic anhydride of carboxylate salt. A
30 minimum grafting level of about 0.01 weight percent of grafting agent based on the weight of the grafted polymer is preferred. The grafted polymers are useful as compatibilizers and/or tougheners. Suitable grafting agents include malefic, acrylic, methacrylic, 3~ itaconic, crotonic, alpha-methyl crotonic and cinnamic acids, anhydrides, esters and their metal salts and fumaric acid and their esters, anhydrides (when appropriate? and metal salts.
1?8 .....,nTm rrr PuCCT ID111 C 7R1 WO 96!23010 cA 02338526 2001-03-O1 PCT/US96101282 Copolymers of linear olefins with 4-~;inylcyclohexene and other dienes may generally be used or all of the applications for which the linear olefins polymersllisted above) may be used. .n addition they may be sulfur cured, so they generally can be used for any use for which EPDM polymers are wised, assuming the olefin/4-vinylcyclohexene polymer is ~iastomeric.
Also described herein are novel copolymers of _inear olefins with various polar monomers such as acrylic acid and acrylic esters. Uses for these polymers are given below. Abbreviations fey references aescribing these uses ir, general with polymers are the same as listed above for polymers made from linear 1 ~ ...;ef ir.s .
1. Tackifiers for low strength adhesives (U, vol. A1, p. 235-236) are a use for these polymers.
Jlastomeric and/or relatively low molecular weight polymers are preferred.
?0 2. The polymers are useful as base resins for :got melt adhesives (U, vol. A1, p. 233-234), pressure sensitive adhesives (U, vol. A1, p. 235-236) or solvent applied adhesives. Thermoplastics are preferred for of melt adhesives. The polymers may also be used in a '_'~ carpet installation adhesive.
3. Base polymer for caulking of various kinds _s another use. An elastomer is preferred. Lower :oiecular weight polymers are often used.
4. The polymers, particularly elastomers, may :0 ~e used for modifying asphalt, to improve the physical properties of the asphalt and/or extend the life of asphalt paving, see U.S. patent 3,980,598.
5. Wire insulation and jacketing may be made rpm any of the polymers Usee EPSE, vol. 17, p. 828-3~ X42). In the case of elastomers it may be preferable to crosslink the polymer after the insulation or acketing is formed, for example by free radicals.

et tacTITI rTF ~HFET (RULE 261 6. The polymers, especially the branched polymers, are useful as base resins for carpet backing, especially for automobile carpeting.
7. The polymers may be used for extrusion or 5 coextrusion coatings onto plastics, metals, textiles or paper webs.
8. The polymers may be used as a laminating adhesive for glass.

9. The polymers are useful as fcr blown or cast Films or as sheet (see EPSE, vol. 7 p. 88-106; ECT4, vol. ~~, p. 843-856; PM, p. 252 and p. 432ff). The films mGy be single layer or multilayer, the multilayer fi'~ms may include other polymers, adhesives, etc. For packaginc the films may be stretch-wrap, shrink-wrap or 1~ cline wrap. '',he films are useful form many applications such as packaging foods, geomembranes and pond liners. It is preferred that these polymers have some crystallinity.

10. The polymers may be used to form flexible ?0 or rigid foamed objects, such as cores for various sports items such as surf boards and liners for protective headgear. Structural foams may also be made. It is preferred that the polymers have some crystallinity. The polymer of the foams may be crosslinked.
1~. In powdered form the polymers may be used to coat objects by using plasma, flame spray or fluidized bed techniques.
12. Extruded films may be formed from these 30 polymers, and these films ma~~ be treated, for example drawn. Such extruded films are useful for packaging of various sorts.
13. The pciymers, especially those that are elastomeric, may be used in various types of hoses, 3~ such as automotive heater hose.
14. The polymers may be used as reactive diluents in automotive finishes, and for this purpose .

m ~ecTrr~ tTC CuCCT IRI 11 F ~Rl WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96101282 it is preferred that they have a relatively low molecular weight and/or have some crystallinity.
15. The polymers can be converted to ionomers, which when the possess crystallinity can be used as molding resins. Exemplary uses for these ionomeric molding resins are golf ball covers, perfume caps, sporting goods, film packaging applications, as tougheners in other polymers, and usually extruded) detonator cords.
16. The functional groups on the polymers can be used to initiate the polymerization of other types of monomers or to copolymerize with other types of monomers. IF the polymers are elastomeric, they can act as toughening agents.
l~ 7. The polymers can act as compatibilizing agents between various other polymers.
18. The polymers can act as tougheners for various other polymers, such as thermoplastics and thermosets, particularly if the olefin/polar monomer ?0 polymers are elastomeric.
19. The polymers may act as internal plasticizers for other polymers in blends. A polymer which may be plasticized is polyvinyl chloride).
20. The polymers can serve as adhesives between '_'' other colvmers .
2i. with the appropriate functional groups, the polymers may serve as curing agents for other polymers with complimentary functional groups (i.e., the functional groups of the two polymers react with each 30 other).
22. The polymers, especially those that are branched, are useful as pour point depressants for fuels and oils.
23. Lubricating oil additives as viscosity 3~ Index Improvers for multigrade engine oil (ECT3, Vol 14, p. 495-496) are another use. Branched polymers are preferred. Ethylene copolymer with acrylates or other polar monomers will also function as Viscosity Index m me~~ rTG cuccT rQl II F ~Rl Improvers for multigrade engine oil with the additic:~al advantage of providing some dispersancy.
24. The polymers may be used for roofing membranes.
25. The polymers may be used as additives to various molding resins such as the so-called thermoplastic olefins to improve paint adhesicn, as i.r_ automctive uses.
10 Polymers with or without polar monomers present are useful in the following uses. Preferred polymers with cr without polar monomers are those listed above in the uses for each "type".
1. A flexible pouch made from a single layer cr I~ mint=layer film ias described above) which may be used for packaging various liquid products such as milk, cr powder such as hot chocolate mix. The pouch may be heat sealed. It may also have a barrier layer, such as a metal foil layer.
~0 2. A wrap packaging film having differential cling is provided by a film laminate, comprising at least two layers; an outer reverse which is a polymer (or a blend thereof) described herein, which contains a tackifier in sufficent amount to impart cling properties; and an outer obverse which has a density of at -_east about 0.916 g/mL which has little or ne cling, provided that a density of the outer reverse layer is at -east 0.008 g/mL less than that of the dens=ty of the outer obverse layer. It is preferred that the 30 cuter cbverse layer is linear low density polyethylene, and the polymer of the outer obverse layer have a density of less than 0.90 g/mL. All densities are measured at 25°C.
3. Fine denier fibers and/or multifilaments.
3~ These ,«ay be melt spun. They may be in the form of a filament bundle, a non-woven web, a woven fabric, a knitted fabric or staple fiber.
13'_' m ~eeT~Ti m cuCCT IRI II F 'JRl WO 96/23010 ~ 02338526 2001-03-O1 PCTIUS96/01282 4. A composition comprising a mixture of the polymers herein and an antifogging agent. This composition is especially useful in film or sheet form because of its antifogging properties.
~. Elastic, randomly-branched olefin polymers are disclosed which have very good processability, including processing indices (PI's) less than or equal to 70 percent of those of a comparative linear olefin polymer and a cr,.'~tical shear rate at onset of surface melt =racture of at least 50 percent greater than. the criticGl shear rate at the onset of surface melt fracture of a traditional linear olefin polymer at abOllt the same I2 and Mw/Mn. The novel polymers may have higher low/zero shear viscosity and lower high l; shear .iscosity than comparative linear olefin polymers made by other means. These polymers may be characterized as having: al a melt flow ratio, I10/I2, 5.53, b) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mn < (I10/I2)-4.63, and c) '_'0 a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear olefin polymer having about the same I2 and Mw/Mn.
Some blends of these polymer are characterized as ~~ havinc: al a melt flow ratio, I10/I2, > 5.63, b) a moiec;:lar weight distribution, Mw/Mn, defined by the equaticn: Mw/Mn <_ (I10/I2)-4.63, and c) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate .0 at the onset of surface melt fracture of a linear olefin polymer having about the same I2 and Mw/Mn and (b) at least one other natural or synthetic polymer chosen from the polymer of claims 1, 3, 4, 6, 332, or 343, a conventional high density polyethylene, low ~~ density polyethylene or linear low density polyethylene polymer. The polymers may be further characterized as having a melt flow ratio, I10/I2, >_ 5.63, a molecular weight distribution, Mw/Mn, defined by the equation:
1~~
Ct tt7CTtTt fTC CNFFT IRI II F ~Rl Mw/Mn <_ tIlO/I2)-4.63, and a critical shear stress at onset of gross melt fracture ef greater than about 400 kFa (4x106 dyne/cmz) and their method cf manufacture are disclosed. The randomly-branched olefin polymers preferably have a molecular weight distribution from about 1.5 to about 2.5. The pciymers described herein ofte:: have improved processability over conventional olefin polymers and are useful in producing fabricated articles such as fibers, films, and molded parts. For 10 this paragraph, the value I2 is measured in accordance with ASiM ~-1236-190/2.16 and I10 is measured in acccrdance with ASTM D-1236-190/10; critical shear rate at onset ef surface melt fractu=a and processing index tFI) are defined in U.S. Patent 5,278,272, 1~ which may be referred to.
In. another process described herein, the product of the process described herein is an a-olefin. It is preferred that in the process a linear a-olefin. is produced. It is also preferred that the a-olefin ?0 contain 4 to 32, preferably 8 to 20, carbon atoms.

~N~
~- N~ ~ S

l (XXXI) When (XXXI) is used as a catalyst, a neutral Lewis acid or a cationic Lewis cr Hronsted acid whose counterion is a weakly coordinating anion is also present as part of the catalyst system (sometimes called a "first compound" in the claims).. Hy a "'neutral Lewis acid" is meant a compound which is a Lewis acid capable for abstracting X~ from (I) to form 30 a weakly coordinating anion. The neutral Lewis acid is originally uncharged (1.e., not ionic). Suitable neutral Lewis acids include SbFs, Ar~H (wherein Ar is WO 96123010 PC'TIUS96101282 aryl) , arid B~_ By a catior:.. Lewis ac=d ._ men.~.w a cation with a positive charge such as Ag', .:', and Na' A preferred neutral Lewis acid is an a~.:kyi aluminL,:~ compound, such as R',A1, RS~A1C1, R'A1C~_, and ~~R5A10" (alkylaluminoxane), wherein Rs is alkyl containing ? to 25 carbon atoms, preferably 1 to 4 carboy. moms . Suitabl a alkyl aluminum cc-;pouads '_nClude lTct)'1V1 aluT':i nOXane, (C'~H~) ~Al ~1, ~,riSA~W:, anQ
(CH3) ~C'_-'.~.'_'L~] ~A1 .
10 Relative_y noncoordinatina anions are known in the ay t, and t:e coordinating abil ity of suc'r. a__~.io~s is known G :~ i-~as been discussed i.~. the literature, see for instance V. Beck., et al., C:em. Rev., vc_. 8E p. 1405-1421 (1966), and S. H. Strauss, Chem. Rev., vcl. 9~, p...
1 f 92 ~ - ~4 2 _: ~: : , both cf whic: may be referred to .
Among such anions are those t~=med from the aluminum compounds in the immediately preceding paragraph and X , including R'~A1X , R~2A1C1X , R~AICIzX' , and ~R9Ai0X'". Other useful noncoordina~i.4 anions ?0 include BAF jEAF = tetrakis(3,5-bis ( trif ~.uorcmethyl ) phenyl ] borate ) , SbF 6' , PF;' , and BF s triflucromethanesulfonate, p-toiuenesul=onate, (R~SO:),N , and (CEFS)4B .
The temperature at which: the process is carried out is about -l00"C to about T200'C, preferably about 0'C to about 150'C, more preferably about 5'C t.. abo;:t 100'C. Tt is believed that at higher temperatures, lower mc';ecular weight a-olefins are produced, all other factors being equal. The pressure at which the 30 polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. .t is also believed that increasing the pressure increases the relative amount of a-olefin (as opposed to internal olefin) produced.
35 The process to make a-olefins may be run in a solvent (liquiad), and that is preferred. The solvent may in fact be the a-olefin produced. Such a process may be started by using a deliberately added solvent 13~

which is gradually displaced as the reaction proceeas.
By solvent it is not necessarily meant that any or all of the starting materials and/or products are soluble in the (liquid) solvent.
s in (I) it is preferred that R3 and R~ are both hydrogen cr methyl or R~ and R4 taken together are \ \
/ /
(An) 10 .t is also preferred that each of Q and S is independently chlorine or bromine, and it is more preferred trat both of Q and S in (XXXI) are chlorine or bromine.
In (XXXI) R' and RS are hydrocarbyl or substituted l~ hydrocarbyl. What these groups are greatly determines whether the a-olefins of this process are made, or whether higher polymeric materials, i.e., materials containing over 25 ethylene units, are coproduced or produced almost exclusively. If R2 and RS are highly ?0 sterically hindered about the nickel atom, the tendency is to produce higher polymeric material. For instance, when R- and RS are both 2,6-diisopropylphenyl mostly higher polymeric material is produced. However, when R' and RS are both phenyl, mostly the a-olefins of this process are produced. Of course this will also be influenced by other reaction conditions such as temperature and pressure, as noted above. Useful groups for R' and RS are phenyl, and p-methylphenyl.
As is understood by the artisan, in .0 ..-iaomerization reactions of ethylene to produce a-olefins, usually a mixture of such a-olefins is obtained containing a series of such a-olefins differing from one another by two carbon atoms (an ethylene unit). The process for preparing a-olefins 3~ described herein produces products with a high m meTm tTC cu>=FT fRl I1 F ?61 WO 96123010 ~ 02338526 2001-03-O1 PCT/US96I01282 percentage of terminal olefinic groups (as opposed to _nternal olefinic groups). The product mixture also contains a relatively high percentage of molecules which are linear. Finally relatively high catalyst efficiencies can be obtained.
The a-olefins described as being made herein may also be made by contacting ethylene with one of the compounds R2 ~ +
Rs~N T' ~N~
R4~N
~5 (III) or l~
R2 ~ +
_N U
f~N
(XXXIV) wherein R', R3, R', and RS are as defined (and preferred) as described above (for the preparation of a -olefins), and T' is hydrogen or n-alkyl containing up to 38 carbon atoms, Z is a neutral Lewis base wherein ?0 she donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, U is n-alkyl containing up to 38 carbon atoms, and X is a noncoordinating anio.~.
2~ ;see above). The process conditions for making a-oiefins using (III) or (XXXIV) are the same as for using (XXXI) to make these compounds except a Lewis or Bronsted acid need not be present. Note that the double line in (XXXIV) represents a coordinated of ~ecTtT~ tTC CL1~CT IQI II F ~Rl WO 96/23010 ~ 02338526 2001-03-O1 ethylene molecule. (XXXIV) may be made from (II) by reaction of (III) with ethylene. In other words, (XXXIV) may be considered an active intermediate in the formation of a-olefin from (III). Suitable groups for Z include dialkyl ethers such as diethyl ether, and alkyl nitrites such as acetonitrile.
In general, a-olefins can be made by this process using as a catalyst a Ni[II] complex of an a-diimine of formula (VIII), wherein the Ni[II] complex is made by any of the methods which are described above, using Ni [ 0 ] , Ni [ I ] or Ni [ I I ] precursors . Al l of the process conditions, and preferred groups on (VIII), are the same as described above in the process for making a-olefins.
l~
FXAMPT,F~
In the Examples, the following convention is used for naming a-diimine complexes of metals, and the a-diimine itself. The a-diimine is indicated by the ?0 letters "DAB". To the left of the "DAB" are the two groups attached to the nitrogen atoms, herein usually called R2 and R5. To the right of the "DAB" are the groups or_ the two carbon atoms of the a-diimine group, herein usually termed R3 and R'. To the right of all this appears the metal, ligands attached to the metal (such as Q, S and T), and finally any anions (X), which when "free" anions are designated by a superscript minus sign (i.e., X-). Of course if there is a "free"
anion present, the metal containing moiety is cationic.
30 Abbreviations for these groups are as described in the Specification in the Note after Table 1. Analogous abbreviations are used for a-diimines, etc.
In the Examples, the following abbreviations are used:
35 OHf - heat of fusion acac - acetylacetonate Bu - butyl t-BuA - t-butyl acrylate ei iaeTm r~ euccT IRI II F ~Rl DMA - Dynamic Mechanical Analysis DME - 1,2-dimethoxyethane DSC - Differential Scanning Calorimetry E - ethylene EOC - end of chain Et - ethyl FC-75 - perfluoro(n-butyltetrahydrofuran) FOA - fluorinated octyl acrylate GPC - gel permeation. chromatography MA - methyl acrylate MAO - methylaluminoxane Me - methyl MeOH - methanol MMAO - a modified methylaluminoxane in which l~ about 25 e percent of the methyl groups have mol been replaced isobutyl groups by M-MAO - see MMAO

MMAO -3A - see MMAO

Mn - number average molecular weight MVK - methyl vinyl ketone Mw- weight average molecular weight Mz - viscosity average molecular weight PD or P/D
- polydispersity, Mw/Mn Ph - phenyl 'S PMAO - see MAO

PMMA - poly(methyl methacrylate) Pr - propyl PTFE - polytetrafluoroethylene RI - refractive index RT (or rt) - room temperature TCE - 1,1,2,2-tetrachloroethane Tc - temperature of crystallization Td - temperature of decomposition.

Tg - glass transition temperature >> TGA - Thermogravimetric Analysis THF - tetrahydrofuran Tm - melting temperature SUHSTITlITE SHEET (RULE 26) WO 96123010 ~ 02338526 2001-03-O1 PCTIUS96/01282 TO - turnovers , the number of mdl'~3 "~" mo?ioti~'e=
polymerized per g-atom of metal in the catalyst used Uv - ultraviolet Unless otherwise noted, all pressures are gauge pressures.
In the Examples, the following procedure was used to quantitatively determine branching, and the distribution of branch sizes in the polymers (but not necessarily the simple number of branches as measured 10 by total number bf methyl groups per 1000 methylene groups). 100 MHz 13C NMR spectra were obtained on a Varian Unity 400 MHz spectrometer using a 10 mm probe en typically 15-20 wt% solutions of the polymers and 0.05 M Cr(acetylacetonate)3 in 1,2,4-trichlorobenzene 1~ (TCB) unlocked at 120-140°C using a 90 degree pulse o 12.5 to 18.5 sec, a spectral width of 26 to 35 kHz, a relaxation delay of 5-9 s, an acquisition time of 0.64 sec and gated decoupling. Samples were preheated for at least 15 min before acquiring data. Data ?0 acquisition time was typically 12 hr. per sample. The T1 values of the carbons were measured under these conditions to be all less than 0.9 s. The longest T1 measured was for the Bu+, end of chain resonance at 14 ppm, which was 0.84 s. Occasionally about 16 vol. o benzene-d~ was added to the TCB and the sample was run locket. Some samples were run in chloroform-dl, CDC1~-dl, (locked) at 30°C under similar acquisition parameters. T1's were also measured in CDC13 at ambient temperature on a typical sample with o.05 M
~0 Cr(acetylacetonate)3 to be all less than 0.68 s. In rare cases when Cr(acetylacetonate)3 was not used, a 30-40 s recycle delay was used to insure quantitation.
':he a~ycidyl acrylate copolymer was run at 100°C with Cr(ace~ylacetonate);. Spectra are referenced to the 3~ sclver.~ - either the TCB highfield resonance at 127.8 ppm er the chloroform-dl triplet at 77 ppm. A DEPT 135 spectrum was done on most samples to distinguish methyls and methines from methylenes. Methyls were c~ mSTm 1TF SHEET rRULE 261 ,listinguished from methines by chemical shift. EOC is end-of-chain. Assignments reference to following naming scheme:
1. xBy: By is a branch of length y carbons; x is the carbon being discussed, the methyl at the end of the branch is numbered 1. Thus the second carbon from the end of a butyl branch is 2B4. Branches of length y or greater are designated as y+.
2. xEBy: EB is an ester ended branch containing y methylenes. x is the carbon being discussed, the first methylene adjacent to the ester carbonyl is labeled 1.
Thus the second methylene from the end of a 5 methylene ester terminated branch would be 2EB5. 13C NMR of model compounds for EBy type branches for y=0 and y=5+
confirm the peak positions. and assignments oz these branches. In addition, a model compound for an EB1 branch is consistent with 2 dimensional NMR data using the well know 2D NMR techniques of hsqc, hmbc, and hsqc-tocsy; the 2D data confirms the presence of the ?0 EB5+, EBO, EB1 and other intermediate length EB
branches 3. The methylenes in the backbone are denoted with Greek letters which determine how far from a branch point methine each methylene is. Thus (3~3 (beta beta) B denotes the central methylene in the following PCHRCH2CH2CH2CHRP. Methylenes that are three or morer carbons from a branch point are designated as y+
(gamma+).
4. When x in xBy or xEBy is replaced by a M, the ~0 methine carbon of that branch is denoted.
Integrals of unique carbons in each branch were measured and were reported as number of branches per 1000 methylenes (including methylenes in the backbone and branches). These integrals are accurate to +/- 50 relative for abundant branches and +/- 10 or 20%
relative for branches present at less than 10 per 1000 methylenes.

SUBSTITUTE SHEET (RULE 26) WO 96/23010 cA 02338526 2001-03-O1 PCT/US96/01282 Such types of analyses are generall~~ mown, see for instance "A Quantitative Analysis of Low Density (Branched) Polyethylenes by Carbon-13 Fourier Transform Nuclear Magnetic Resonance at 67.9 MHz", D. E. Axelson, 5 et al., Macromolecules 12 (1979) pp. 41-52; "Fine Branching Structure in High-Pressure, Low Density Polyethylenes by 50.10-MHz 13C NMR Analysis", T. Usami et al., Macromolecules 17 (1984) pp. 1757-1761; and "Quantification of Branching in Polyethylene by 13C NMR
10 Using Paramagnetic Relaxation Agents", J. V. Prasad, et al., Eur. Polym. J. 27 (1991) pp. 251-254 (Note that this latter paper is believed to have some significant typographical errors in it).
It is believed that in many of the polymers 1~ described herein which have unusual branching, i.e., they have more or fewer branches than would be expected for "normal" coordination polymerizations, or the distribution of sizes of the branches is different from that expected, that "branches on branches" are also ?0 present. By this is meant that a branch from the main chain on the polymer may itself contain one or more branches. It is also noted that the concept of a "main chain" may be a somewhat semantic argument if there are sufficient branches on branches in any particular polymer.
By a polymer hydrocarbyl branch is meant a methyl group to a methine or quaternary carbon atom or a group of consecutive methylenes terminated at one end by a methyl group and connected at the other end to a 30 methine or quaternary carbon atom. The length of the branch is defined as the number of carbons from and including the methyl group to the nearest methine or quaternary carbon atom, but not including the methine cr quaternary carbon atom. If the number of consecutive methylene groups is "n" then the branch contains (or the branch length is) n+1. Thus the structure (which represents part of a polymer) -~~ iRSTITItTE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 PCT'~1S96/01282 .H2CHzCH [CH;CH2CH~CH~CH (CH3) CH~CH3) CH~CH~CHzCH=- ccntains 2 branches, a methyl and an ethyl branch.
For ester ended branches a similar definition is used. An ester branch refers to a group of consecutive methyiene groups terminated at one end by an ester -COOR group, and connected at the other end to a methine or quaternary carbon atom. The length of t:~e branch is defined as the number of consecutive methylene groups from the ester group to the nearest methine or 10 quaternary carbon atom, but not including the methine er quaternary carbon atom. If the number of methylene groups is "n", then the length of the branc:~: is n.
Thus -CH~CH,CH[CH~CHzCH~CH~CH(CH,)CH~COORJCH,CE_CH2CHz-contains 2 branches, a methyl and an n=1 ester branch.
l~ The -'C NMR peaks for.copolymers of cyciopentene and ethylene are described based on the labeling scheme and assignments of A. Jerschow et al, Macromolecules 1995, 28, 7095-7099. The triads and pentads are described as 1-cme, 1,3-ccmcc, 1,3-cmc, 2-cme, 2-cmc, 20 1,3-eme,3-cme, and 4,5-cmc, where a = ethylene, c =
cyclopentene, and m = meta cyclopentene (i.e. 1,3 enchainment). The same labeling is used fer cyclopentene/1-pentene copolymer substituting p =
pentane for e. The synthesis of diimines is reported in the literature (Tom Dieck, H.; Svoboda, M.; Grieser, T. Z. Naturforsch 1981, 36b, 823-832. Klieaman, J. M.;
Barnes, R. K. J. Org. Chem. 1970, 35, 3140-3143.) Example 1 [(2,6-i-PrPh)2DABMez]PdMeCl 30 Et20 (75 mL) was added to a Schlenk flask containing CODPdMeCl (COD = 1,5-cyclooctadiene) (3.53 g, 13.3 mmol) and a slight excess of (2,6-_ PrPh)2DABMe- (5.43 g, 13.4 mmol, 1.01 equiv). An orange precipitate began to form immediately upon 3~ mixing. The reaction mixture was stirred overnight and the Et20 and free COD were then removed via filtration.
The product was washed with an additional 25 mL of Et20 and then dried overnight in vacuo. A pale orange SUBSTITUTE SHEET (RULE 26) i powder (7.18 g, 95.80) was isolated: '-H NMR (CD2Ci~, 400 MHz) 8 7.4 - 7.2 (m, 6, Hary1). 3.06 (septet, 2, J -6.81, CHMe2), 3.01 (septet, 2, J = 6.89, C'HMe2), 2.04 and 2.03 (N=C(Me)-C'(Me)=N), 1.40 (d, 6, J = 6.79, J C'HMeMe'), 1.36 (d, 6, J = 6.76, CHMeMe'), 1.19 (d, 6, J = 6.83, CHMeMe'), 1.18 (d, 6, J = 6.87, C'HMeMe'), 0.36 (s, 3, PdMe); 13C NMR (CDZC12, 400 MHz) b 175.0 and 170.3 (N=C-C'=N), 142.3 and 142.1 (Ar, Ar': Cipso) 138.9 and 138.4 (Ar, Ar': Co), 128.0 and 127.1 (Ar, Ar': Cp), 124.3 and 123.5 (Ar, Ar': Cm), 29.3 (CHMe2), 28.8 (C'HMe2), 23.9, 23.8, 23.5 and 23.3 (CHMeMe', C'HMeMe'), 21.5 and 20.1 (N=C(Me)-C'(Me)=N), 5.0 (J~H =
135.0, PdMe).
14.~
suss~TUTE SHEET (RULE 26) WO 96123010 ~ 02338526 2001-03-O1 PCT/US96101282 Exam l~
[(2,6-i-PrPh)zDABH2)PdMeCl Following the procedure of Example 1, an orange powder was isolated in 97.1% yield: 1H NMR (CDZCIz, 0 400 MHz) s 8.31 and 8.15 (s, 1 each, N=C(H)-C'(H)=N), 7.3 - 7.1 (m, 6, Hary1), 3.22 (septet, 2, J = 6.80, CF~Ie2) , 3.21 (septet, 2, J = 6.86, C'HMe2) , 1.362, . 1.356, 1.183 and 1.178 (d, 6 each, J = 7.75 - 6.90;
CHMeMe', C'HMeMe'), 0.67 (s, 3, PdMe); 13C NMR
(CD2C12, 100 MHz) 8 164.5 (J~g = 179.0, N=C(H)), 160.6 (J~H = 178.0, N=C'(H)), 144.8 and 143.8 (Ar, Ar' Cipso)~ 140.0 and 139.2 (Ar, Ar': Co), 128.6 and 127.7 (Ar, Ar': Cp), 124.0 and 123.4 (Ar, Ar': Cm), 29.1 (CHMe2), 28.6 (C'HMe2), 24.7, 24.1, 23.1 and 22.7 1 ~ , ~~HMeMe ' , C ' HMeMe ' ) , 3 . 0 ( J~H = 13 4 . 0 , PdMe ) . Anal .
Calcd for (CZ~H39C1N2Pd): C, 60.79; H, 7.37; N, 5.25.
Found: C, 60.63; H, 7.24; N, 5.25.
Examp 1~3 [(2,6-MePh)2DABMe2JPdMeC1 Following the procedure of Example 1, a yellow powder was isolated in 90.60 yield: 2H NMR (CD2C12, 400 MHz) 8 7.3 - 6.9 (m, 6, Haryl), 2.22 (s, 6, Ar, Ar':
Me), 2.00 and 1.97 (N=C(Me)-C'(Me)=N), 0.25 (s, 3, PdMe ) .
[(2,6-MePh)zDABMe~]PdMeCl Following the procedure of Example 1, an orange powder was isolated in 99.0o yield: 1H NMR (CD2C1~, 400 MHz, 41 °C) b 8.29 and 8.14 (N=C(H)-C'(H)=N), 7.2 -30 7.1 (m, 6, Haryl), 2.33 and 2.30 (s, 6 each, Ar, Ar':
Me), 0.61 (s, 3, PdMe); 13C NMR (CD2C12, 100 MHz, 41 °C) b 165.1 (Jcg = 179.2, N=C(H)), 161.0 (Jcg = 177.8 (N=C'(H)), 147.3 and 146.6 (Ar, Ar': Cipso). 129.5 and 128.8 (Ar, Ar': Co), 128.8 and 128.5 (Ar, Ar': Cm), 3~ i27.9 and 127.3 (Ar, Ar': Cp), 18.7 and 18.2 (Ar, Ar':
Me), 2.07 (J~H = 136.4, PdMe).

SUBSTITUTE SHEET (RULE 26) Example 5 [4-MePh) 2DABMe2] PdMeCl Following the procedure of Example 1, a yellow powder was isolated in 92.1% yield: 1H NMR (CD2C12, 5 400 MHz) b 7.29 (d, 2, J = 8.55, Ar: Hn,) , 7.26 (d, 2, J
- 7.83, Ar': Hm), 6.90 (d, 2, J = 8.24, Ar': Ho), 6.83 (d, 2, J = 8.34, Ar: Ho), 2.39 (s, 6, Ar, Ar': Me), 2.15 and 2.05 (s, 3 each, N=C(Me)-C'(Me)=N), 0.44 (s, 3, PdMe); 13C NMR (CD2C12, 100 MHz) 8 176.0 and 169.9 10 (N=C-C'=N) , 144.9 and 143.7 (Ar, Ar' : Cipso) , 137.0 and 136.9 (Ar, Ar': Cp), 130.0 and 129.3 (Ar, Ar': Cm), 122.0 and 121.5 (Ar, Ar': Co), 21.2 (N=C(Me)), 20.1 (Ar, Ar': Me), 19.8 (N=C'(Me)), 2.21 (J~H = 135.3, PdMe). Anal. Calcd for (C19H23C1N2Pd): C, 54.17; H, 1~ 5.50; N, 6.65. Found: C, 54.41; H, 5.37; N, 6.69.
Example 6 [ (4-MePh) 2DABH2] PdMeCl Following the procedure of Example 1, a burnt orange powder was isolated in 90.50 yield: Anal. Calcd 20 for (C1~H19C1N2Pd): C, 51.93; H, 4.87; N, 7.12. Found:
C, 51.36; H, 4.80; N, 6.82.
Example 7 ({ [ (2, 6-i-PrPh) 2DABMe2] PdMe}z (~-C1) )BAF-Et20 (25 mL) was added to a mixture of [(2,6-i-2J PrPh)ZDABMe2]PdMeCl (0.81 g, 1.45 mmol) and 0.5 equiv cf NaBAF (0.64 g, 0.73 mmol) at room temperature. A
golden yellow solution and NaCl precipitate formed immediately upon mixing. The reaction mixture was stirred overnight and then filtered. After the Et20 30 was removed in vacuo, the product was washed with 25 mL
of hexane. The yellow powder was then dissolved in 25 mL of CH2C12 and the resulting solution was filtered in order to removed traces of unreacted NaBAF. Removal of CH2C12 in vacuo yielded a golden yellow powder (1.25 g, 3~ 88.20): 1H NMR (CD2C12, 400 MHz) 8 7.73 (s, 8, BAF:
Ho), 7.57 (s, 4, BAF: Hp), 7.33 (t, 2, J = 7.57, Ar:
Hp), 7.27 (d, 4, J = 7.69, Ar: Ho), 7.18 (t, 2, J =
7.64, Ar: Hp), 7.10 (d, 4, J = 7.44, Ar': Ho), 2.88 ~ues~ITUTE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96I01282 tseptet, 4, J = 6.80, CHMe2), 2.75 (septet, 4, J =

6 82, C'HMez), 2.05 and 2.00 (s, 6 each, N=C(Me)-C'(Me)=N), 1.22, 1.13, 1.08 and 1.01 (d, 12 each, J =

6.61-6.99, CHMeMe', C'HMeMe'), 0.41 (s, 6, PdMe); 13C

NMR (CD2C12, 10 0 MHz) 8 177.1 and 171.2 (N=C-C'=N), 162.2 (q, Jg~ = 49.8, BAF: Cipso), 141.4 and 141.0 (Ar, Ar': Cipso), 138.8 and 138.1 (Ar, Ar': Co), 135.2 (BAF:

Cp), 129.3 (q, J~p = 31.6, BAF: Cm), 128.6 and 127.8 (Ar, Ar': Cp), 125.0 (q, J~F = 272.5, BAF: CF3), 124.5 and 123 . 8 (Ar,Ar' : Cm) , 117.9 (BAF: Cp) , 29.3 (C~le2) , 29.0 (C'HMe2), 23.8, 23.7, 23.6 and 23.0 (CHMeMe', C'HMeMe'), 21.5 and 20.0 (N=C(Me)-C'(Me)=N), 9.8 (J~H
-_ 136.0, PdMe) . Anal. Calcd for (C9oH98BC1F24N4Pd2) : C, 55.41; H, 5.06; N, 2.87. Found: C, 55.83; H, 5.09; N, I~ 2.63.

Rxam 1~_8 (~ ( (2, 6-i-PrPh) 2DABHz] PdMe}2 (~-C1) )BAF-The procedure of Example 7 was followed with one exception, the removal of CH2C12 in vacuo yielded a 20 product that was partially an oil. Dissolving the compound in Et20 and then removing the Et20 in vacuo yielded a microcrystalline red solid (85.50): 1H NMR
(CD2C12, 400 MHz) 8 8.20 and 8.09 (s, 2 each, N=C(H)-C'(H)=N), 7.73 (s, 8, BAF: Ho), 7.57 (s, 4, BAF: Hp), 25 7.37 (t, 2, J = 7.73, Ar: Hp), ?.28 (d, 4, J = 7.44, Ar: Hm), 7.24 (t, 2, Ar': Hp), 7.16 (d, 4, J = 7.19, Ar' : Hm) , 3 .04 (septet, 4, J = 6.80, CI~Ie2) , 2.93 (septet, 4, J = 6.80, C'HMe2), 1.26 (d, 12, J = 6.79, CHMeMe'), 1.14 (d, 12, J = 6.83, CHMeMe'), 1.11 (d, 12, 30 J = 6.80, C'HMeMe'), 1.06 (d, 12, J = 6.79, C'HMeMe'), 0.74 (s, 6, PdMe); 13C NMR (CD2C12 , 100 MHz) b 166.0 (J~g = 180.4, N= C(H)), 161.9 (q, JB~ = 49.6, BAF:
Cipso)~ 160.8 (J~H = 179.9, N=C'(H)), 143.5 and 143.0 (Ar, Ar': Cipso), 139.8 and 138.9 (Ar, Ar': Co), 135.2 35 (BAF: Co), 129.3 (q, J~F = 31.4, BAF. Cn,), 129.3 and 128.5 (Ar, Ar': Cp), 125.0 (q, J~F = 272.4, BAF: CF3), 124.3 and 123.7 (Ar, Ar': Cm), 117.9 (BAF: Cp), 29.2 and 28.9 (CHMe2, C'HMe2), 24.5, 24.1, 23.0, and 22.5 SUBSTITUTE SHEET (RULE 26) WO 96123010 ~ 02338526 2001-03-O1 PCT/US96/01282 (CHMeMe', C'HMeMe'), 10.3 (PdMe). Anal. Calcd for (Cg6H9pBC1F24N4Pd2) : C, 54.52; H, 4.97; N, 2.96.
Found: C, 54.97; H, 4.72; N, 2.71.
Exam In a 9 5 Alternatively, the products of Examples 7 and 8 have been synthesized by stirring a 1:1 mixture of the appropriate PdMeCl compound and NaBAF in Et20 for -.1 h.
Removal of solvent yields the dimer + 0.5 equiv of Na+(OEt2)2BAF-. Washing the product mixture with 10 hexane yields ether-free NaBAF, which is insoluble in CH2C12. Addition of CHZC12 to the product mixture and filtration of the solution yields salt-free dimer:
1H NMR spectral data are identical with that reported above.
15 For a synthesis of CODPdMe2, see: Rudler-Chauvin, M., and Rudler, H. J. Organomet. Chem. 1977, 134, 115-119.
xa ~, a 10 [(2,6-i-PrPh)2DABMe2]PdMez 20 A Schlenk flask containing a mixture of [(2,6-i-PrPh)2DABMe2]PdMeCl (2.00 g, 3.57 mmol) and 0.5 equiv of Me2Mg (97.2 mg, 1.79 mmol) was cooled to -78 °C, and the reaction mixture was then suspended in 165 mL of Et20. The reaction mixture was allowed to warm to room 25 temperature and then stirred for 2 h, and the resulting brown solution was then filtered twice. Cooling the solution to -30 °C yielded brown single crystals (474.9 mg, 24.6%, 2 crops): 1H NMR (C6D6, 400 MHz) 8 7.2-7.1 (m, 6, Haryl) , 3.17 (septet, 4, J = 6.92, CFINIe2) , 1.39 30 (d, 12, J = 6.74, CHMeMe'), 1.20 (N=C(Me)-C(Me)=N), 1.03 (d, 12, J = 6.89, CHMeMe'), 0.51 (s, 6, PdMe); 13C
NMR (C6D6, 100 MHz) b 168.4 (N=C-C=N), 143.4 (Ar:
Cipso) . 138. 0 (Ar: Co) , 126.5 (Ar: Cp) , 123.6 (Ar: Cn,) , 28.8 (CHMe2), 23.6 and 23.5 (CHMeMe'), 19.5 (N=C(Me)-35 C (Me) =N) , -4 . 9 (J~ = 127. 9, PdMe) . Anal . Calcd for (C3pH46N2Pd): C, 66.59; H, 8.57; N, 5.18. Found: C, 66.77; H, 8.62; N, 4.91.

SUBSTITUTE SHEET (RULE 26) Fxamt~le [(2,6-i-PrPh)2DABH2)PdMe2 The synthesis of this compound in a manner analogous to Example 10, using 3.77 mmol of ArN=C(H)-C(H)=NAr and 1.93 mmol of Me2Mg yielded 722.2 mg (37.4%) of a deep brown microcrystalline powder upon recrystallization of the product from a hexane/toluene solvent mixture.
This compound was also synthesized by the 10 following method: A mixture of Pd(acac)2 (2.66 g, 8.72 mmol) and corresponding diimine (3.35 g, 8.90 mmol) was suspended in 100 mL of Et20, stirred for 0.5 h at room temperature, and then cooled to -78°C. A solution of Me2Mg (0.499 g, 9.18 mmol) in 50 mL of Et20 was then 15 added via cannula to the cold reaction mixture. After stirring for 10 min at -78°C, the yellow suspension was allowed to warm to room temperature and stirred for an additional hour. A second equivalent of the diimine was then added to the reaction mixture and stirring was 20 continued for -4 days. The brown Et20 solution was then filtered and the solvent was removed in vacuo to yield a yellow-brown foam. The product was then extracted with 75 mL of hexane, and the resulting solution was filtered twice, concentrated, and cooled 25 to -30°C overnight to yield 1.43 g (32.0%) of brown powder: 1H NMR (C6D6, 400 MHz) b 7.40 (s, 2, N=C(H)-C(H)=N) , 7.12 (s, 6, Har.yl) , 3.39 (septet, 4, J = 6.86, CHMe2), 1.30 (d, 12, J = 6.81, CHMeMe~), 1.07 (d, 12, J
- 6.91, CHMeMe'), 0.77 (s, 6, PdMe); 13C NMR (C6D6, 100 30 MHz) 8 159.9 (JcH = 174.5, N=C(H)-C(H)=N), 145.7 (Ar:
Cipso) . 138 . 9 (Ar: Co) , 127.2 (Ar: Cp) , 123 .4 (Ar: Cm) , 28.5 (CHMe2), 24.4 and 22.8 (CHMeMe'), -5.1 (JcH =
128.3, PdMe). Anal. Calcd for (C28H42N2Pd): C, 65.55, H, 8.25; N, 5.46. Found: C, 65.14; H, 8.12; N, 5.14.

SuBSTiTUTE SHEET (RULE 26) Exams [(2,6-MePh)2DABH~]PdMe2 This compound was synthesized in a manner similar to the second procedure of Example 11 (stirred for 5 h 5 at rt) using 5.13 mmol of the corresponding diimine and 2.57 mmol of Me2Mg. After the reaction mixture was filtered, removal of Et20 in vacuo yielded 1.29 g (62.20) of a deep brown microcrystalline solid: 1H NMR
(C6D6, 100 MHz, 12°C) 8 6.98 (s, 2, N=C(H)-C(H)=N), 10 6.95 (s, 6, Ha~,l) , 2.13 (s, 12, Ar: Me) , 0.77 (s, 6, PdMe); 13C NMR (C6D6, 400 MHz, 12°C) b 160.8 (J~H =
174 . 6, N=C(H) -C(H) =N) , 147. 8 (Ar: Cipso) , 128.2 (Ar:
Cm), 128.15 (Ar: Co), 126.3 (Ar: Cp), 18.2 (Ar: Me), -5.5 (J~H = 127.6, Pd-Me).
1 S Exam P 13 [ (2, 6-i-PrPh) 2DABH2] NiMe2 The synthesis of this compound has been reported (Svoboda, M.; tom Dieck, H. J. Organomet. Chem. 1980, 19I, 321-328) and was modified as follows: A mixture 20 of Ni(acac)2 (1.89 g, 7.35 mmol) and the corresponding diimine (2.83 g, 7.51 mmol) was suspended in 75 mL of Et20 and the suspension was stirred for 1 h at room temperature. After cooling the reaction mixture to -78°C, a solution of Me2Mg (401 mg, 7.37 mmol) in 25 mL
2~ of Et20 was added via cannula. The reaction mixture was stirred for 1 h at -78°C and then for 2 h at 0°C to give a blue-green solution. After the solution was filtered, the Et20 was removed 'in vacuo to give a blue-green brittle foam. The product was then dissolved in 30 hexane and the resulting solution was filtered twice, concentrated, and then cooled to -30°C to give 1.23 g (35.90 , one crop) of small turquoise crystals.
Example 14 [ (2, 6-i-PrPh) zDABMe2] NiMe2 35 The synthesis of this compound has been reported (Svoboda, M.; tom Dieck, H. J. Organomet. Chem. 1980, 191, 321-328) and was synthesized according to the above modified procedure (Example 13) using Ni(acac)2 SUBSTIME SHEET (RULE 26) ,;3.02 g, 11.75 mmol), the corresponding diWt~~e 14.80 g, 11.85 mmol) and Me2Mg (640 mg, 11.77 mmol). A
turquoise powder was isolated (620 mg, 10.70).
F_xample ~5 ([(2,6-MePh)2DABMe2JPdMe(MeCN)}BAF
To a mixture of [(2,6-MePh)2DABMe2JPdMeC1 (109.5 mg, 0.244 mmol) and NaBAF (216.0 mg, 0.244 mmol) were added 20 mL each of Et20 and CH2C12 and 1 mL of CH3CN.
The reaction mixture was then stirred for 1.5 h and 10 then. the NaCl was removed via filtration. Removal of the solvent in vacuo yielded a yellow powder, which was washed with 50 mL of hexane. The product (269.6 mg, 83.80 was then dried in vacuo: 1H NMR (CD~C12, 400 MHz) c7 7.73 (s, 8, BAF: Ho) , 7.57 (s, 4, BAF: Hp) , 1~ 7.22-7.~6 (m, 6, Hary1) , 2..23 (s, 6, Ar: Me) , 2.17 (s, 6, Ar~: Me), 2.16, 2.14, and 1.79 (s, 3 each, N=C(Me)-C'(Me)=N, NCMe), 0.38 (s, 3, PdMe); 13C NMR (CD2C12, 100 MHz) d 180.1 and 172.2 (N=C-C'=N), 162.1 (q, JBC =
49.9, BAF: Cipso). 142.9 (Ar, Ar': Co), 135.2 (BAF: Co), 20 129.3 (Ar: Cn,) , 129.2 (q, Jcg = 30.6, BAF: Cn,) , 129.0 (Ar': Cm), 128.4 (Ar: Cp), 128.2 (Ar: Co), 127.7 (Ar':
Cp), 127.4 (Ar': Co), 125.0 (q, JCg = 272.4, BAF: CF3), 121.8 (NCMe), 117.9 (BAF: Cp), 20.2 and 19.2 (N=C(Me)-C'(Me)=N), 18.0 (Ar: Me),17.9 (Ar'~ Me), 5.1 and 2.3 (NCMe, PdMe) . Anal. Calcd for (C55Ha28F24N3Pd) : C, 50.12; H, 3.21; N, 3.19. Found: C, 50.13; H, _.~3, N, 2.99.
Example 16 [ (4-MePh) ~DABMe~] PdMe (MeCN) }BAF
30 Following the procedure of Example 15, a yellow powder was isolated in 85o yield: 1H NMR (CD2C1~, 400 MHz) 8 7.81 (s, 8, BAF: Ho), 7.73 (s, 4, BAF: Hp), 7.30 (d, 4, J - 8.41, Ar, Ar': H~;), 6.89 (d, 2, J = 8.26, Ar: Ho), 6.77 (d, 2, J = 8.19, Ar': Ho), 2.39 (s, 6, 3~ Ar, Ar': Me), 2.24, 2.17 and 1.93 (s, 3 each, N=C(Me)-C' (Me) =N, NCMe) Pd-Me; 13C NMR (CD2C12, 100 MHz) c~ i80. 7 and 171.6 (N=C-C'=N) , 162.1 (q, Jg~ = 49. 8, BAF: Cipso) 143.4 and 142.9 (Ar, Ar': Cipso), 138.6 and 138.5 (Ar, I~1 SUBSTITUTE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96101282 ,-~r': Cp), 135.2 (BAF: Co), 130.6 and 130.4 (Ar, Ar':
Cm) , 129.3 (q, JcF = 31.6, BAF: Cm) , 125.0 (q, J~F =
272.5, BAF: CF3), 122.1 (NCMe), 121.0 and 120.9 (Ar, Ar': Co), 117.9 (BAF: Cp), 21.5 (ArN=C(Me)), 21.1 (Ar, Ar': Me), 19.7 (ArN=C'(Me)), 6.2 and 3.0 (NCMe, PdMe).
Anal. Calcd for (C53H38BFz4N3Pd): C, 49.34; H, 2.97: N, 3.26. Found: C, 49.55; H, 2.93; N, 3.10.
Example 17 [(2,6-MePh)~DABMez]PdMe(EtzO.)BAF
10 A Schlenk flask containing a mixture of [(2,6-i-PrPh)=DABMe2]PdMe2 (501 mg, 0.926 mmol) and H+(OEtz)zBAF- (938 mg, 0.926 mmol) was cooled to -78°C.
Following the addition of 50 mL of EtzO, the solution was allowed to warm and stirred briefly (-15 min) at 1~ room temperature. The soluticn was then filtered and the solvent was removed in vacuo to give a pale orange powder (1.28 g, 94.50), which was stored at -30°C under an inert atmosphere: 1H NMR (CD2Clz, 400 MHz, -60°C) 8 7.71 (s, 8, BAF: Ho), 7.58 (s, 4, BAF: Hp), 7.4 - 7.0 ?0 (m, 6, Haryl) , 3.18 (q, 4, J = 7.10, O(CH2CH3)z) , 2.86 (septet, 2, J = 6.65, CHMez), 2.80 (septet, 2, J =
6.55, C'HMez), 2.18 and 2.15 (N=C(Me)-C'(Me)=N), 1.34, 1.29, 1.14 and 1.13 (d, 6 each, J = 6.4-6.7, CHMeMe', C'HMeMe'), 1.06 (t, J = 6.9, OCCH2CH3)z), 0.33 (s, 3, PdMe); '-3C NMR (CD2Clz, 100 MHz, -60°C) c5 179.0 and 172.1 (N=C-C'=N) , 161.4 (q, Jgc = 49.7, BAF: Cipso) 140.21 and 140.15 (Ar, Ar': Cipso), 137.7 and 137.4 (Ar, Ar': Co), 134.4 (BAF: Cp), 128.3 (q, JcF = 31.3, BAF: Cm), 128.5 and 128.2 (Ar, Ar': Cp), 124.2 (q, JcF
30 - 272.4, BAF: CF3), 117.3 (BAF: Cp), 71.5 (O(CH2CH3)z), 28.7 (CHMez), 28.4 (C'HMez), 23.7, 23.6, 23.1 and 22.6 (CHMeMe', C'HMeMe'), 21.5 and 20.7 (N=C(Me)-C'(Me)=N), 14.2 (O(CHzCH3)z)z, 8.6 (PdMe). Anal. Calcd for (Cs5Hs5BFz4NzOPd): C, 53.35; H, 4.48; N, 1.91. Found:
C, 53.01; H, 4.35; N, 1.68.
1~2 ~1 IRCTITI TTF SNFFT (RULE 261 F,xamnle 18 [ (2, 6-MePh) zDABH~] PdMe (EtZO) BAF
Following the procedure of Example 17, an orange powder was synthesized in 94.3% yield and stored at -30°C: 1H NMR (CD2C12, 400 MHz, -60°C) c~ 8.23 and 8.20 (s, 1 each, N=C(H)-C'(H)=N), 7.72 (s, 8, BAF: Ho), 7.54 (s, 4, BAF: Hp), 7.40 - 7.27 (m, 6, Haryl), 3.32 (q, 4, J = 6.90, O(CH2CH3)2), 3.04 and 3.01 (septets, 2 each, J = 6.9 - 7.1, CHMe2 and C'HMe2), 1.32, 1.318, 1.14 and 1.10 (d, 6 each, J = 6.5 - 6.8, CHMeMe' and C'HMeMe'), 1.21 (t, 6, J = 6.93, O(CH2CH3)2), 0.70 (s, 3, PdMe);
13C NMR (CD2C12, 100 MHz, -60°C) b 166.9 (J~H = 182.6, N=C(H)), 161.5 (Jg~ = 49.7, BAF: Cipso), 161.3 (J~H =
181 . 6 , N=C' (H) ) , 143 . 0 and 141 . 8 (Ar, Ar ' : Cipso) .
138.7 a:~d 137.8 (Ar, Ar': ~o), 134.4 (BAF: Co), 129.1 and 128.8 (Ar, Ar': Cp), 128.3 (J~F = 31.3, BAF: Cm), 124.0 and 123.9 (Ar, Ar': Cm), 117.3 (BAF: Cp), 72.0 (O(CH2CH3)2), 28.5 and 28.4 (CHMe2, C'HMe2), 25.2, 24.1, 21.9 and 21.7 (CHMeMe', C'HMeMe'), 15.2 (O(CHZCH3)2).
~0 11.4 (JcH = 137.8, PdMe) . Anal. Calcd for (Cs3Hs1BF2.~NzOPd): C, 52.72; H, 4.28; N, 1.95. Found:
C, 52.72; H, 4.26; N, 1.86.
Exam,lp a 19 [ (2, 6-MePh) ZDABMe~] NiMe (Et;O) BAF
-'~ Following the procedure of Example 17, a magenta powder was isolated and stored at -30°C: 1H NMR
(CD2C12, 400 MHz, -60°C; A H20 adduct and free Et20 were observed.) c5 7.73 (s, 8, BAF: Ho), 7.55 (s, 4, BAF : Hp ) , 7 . 4 - 7 . 2 ( m , 6 , Haryl ) , 3 . 4 2 ( s , 2 , OH2 ) , 30 3.22 (q, 4, 0(CHzCH3)2), 3.14 and 3.11 (septets, 2 each, J = 7.1, CI~Ie2, C'HMe2) , 1.95 and 1.78 (s, 3 each, N=C(Me)-C'(Me)=N), 1.42, 1.39, 1.18 and 1.11 (d, 6 each, ,,' - 6.6 - 6.9, CHMeMe' and C'HMeMe'), 0.93 (t, J = 7.5, C(CHZCH3)2), -0.26 (s ,3, NiMe); 13C NMR
~ (CD2C12 100 MHz, -58°C) 8 175.2 and 170.7 (N=C-C'=N), 161 .6 (q, JB~ = 49.7, BAF: Cipso) . 141.2 (Ar: Cipso) .
139.16 and 138.68 (Ar, Ar': Co), 136.8 (Ar': Cipso).
134.5 (BAF: Co), 129.1 and 128.4 (Ar, Ar': Cp), 128.5 SUBSTITUTE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 PCTIUS96/01282 (q, Jc~ = 32.4, BAF: Cm), 125.0 and 124.2 (Ar, Ar':
Cm), 124.3 (q, Jig = 272.5, BAF: CF3), 117.4 (BAF: Cp), 66.0 (O(CHzCH3)2), 29.1 (CHMeZ), 28.9 (C'HMe~i, 23.51, 23.45, 23.03, and 22.95 (CHMeMe', C'HMeMe'), 21.0 and 19.2 (N=C (Me) -C' (Me) =N) , 14 .2 (OCHZCH3) ~) , -0 . 86 (JcH =
131.8, NiMe) . Anal. Calcd for (Cs5Hs5BF24N2Ni0) : C, 55.15; H, 4.63; N, 1.98. Found: C, 54.74; H, 4.53; N, 2.05.
Example 20 10 [-(2, 6-MePh) 2DABH~] NiMe (Et~O) BAF
Following the procedure of Example 17, a purple powder was obtained and stored at -30°C: 1H NMR
(CD2C12, 400 MHz, -80°C; H20 and Et20 adducts were observed in an 80:20 ratio, respectively.) 8 8.31 and 8.13 (s, 0.8 each, N=C(H) -.C' (H) =N; H20 Adduce) , 8.18 and 8.00 (s, 0.2 each, N=C(H)-C'(H)=N; Et20 Adduct), 7.71 (s, 8 BAF: Co), 7.53 (s, 4, BAF: Cp), 7.5 - 7.0 (m, 6, Haryl) , 4.21 (s, 1.6, OH2) , 3.5 - 3.1 (m, 8, O ( CH2CH3 ) 2 , CHMe2 , C' f~le2 ) , 1 . 3 8 , 1 . 3 7 , 1 . 16 and 1 . 0 8 20 (d, 4.8 each, CHMeMe', C'HMeMe'; H20 Adduct; These peaks overlap with and obscure the CHMe2 doublets of the Et20 adduct.), 0.27 (s, 2.4, PdMe; H20 Adduct), 0.12 (s, 0.6, PdMe: Et20 Adduct).
Examples 21-23 The rate of exchange of free and bound ethylene was determined by 1H NMR line broadening experiments at -85°C for complex (XI), see the Table below. The NMR
instrument was a 400 MHz Varian0 NMR spectrometer.
Samples were prepared according to the following 30 procedure: The palladium ether adducts {[(2,6-i-PrPh)ZDABMe2)PdMe(OEt2)}BAF, {[(2,6-i-PrPh) 2An) PdMe (OEt2~) )BAF, and { [ (2, 6-i-PrPh)2DABH2)PdMe(OEt2)}BAF were used as precursors to (XI), and were weighed (-15 mg) in a tared 5 mm dia.
NMR tube in a nitrogen-filled drybox. The tube was then capped with a septum and Parafilm~ and cooled to -80°C. Dry, degassed CDZC12 (700 ~L) was then added to the palladium complex via gastight syringe, and the 1 ~-l CI11~CTITI1TF RNFFT lRlILE 26) _ube was shaken and warmed briefly to guV~'~a homogeneous solution. After acquiring a -85°C NMR
spectrum, ethylene was added to the solution via gastight syringe and a second NMR spectrum was acquired at -85°C. The molarity of the BAF counterion was calculated according to the moles of the ether adduct placed in the NMR tube. The molarity of (XI) and free ethylene were calculated using the BAF peaks as an internal standard. Line-widths (w) were measured at 10 half-height in units of Hz for the complexes ethylene signal (usually at 5 to 4 ppm) and were corrected for line widths (Wo) in the absence of exchange.
For (XI) the exchange rate was determined from the standard equation for the slow exchana_e l~ approximation:
k = (W - Wo) n/ (_) , where [_] is the molar concentration of ethylene.
These experiments were repeated twice and an average value is reported below.
Rate Constants for Ethylene Exchangea k Ex. (XI) (L_M-ls-1o 21 {[(2.6-i-PrPh)2DABMe2]PdMe(=)}BAF45 22 {[(2,6-i-PrPh)2An)PdMe(=)}BAF 5~0 {[(2,6-i-PrPh)2DABH2)PdMe(=))BAF 8100 aThe T1 of free ethylene is 15 sec. A pulse delay of 60 sec and a 30° pulse width were used.
Example 24 Anhydrous FeCl2 (228 mg, 1.8 mmol) and (2,6-i-PrPh)2DABAn (1.0 g, 2.0 mmol) were combined as solids and dissolved in 40 ml of CH2Clz. The mixture was stirred at 25°C for 4 hr. The resulting green scl;:tion 30 was removed from the unreacted FeClz via filter cannula. The solvent was removed under reduced l~~
SI IR~TIT11TF RHFFT (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 pressure resulting in a green solid (0.95 g, 840 yield) .
A portion of the green solid (40 mg) was immediately transferred to another Schlenk flask and dissolved in 50 ml of toluene under 1 atm of ethylene.
The solution was cooled to 0°C, and 6 ml of a 10% MAO
solution in toluene was added. The resulting purple solution was warmed to 25°C and stirred for 11 hr. The polymerization. was quenched and the polymer 10 precipitated by acetone. The resulting polymer was washed with 6M HCl, water and acetone. Subseauent drying of the polymer resulted in 60 mg of white polyethylene. 'H NMR (CDC13, 200 MHz) 81.25 (CHz, CH) cS
0 . 85 (m, CH~ ) .
Fxamnie 25 (2-t-BuPh)2DABMe~
A Schlenk tube was charged with 2-t-butylaniline (5.00 mL, 32.1 mmol) and 2,3-butanedione (1.35 mL, 15.4 mmol). Methanol (10 mL) and formic acid (1 mL) were ?0 added and a yellow precipitate began to form almost immediately upon stirring. The reaction mixture was allowed to stir overnight. 'The resulting yellow solid was collected via filtration and dried under vacuum.
The solid was dissolved in ether and dried over Na2S04 for 2-3 h. The ether solution was filtered, condensed and placed into the freezer (-30°C). Yellow crystals were isolated via filtration and dried under vacuum overnight (4.60 g, 85.7°s): 1H NMR (CDC13, 250 MHz) cS
7.41(dd, 2H, J = 7.7, 1.5 Hz, Hm), 7.19 (td, 2H, J= 7.5, 30 1.5 Hz, Hm or Hp), .7.07 (td, 2H, J = 7.6, 1.6 Hz, Hm or-Hp), 6.50 (dd, 2H, J = 7.7, 1.8 Hz, Ho), 2.19 (s, 6H, N=C(Me)-C(Me)=N), 1.34 (s, 18H, C(CH3)3).
Rxamnl_es 26 and 27 General Polymerization Procedure for Examples 26 3~ and 27: In the drybox, a glass insert was loaded with [(t~3-C3H5)Pd(~-C1))2 (11 mg, 0.03 mmol), NaBAF (53 mg, 0.06 mmol), and an a-diimine ligand (0.05 mmol). The insert was cooled to -35°C in the drybox freezer, 5 mL
1~6 c~ ~acTtTi t~ ~NFFT fRl i1 F 261 ~f C5D6 was added to the ccid insert, and the insert was then capped and sealed. Outside of the drybox, the cold tube was placed under 6.9 MPa of ethylene and allowed to warm to RT as it was shaken mechanically for 18 h. An aliquot of the solution was used to acquire a 1H NMR spectrum. The remaining portion was added to --20 mL of MeOH in order to precipitate the polymer.
The polyethylene was isolated and dried under vacuum Exam, 1 a-Diimine was (2,6-i-PrPh)2DABMe~. Polyethylene (50 mg) was isolated as a solid. 1H NMR spectrum 1C6D6) is consistent with the production of 1- and 2-butenes and branched polyethylene.
Rxamnle 2727 a-Diimine was (2,6-i-PrPh)2DABAn. Polyethylene (17 ma) was isolated as a solid. 1H NMR spectrum (C6D6) is consistent with the production of branched polyethylene.
Example 28 [ (2, 6-i-PrPh) zDABH~] NiBrz The corresponding diimine (980 mg, 2.61 mmol) was dissolved in 10 mL of CH2C12 in a Schlenk tube under a N~ atmosphere. This solution was added via cannula to a suspension of (DME)NiBr2 (DME = 1,2-dimethoxyethane) (787 mg, 2.55 mmol) in CH2C12 (20 mL). The resulting red/brown mixture was stirred for 20 hours. The solvent was evaporated under reduced pressure resulting in a red/brown solid. The product was washed with 3 x 10 mL of hexane and dried in vacuo. The product was 30 isolated as a red/brown powder (1.25 g, 82% yield).
Example 29 [ (2, 6-i-PrPh) ZDABMe2] NiBr2 Using a procedure similar to that of Example 28, 500 ma (1.62 mmol) (DME)NiBr2 and 687 mg (1.70 mmol) of 3~ the corresponding diimine were combined. The product was isolated as an orange/brown powder (670 mg, 67%
yield) .

CI IR~TfTI ITF ~HFFT !RI 1l F ~R1 WO 96123010 ~ 02338526 2001-03-O1 , Example 30 [ (2 , 6-MePh) zDABH2] NiBr=
Using a procedure similar to that of Example 28, 500 mg (1.62 mmol) (DME)NiBrz and 448 mg (1.70 mmol) of the corresponding diimine were combined. The product was isolated as a brown powder (622 mg, 80o yield).
Exansnle 31 [(2,6-i-PrPh)ZDABAn]NiBr~
Using a procedure similar to that cf Example 28, 10 500 mg (1.62 mmol) (DME)NiBrz and 850 mg (1.70 mmol) of the corresponding diimine were combined. The product was isolated as a red powder (998 mg, 86% yield).
Anal. Calcd. for C36H4oN2Br2Ni: C, 60.12; H, 5.61; N, 3.89. Found C, 59.88; H, 5.20; N, 3.52.
1~ Example 32 [(2,6-MePh)2DABAn]NiBr~
The corresponding diimine (1.92 g, 4.95 mmol) and (DME)NiBr2 (1.5 g, 4.86 mmol) were combined as solids in a flame dried Schlenk under an argon atmosphere. To 217 this mixture 30 mL of CH2C1~ was added giving an orange solution. The mixture was stirred for 18 hours resulting in a red/brown suspension. The CH2C12 was removed via filter cannula leaving a red/brown solid.
The product was washed with 2 x 10 mL of CHZC12 and dried under vacuum. The product was obtained as a red/brown powder (2.5 g, 83o yield).
Example 33 [(2,6-MePh)ZDABMez]NiBr2 Using a procedure similar to that of Example 32, 30 the title compound was made from 1.5 g (4.86 mmol) (DME)NiBr2 and 1.45 g (4.95 mmol) of the corresponding diimine. The product was obtained as a brown powder ;2.05 a, 81o yield).
Example 34 3~ [(2,6-i-PrPh)2DABMe~]PdMeCl (COD)PdMeCl (9.04 g, 34.1 mmol) was dissolved in 200 ml of methylene chloride. To this solution was added the corresponding diimine (13.79 g, 34.1 mmol).
1~8 m tac~n~ tTC SNFFT !RI II F 26) VVO 96/2.3010 PC?/I~S96/01282 .. h--_ .=s~u_''_rg sclut:cn rap'd_y c~.a.~.a~c co_c_ ___...
Ve_!Ok' t0 OrariCe_r°_.~,~.. ezfter St2rr_:1C aZ rOCm te;tperazure icr several hours it was conce :trite.. to for; a saturated sclution or the desire;: procuc', and W .a~_e.r u.v . v'~l_ Cw e_~ ..... a~'L-i C!_.:. ~ W.~~u crys~ai?ize~ from the SClutiOn, and was isolated by _____~__.,_ , was'.~.=c w_=.. petroleu;~ e=~e~, a::c dr_e a=~~r: 12 . ~G g Ci t~°_ tltl °_ COiTlDOI::.Q aS au Orangc DOWder . S°_COrI'.~' a..~.d third Cr0'-'JS O. Crystals O~"JZa_.~.°_~
fog;,~ the mother licuor a'forded a_~. additional 3.a2 c c_ oc~~c _ . :'oral V_el c = 67 0 .
_ ~-,i ec i~_7c o., _ the "._lowinc co:~,,pounds were made by a meth's sir.:____ .._ t:.at used _.. Exar.:pi a 3~ .
l~
Lxac;.pla Compound 3~ [ (2, 5-i -PrPh) zD.~H:] PdMe 35 [ (2, 6-i-Pr?h) ZDn.EAnj PdMeCI
3 7 [ ( Ph ) ZDABM°; ] PdfIIe C l ?0 38 [(2,6-EtPhI~DABMe:]PdMeC'_ 39 [ (2,4, 6-MePh)~D.~l3Me_~?dMeCl r.'ot?: '.'h= diethyl ether comp_exes descr ibe ..~.
Exi.-"ples ~i-4o are unstable in~ no:~-coordinating S :W'e.~._S Sa:..~_.. as met::Vl~.'n~.' C::lOrlCe a: ..~. C~IOrO~C:.'...
'~2raCter_ZeC bV j.: NMR S.~.eC~=a reCOrae: _:.
CDZCr:; under these conditio~s the aceto::itrile adduct c. t~e Pd methyl cation is formed. Ty~icaily, less than a whole eauivalent of free diethvlether is J0 .._,Se. :~=_o ~:' ~.. NMR whe:: [ (R) 2DP5 (R' I 2] PdMe (vr.'..~ ) i. ;s dissolved in. CD3CN. Therefore, it is believed the co.;,Plexes designated as " ( [ (R) 2DA3 (R' ) 2] PdMe (OEt~ ) ~X"
ce_o~~ a=~ 1 i:celv mixtures o.
lf(EI~E:ia(~')'JP'3lvj°-('JEtt)1X aT_:~C [(=)~D=?!~r'~'~.iM.y' ~-.
_.. _~°_ ~ otter COLTl-.~..~ ex°S t~:e X llga:~.'= IC~:c C~y r,-P: ~ I -S weakly COOrC=riateQ t0 pallaClL:~;.. n iOrm;::a Oi ti:e tyke " ( [ (R) 2DAB (R' ) ZJ PdMe (OEt2) }X" is a "for;:~al"
way c. co: ve,; ing th°_ aPprox_i;,iate ever all composition of I~9 SUBSTITUTE SHEET (RULE 26) . . . , _ , .. ,.
this compound, but may not accurately depict the e~ 't coordination to the metal atom.
Listed below are the 13C NMR data for Example 36.
13C NMR data TCB, 120C, O.OSM Crrlcac freQ o~m intensstv 46.5568 24.6005 1 cmp and/or 1,3 ccmcc 44.9321 3.42517 1,3 cmc 40.8118 55.4341 2 pmp 40.3658 145.916 1,3 pmp 39.5693 18.458 methylenes from 2 cmp and/or 2 cmc 38.7782 4.16118 38.6295 5.84037 38.2844 8.43098 38.1198 8.29802 37.8384 3.83966 37.5198 13.4977 37.2384 23.4819 'i 37.1163 16.8339 36.7446 114.983 36.0012 6.19217 35.7198 5.17495 34.2278 4.83958 32.9216 20.2781 386+, 3EOC
, 32.619 3.6086 32.4172 2.98497 32.1995 10.637 31.9765 42.2547 31.8809 143.871 30.4686 27.9974 30.3199 47.1951 30.022 36.1409 29.7411 102.51 -29.31i 4.83244 28.7111 117.354 28.2597 9.05515 27.1659 22.5725 27.0067 5.81855 26.1146 13.5772 24.5642 2.59695 p~3B

22.6368 12.726 285+, 2EOC

20.1413 3.7815 2B3 19.7271 20.0959 181 17.5236 7.01554 end group 14.2528 3.03535 1B3 13.8812 12.3535 1B4+, lEOC

Exama2,LP 4 0 ( [ (4-Me2NPh) 2DABMe2] PdMe (MeCN) }SbF6~MeCN

AMENDED SHEET

A procedure analogous to that used in Example 54, using (4-Me2NPh)2DABMe2 in place of (2-C6H4-tBu)2DABMe2, afforded {[(4-NMezPh)2DABMe2]PdMe(MeCN)~SbF6~MeCN as a purple solid (product was not recrystallized in this instance). 1H NMR (CD2C12) 8 6.96 (d, 2H, Hary1)~ 6.75 (mutt, Sri, Haryl), 3.01 (s, 6H, NMe2), 2.98 (s, 6H, NMe'2), 2.30, 2.18, 2.03, 1.96 (s's, 3H each, N=CMe, N=CMe', and free and coordinated N=CMe), 0.49 (s, 3H, Pd-Me).
' Example 41 { [ (2, 6-i-PrPh) ZDABMe2) PdMe (Et20)n}SbFS
[(2,6-i-PrPh)~DABMe2]PdMeCl (0.84 g, 1.49 mmol) was suspended in 50 mL of diethylether and the mixture cooled to -40'C. To this was added AgSbF6 (0.52 g, 1~ 1.5u mrno~~.~:. The reaction mixture was allowed to warm to room temperature, and stirred at room temperature for 90 min. The reaction mixture was then filtered, giving a pale yellow filtrate and a bright yellow precipitate. The yellow precipitate was extracted with ?0 4 x 20 mL 50/50 methylene chloride/diethyl ether. The filtrate and extracts were then combined with an additional 30 mL diethyl ether. The resulting solution was they. concentrated to half its original volume and l00 mL cf petroleum ether added. The resulting precipitate was filtered off and dried, affording 1.04 a of the title compound as a yellow-orange powder (83%
yield). =H NMR (CD3CN) 8 7.30 (rnult, 6H, Haryl), 3.37 [q, free O(CH~CH3)2], 3.05-2.90 (overlapping sept's, 4H, CHMe~), 2.20 (s, 3H, N=CMe), 2.19 (s, 3H, N=CMe'), 30 1.35-1.14 (overlapping d's, 24H, CHMe2), 1.08 (t, free O(CH2CH;)~], 0.28 (s, 3H, Pd-Me). This material contained 0.4 equiv of Et20 per Pd, as determined by 1H
NMR integration.
Example 42 3~ { [ (2, 6-i-PrPh)2DABMe2] PdMe (Et20)n}BFQ
A procedure analogous to that used in Example 41, using AaBF~ in place of AgSbF6, afforded the title compound as a mustard yellow powder in 61o yield. This CI II~cTITI IT>= ~HFFT (RULE 267 WO 96/23010 ~ 02338526 2001-03-O1 p~/ug96101282 material contained 0.3 equiv of Et20 per Pd, as determined by 1H NMR integration. 1H NMR in CD3CN was otherwise identical to that of the compound made in Example 41.

Exam 43 [ (2 , 6-i-PrPh) zDABMe2] PdMe (Et~O) n}PF6 A procedure analogous to that used in Example 41, using AgPF6 in place of AgSbF6, afforded the title 10 compound as a yellow-orange powder in 72% yield. This material contained 0.4 equiv of Et20 per Pd, as determined by 1H NMR integration. 1H NMR in CD3CN was identical to that of the compound of Example 41.
Example 4a I~ { [ (2, 6-i-PrPh) ~DABH~] PdMe (EtzO) n}SbF6 A procedure analogous to that used in Example 41, using [(2,6-i-PrPh)2DABH2]PdMeCl in place of [(2,6-i-PrPh)2DABMe2]PdMeCl, afforded the title compound in 710 yield. 1H NMR (CD3CN) b 8.30 (s, 2H, N=CH and N=CH'), 20 7.30 (s, 6H, Haryi) , 3.37 [q, free O(CH2CH3) 2) , 3.15 (br, 4H, CF~Ie2) , 1.40-1.10 (br, 24H, CHMe2) , 1.08 (t, free O(CH2CH3)2], 0.55 (s, 3H, Pd-Me). This material contained 0.5 equiv of Et20 per Pd, as determined by 1H
NMR integration.
Examral a 45 [(2,4,6-MePh)2DABMe2)PdMe(EtzO)rjSbF6 /(2,4,6-MePh)ZDABMe2]PdMeCl (0.50 g, 1.05 mmol) was partially dissolved in 40 mL 50/50 methylene chloride/diethylether. To this mixture at room 30 temperature was added AgSbF6 (0.36 g, 1.05 mmol). The resulting reaction mixture was stirred at room temperature for 45 min. It was then filtered, and the filtrate concentrated in vacuo to afford an oily solid.
The latter was washed with diethyl ether and dried to 3~ afford the title compound as a beige powder. 1H NMR
(CD3CN) 8 6.99 (s, 4H, Haryl) , 3.38 [q, free O(CH2CH3)2], 2.30-2.00 (overlapping s's, 24H, N=CMe, N=CMe' and aryl Me's), 1.08 (t, free O(CH2CH3)2), 0.15 ei mc~Tn~ cuG~T tRl 11 F 9R1 .s, 3H, Pd-Me). This material containedW :7 equiv of Et20 per Pd, as determined by 1H MR integration.
Example 46 ( [ (2, 6-i-PrPh) zDABAn] PdMe (EtzO)"~SbF6 A procedure analogous to that used in Example 41, using ((2,6-i-PrPh)2DABAn]PdMeCl in place of [(2,6-i-PrPh)ZDABMe~]PdMeCl, afforded the title compound in 920 yield. 1H NMR (CD3CN) 8 8.22 (br t, 2H, Haryl), 7.60-7.42 (br mult, 8H, Haryl) , 6.93 (br d, 1H, Haryl) , 6.53 10 (br d, 1H, Haryl) , 3.38 [q, free 0(CH2CH3)2] , 3.30 (br mult, 4H, CHMe2), 1.36 (br d, 6H, CHMe2), 1.32 (br d, 6H, CHMe2) , 1. OS (t, free O (CHZCH3) 2] , 1.02 (br d, 6H, CHMe2), 0.92 (br d, 6H, CHMe2), 0.68 (s, 3H, Pd-Me).
The amount of ether contained in the product could not l~ be determined precisely by iH NMR integration, due to overlapping resonances.
Example 47 [ (2, 6-i-PrPh) 2DABMez] PdMe (OS02CF3) A procedure analogous to that used in Example 41, ?0 using AgOS02CF3 in place of AgSbF6, afforded the title compound as a yellow-orange powder. 1H NMR in CD3CN
was identical to that of the title compound of Example 41, but without free ether resonances.
Example 48 1'~ ( [ (2, 6-i-PrPh) ~DABMe2) PdMe (MeCN) )SbF6 [(2,6-i-PrPh)ZDABMe2]PdMeCl (0.40 g, 0.71 mmoi) was dissolved in 15 mL acetonitrile to give an orange solution. To this was added AgSbF6 (0.25 g, 0.71 mmol) at room temperature. AgCl immediately precipitated 30 from the resulting bright yellow reaction mixture. The mixture was stirred at room temperature for 3 h. It was then filtered and the AgCl precipitate extracted with 5 mL of acetonitrile. The combined filtrate and extract were concentrated to dryness affording a yellow solid. This was recrystallized from methylene chloride/petroleum ether affording 0.43 g of the title compound as a bright yellow powder (Yield = 75%). 1H
NMR (CDC13) S 7.35-7.24 (mult, 6H, Haryl), 2.91 (mult, ci iacTm tTF SHFFT (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96/01282 . 4H, CHMe2) , 2.29 (s, 3H, N=CMe) , 2.28 (s, 3H,-2~'=CM~."~> , _ _ _ 1.81 (s, 3H, N=CMe), 1.37-1.19 (overlapping d's, 24H, CHMe's), 0.40 (s, 3H, Pd-Me). This compound can also be prepared by addition of acetonitrile to ([(2,6-i-PrPh) 2DABMe2] PdMe (Et20) }SbF6 .
Example 49 { [ (Ph) 2DABMe2] PdMe (MeCN) ~SbF6 A procedure analogous to that used in Example 48, using [(Ph)2DABMe2)PdMeCl in place of [(2,6-1-10 PrPh)ZDABMe2]PdMeCl, afforded the title compound as a yellow microcrystalline solid upon recrystallization from methylene chloride / petroleum ether. This complex crystallizes as the acetonitrile solvate from acetoritrile solution at -40°C. 1H NMR of material l~ recrystallize~ from methylene chloride/petroleum ether:
(CDC13) cS 7.46 (molt, 4H, Haryl). 7.30 (t, 2H, Haryl) .
7.12 (d, 2H, Haryl) , 7.00 (d, 2H, Haryl) . 2.31 (s, 3H, N=CMe), 2.25 (s, 3H, N=CMe'), 1.93 (s, 3H, N=CMe), 0.43 (s, 3H, Pd-Me) .
20 Example 50 { [ (2, 6-EtPh) ~DABMe~] PdMe (MeCN) }BAF
[(2,6-EtPh)2DABMe2]PdMeCl (0.200 g, 0.396 mmol) was dissolved in 10 mL of acetonitrile to give an orange solution. To this was added NaBAF (0.350 g, 0.396 mmol). The reaction mixture turned bright yellow and NaCl precipitated. The reaction mixture was stirred at room temperature for 30 min and then filtered through a Celite~ pad. The Celite~ pad was extracted with 5 mL of acetonitrile. The combined 30 filtrate and extract was concent-~ated in vacuo to afford an orange solid, recrystallization of which from methylene chloride / petroleum ether at -40°C afforded 0.403 g of the title compound as orange crystals (Yield - 74%) . 1H NMR (CDC13) 8 7.68 (s, 8H, Hortho of anion) , 35 7.51 (s, 4H, Hpara of anion), 7.33-7.19 (mult, 6H, Haryl of cation), 2.56-2.33 (mult, 8H, CH2CH3), 2.11 (s, 3H, .
N=CMe), 2.09 (s, 3H, N=CMe'), 1.71 (s, 3H, N=CMe), 1.27-1.22 (mutt, 12H, CH2CH3), 0.41 (s, 3H, Pd-Me).

~~ n~~n~ sHFSr rRmE 2s~

Example 5~
[ (2, 6-EtPh) zDABMe~] PdMe (MeCN) }SbFE
A procedure analogous to that used in Example 50, using AgSbF6 in place of NaBAF, afforded the title compound as yellow crystals in 99o yield after recrystailization from methylene chloride/petroleum ether at -40°C.
Examnla 52 [ ( COD ) PdMe (NCMe ) ] SbF6 10 To (COD)PdMeCl (1.25 g, 4.70 mmol) was added a solution of acetonitrile (1.93 g, 47.0 mmol) in 20 mL
methylene chloride. To this clear solution was added AgSbF6 (1.62 g, 4.70 mmol). A white solid immediately precipitated. The reaction mixture was stirred at room 1~ temperature for 45 min, and then filtered. The yellow filtrate was concentrated to dryness, affording a yellow solid. This was washed with ether and dried, affording 2.27 g of [(COD)PdMe(NCMe)]SbFs as a light yellow powder (yield = 95%). iH NMR (CD2C12) cS 5.84 20 (mutt, 2H, CH=CH), 5.42 (mult, 2H, CH'=CH'), 2.65 (mult, 4H, CHH'), 2.51 (mult, 4H, CHH'), 2.37 (s, 3H, NCMe), 1.18 (s, 3H, Pd-Me).
$xamnle 53 [(COD)PdMe(NCMe)]BAF
?s A procedure analogous to that used in Example 52, using NaBAF in place of AgSbF6, afforded the title compound as a light beige powder in 96o yield.
16~
e. iacTiTi rr~ ~NFFT rRULE 2s1 WO 96123010 ~ 02338526 2001-03-O1 PC'TIUS96101282 Example 5a { [ (2-t-BuPh) ZDABMe2) PdMe (MeCN) ]SbFs To a suspension of (2-t-BuPh)2DABMe2 (0.138 g, 0.395 mmol) in 10 mL of acetonitrile was added [(COD)PdMe(NCMe)]SbFs (0.200 g, 0.395 mmoi). The resulting yellow solution was stirred at room temperature for 5 min. It was then extracted with 3 x 10 mL of petroleum ether. The yellow acetonitrile phase was concentrated to dryness, a~fordng a bright 10 yellow powder. Recrystallization from methylene chloride/petroleum ether at -40 °C afforded 180 mg of the title product as a bright yellow powder (yield =
61%). 1H NMR (CD2C12) 8 7.57 (dd, 2H, Haryl), 7.32 (mult, 4H, Haryl) , 6.88 (dd, 2H, Haryl) , 6.78 (dd, 2H, Harvl)~ 2.28 (s, 3H, N=CMe), 2.22 (s, 3H, N=CMe'), 1.78 (s, 3H, N=CMe), 1.48 (s, 18H, tBu), 0.52 (s, 3H, Pd-Me ) .
Example 55 { [ (Np) 2DABMe~] PdMe (MeCN) }SbF6 20 A procedure analogous to that used in Example 54, using (Np)~DABMe2 in place of (2-t-BuPh)?DABMe2, afforded the title compound as an orange powder 520 in yield after two recrystallizations from methylene chlcride/petroleum ether. 1H NMR (CDZC12) c7 8.20-7.19 (molt, 14 H, Haromatic) . 2.36 (d, J = 4.3 Hz, 3H, N=CMe), 2.22 (d, J = 1.4 Hz, 3H, N=CMe'), i.32 3H, (s, NCMe), 0.22 (s, 3H, Pd-Me).

Example 56 { [ (Ph2CH) 2DABH~] PdMe (MeCN) }SbF6 30 A procedure analogous to that used in Example 54, using (Ph~CH)2DABH2 in place of (2-t-BuPh)2DABMe2, afforded the title compound as a yellow r"icrccrystalline solid. 1H NMR (CDC13) 8 7.69 1H, (s, N=Cii), 7.65 (s, 1H, N=CH'), 7.44-7.08 (muit, 20H, Haryl). 6.35 (2, 2H, CHPh2), 1.89 (s, 3H, NCMe), 78 0.

(s, 3H, Pd-Me). , c~ mc~rrTi tTC cNFFT IR! 11 F ~Rl Example 57 ( [ (2-PhPh) zDABMez] PdMe (MeCN) ~SbF6 A procedure analogous to that used in Example 54, using (2-PhPh)2DABMe2 in place of (2-t-BuPh)2DABMe2, afforded the title compound as a yellow-orange powder~
in 90o yield. Two isomers, due to cis or traps orientations of the two ortho phenyl groups on either side of the square plane, were observed by 1H NMR. 1H
NMR (CD2C12) cS 7.80-5.82 (mult, 18H, Haryl). 1.98, 1.96, 10 1.90, 1.83, 1.77, 1.73 (singlets, 9H, N=CMe, N=CMe', NCMe for cis and traps isomers), 0.63, 0.61 (singlets, 3H, Pd-Me for cis and traps isomers).
Example 58 ([(Ph)DAB(cycio-CMe~CH2CMez-)]PdMe(MeCN)}BAF
I~ To a solution o= [(COD)PdMe(NCMe)]BAF (0.305 g, 0.269 mmol) dissolved in 15 mL of acetonitrile was added N,N'-diphenyl-2,2',4,4'-tetramethyl-cyclopentyldiazine (0.082 g, 0.269 mmol). A gold colored solution formed rapidly and was stirred at room 20 temperature for 20 min. The solution was then extracted with 4 x 5 mL petroleum ether, and the acetonitrile phase concentrated to dryness to afford a yellow powder. This was recrystallized from methylene chloride/petroleum ether at -40°C to afford 0.323 g 2~ (900) of the title compound as a yellow-orange, crystalline solid. 1H NMR (CDC13) 8 7.71 (s, 8H, Hortno of anion), 7.54 (s, 4H, Hpara of anion), 7.45-6.95 (mult, 10H, Haryl of cation), 1.99 (s, 2H, CH2), 1.73 (s, 3H, NCMe), 1.15 (s, 6H, Me2), 1.09 (s, 6H, Me'2), 30 0.48 (s, 3H, Pd-Me).
$,xam~ a 5 9 ([(2,6-i-PrPh)2DABMe2JPd(CH2CH2CHzC02Me)}SbF6 Under a nitrogen atmosphere {[(2,6-i-PrPh) ~DABMe,] PdMe (Et,O) }SbF6 (3.60 g, 4 .30 mmol) was 3~ weighed into a round bottom flask containing a magnetic stirbar. To this was added a -40°C solution of methyl acrylate (1.85 g, 21.5 mmol) dissolved in 100 ml of methylene chloride. The resulting orange solution was c~ iacTm rrF ~HFET (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 PCTILTS96/01282 stirred for 10 min, while being allowed to warm to room temperature. The reaction mixture was then concentrated to dryness, affording a yellow-brown .
solid. The crude product was extracted with methylene chloride, and the orange-red extract concentrated, layered with an equal volume of petroleum ether, and cooled to -40°C. This afforded 1.92 g of the title compound as yellow-orange crystals. An additional 1.39 g was obtained as a second crop from the mother liquor;
10 total yield = 910. 1H NMR (CD2C12) b 7.39-7.27 (mult, 6H, Hary1). 3.02 (s, 3H, OMe), 2.97 (sept, 4H, CHMe2), 2.40 (mule, 2H, CHz), 2.24 (s, 3H, N=CMe), 2.22 (s, 3H, N=CMe'), 1.40-1.20 (mult, 26H, CHMe2 and CHZ'), 0.64 (mutt, 2H, CH2" ) .
Example 60 {[(2,6-i-PrPh)ZDABH2]Pd(CH2CH2CH2C02Me))SbF6 AgSbF6 (0.168 g, 0.489 mmol) was added to a -40°C
solution of ([(2,6-i-PrPh)2DABH2]PdMeCl (0.260 g, 0.487 mmol) and methyl acrylate (0.210 g, 2.44 mmol) in 10 mL
_'0 methylene chloride. The reaction mixture was stirred for 1 h while warming to room temperature, and then filtered. The filtrate was concentrated in vacuo to give a saturated solution of the title compound, which was then layered with an equal volume of petroleum ether and cooled to -40°C. Red-orange crystals precipitated from the solution. These were separated by filtration and dried, affording 0.271 g of the title compound (68°s yield). 1H NMR (CD2Clz) 8 8.38 (s, 1H, N=CH), 8.31 (s, 1H, N=CH'), 7.41-7.24 (mult, 6H, 30 Hary1), 3.16 (mult, 7H, OMe and CHMe2), 2.48 (mult, 2H, CH2), 1.65 (t, 2H, CH2'), 1.40-1.20 (mutt, 24H, CHMe2), 0 . 72 (mult , 2H, CH2 " ) .
Examt~le 61 {[(2,6-i 3~ PrPh) 2DABMe2) Pd (CH2CH2CH2C02Me) } [B (C6F5) 3C1]
[(2,6-i-PrPh)ZDABMe2]PdMeCl (0.038 g, 0.067 mmol) and methyl acrylate (0.028 g, 0.33 mmol) were dissolved in CD2C12. To this solution was added B(C6F5)3 (0.036 SUBSTITInE SHEET (RULE 26) _g, 0.070 mmol). 1H NMR cf the resulting reac:.ion mixture showed formation of the title compound.
Example 62 A 100 mL autoclave was charged with chloroform (50 ~ mL), {[(2-t-BuPh)2DABMe2]PdMe(NCMe))SbF6- (0.090 g, 0.12 mmol), and ethylene (2.1 MPa). The reaction mixture was stirred at 25°C and 2.1 MPa ethylene for 3 h. The ethylene pressure was then vented and volatiles removed from the reaction mixture in vacuo to afford 2.695 g of 10 branched polyethylene. The number average molecular weight (Mn), calculated by 1H NMR integration of aliphatic vs. olefinic resonances, was 1600. The degree of polymerization, DP, was calculated on the basis of the 1H NMR spectrum to be 59; for a linear l~ polymer tis would result .in 18 methyl-ended branches per 1000 methylenes. However, based on the iii NMR
spectrum the number of methyl-ended branches per lOGO
methylenes was calculated to be 154. Therefore, it may be concluded that this material was branched ?0 polyethylene. 1H NMR (CDC13) 8 5.38 (mult, vinyl H's), 1.95 (mutt, allylic methylenes), 1.62 (mult, allylic methyls), 1.24 (mult, non-allylic methylenes and methines), 0.85 (mult, non-allylic methyls).
Example 63 A suspension of ([(2-t-BuPh)2DABMe2]PdMe(NCMe))SbF6 (0.015 g, 0.02 mmol) in 5 mL FC-75 was agitated under 2.8 MPa of ethylene for 30 min. The pressure was then increased to 4.1 MPa and maintained at this pressure for 3 h. During this time 30 the reaction temperature varied between 25 and 40°C. A
viscous oil was isolated from the reaction mixture by decanting off the FC-75 and dried in vacuo. The number average molecular weight (Mn), calculated by 1H
NMR integration of aliphatic vs. olefinic resonances, 3~ was 2600. DP for this material was calculated on the basis of the 1H NMR spectrum to be 95; for a linear polymer this would result in 11 methyl-ended branches per 1000 methylenes. However, based on the 1H NMR

SI 1R~'tTt n'F ~HFFT (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 p~'/US96/01282 ,spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 177.
Example 64 A 100 mL autoclave was charged with chloroform (55 mL), {[(2-PhPh)2DABMe2]PdMe(NCMe)}SbF6 (0.094 g, 0.12 mmol), and ethylene (2.1 MPa). The reaction mixture was stirred at 25°C and 2.1 MPa ethylene for 3 h. The ethylene pressure was then vented and volatiles removed from the reaction mixture ir. vacuo to afford 2.27 g of 10 a pale yellow oil. Mn was calculated on the basis of '-H NMR integration of aliphatic vs. olefinic resonances to be 200. The degree of polymerization, DP, was calculated on the basis of the 1H NMR spectrum to be 7.2; for a linear polymer this would result in 200 1~ methyl-enaed branches per .1000 methylenes. However, based on the 1H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 283.
Example 65 A suspension of ((2-PhPh)2DABMe2JPdMe(NCMe)~SbF6 20 (0.016 g, 0.02 mmol) in S mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40 min. During this time the reaction temperature varied between 23 and 41°C. A
viscous oil (329 mg) was isolated from the reaction mixture by decanting off the FC-75 and dried in vacuo.
Mn was calculated on the basis of 1H NMR intecrration of aliphatic vs. olefinic resonances to be 700. The degree of polymerization, DP, was calculated on the basis of the 1H NMR spectrum to be 24.1; for a linear polymer this would result in 45 methyl-ended branches per 1000 30 methylenes. However, based on the 1H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 173.
E~mnle 66 A 100 mL autoclave was charged with FC-7S (50 mL), 3~ t(Ph2DABMe2)PdMe(NCMe)}SbF6 (0.076 g, 0.12 mmol) and ethylene (2.1 MPa). The reaction mixture was stirred at 24°C for 1.5 h. The ethylene pressure was then vented, and the FC-75 mixture removed from the reactor.

c1 lacTITI tTF SHFFT IRI 11 E 261 small amount of insoluble oil was isolated from the mixture by decanting off the FC-75. The reactor was washed out with 2 x 50 mL CHC13, and the washings added to the oil. Volatiles removed. from the resulting solution in vacuo to afford 144 mg of an oily solid.
Mn was calculated on the basis of 1H NMR integration of aliphatic vs. olefinic resonances to be 400. The degree of polymerization, DP, was calculated or, the basis of the 1H NMR spectrum to be 13.8; for a linear polymer this would result in 83 methyl-ended branches per 1000 methylenes. However, based on the 1H NMR
spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 288.
Examnie 67 1J A 100 mL autoclave was charged with chleroferm (50 mLi, {[(2,6-EtPh)2DABMe2]PdMe(NCMe)}BAF (0.165 a, O.i2 mmol), and ethylene (2.1 MPa). The reaction mixture was stirred under 2.1 MPa of ethylene for 60 min;
during this time the temperature inside the reactcr increased from 22 to 48°C. The ethylene pressure was then vented and volatiles removed from the reaction mixture in vacuo to afford 15.95 g of a viscous oil.
1H NMR of this material showed it to be branched polyethylene with 135 methyl-ended branches per 1000 methylenes. GPC analysis in trichlorobenzene (vs. a linear polyethylene standard) gave Mn = 10,400, M.,; _ 22,100.
Example 68 This was run identically to Example 67, but with {[(2,6-EtPh)ZDABMe2]PdMe(NCMe)}SbF6 (0.090 g, 0.12 mmol) in place of the corresponding BAF salt. The temperature of the reaction increased from 23 to 30°C
during the course of the reaction. 5.25 g of a viscous oil was isolated, 1H NMR of which showed it to be 3~ branched polyethylene with 119 methyl-ended branches per 1000 methylenes.

SUBSTITUTE SHEET (RULE 26) Example 69 A suspension of ([(Np)2DABMe2)PdMe(NCMe))SbF6 (0.027 g, 0.02 mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h; during this time the temperature inside the reactor varied between 25 and 40°C. Two FC-75 insoluble fractions were isolated from the reaction mixture. One fraction, a non-viscous oil floating on top of the FC-75, was removed by pipette and shown by 1H NMR tc be branched ethylene oligomers 10 for which Mn = 150 and with 504 methyl-ended branches per 1000 methylenes. The other fraction was a viscous oil isolated by removing FC-75 by pipette; it was shown by 1H NMR to be polyethylene for which Mn = 650 and with 240 methyl-ended branches per 1000 methyienes.
1~ Example 70 A suspension of ( [ ( PhzCH ) ZDABH2 ) PdMe (NCMe ) ~ SbF6 (0.016 g, 0.02 mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40 min. During this time the reaction temperature varied between 23 and 41°C. A
~0 viscous oil (43 mg) was isolated from the reaction mixture by decanting off the FC-75 and dried in vacuo.
Mn was calculated on the basis of 1H NMR integration of aliphatic vs. olefinic resonances to be approximately 2000. The degree of polymerization, DP, was calculated on the basis of the 1H NMR spectrum to be 73; for a linear polymer this would result in 14 methyl-ended branches per 1000 methylenes. However, based on the 1H
NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 377.
30 Example 71 A 100 mL autoclave was charged with FC-75 (50 mL), ({Ph2DAB(cyclo -CMe2CH2CMez-))PdMe(MeCN))BAF (0.160 g, 0.12 mmol) and ethylene (2.1 MPa). The reaction mixture was stirred at 24-25°C for 3.5 h. The ethylene pressure was then vented, and the cloudy FC-75 mixture removed from the reactor. The FC-75 mixture was extracted with chloroform, and the chloroform extract concentrated to dryness affording 0.98 g of an oil. Mn SUBSTITUTE SHEET (RULE 26) WO 96123010 ~ 02338526 2001-03-O1 PCT/17S96/01282 aas calculated on the basis of 1H NMR integration of aliphatic vs. olefinic resonances to be 500. The degree of polymerization, DP, was calculated on the basis of the 1H NMR spectrum to be 19.5; for a linear polymer this would result in 57 methyl-ended branches per 1000 methylenes. However, based on the 1H NMR
spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 452.
xamnle 72 A 100 mL autoclave was charged with FC-75 (50 mL), [ (4-NMe~Ph) zDABMe2] PdMe (MeCN) }SbFs (MeCN) (0 . 091 g, 0.12 mmol) and ethylene (2.1 MPa). The reaction mixture was stirred at 24°C for 1.5 h. The ethylene pressure was then vented, and the cloudy FC-75 mixture 1~ removed from the reactor. The FC-75 was extracted with 3 x 25 mL of chloroform. The reactor was washed out with 3 x 40 mL CHC13, and the washings added to the extracts. Volatiles removed from the resulting soluticn in vacuo to afford 556 mg of an oil. Mn was calculated on the basis of 1H NMR integration of aliphatic vs. olefinic resonances to be 200. The degree of polymerization, DP, was calculated on the basis cf the 1H NMR spectrum to be B.4; for a linear polymer this would result in 154 methyl-ended branches per 1000 methylenes. However, based on the 1H NMR
spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 261.
Example 73 Under nitrogen, a 250 mL Schlenk flask was charged with Ø0 g of the monomer CH2=CHCOZCH2CH2(CF2)nCF3 (avg n = 9), 40 mL of methylene chloride, and a magnetic stirbar. To the rapidly stirred solution was added [(2,6-i-PrPh)2DABMe2]PdMe(OEt2)~SbFE (0.075 g, 0.089 mmol) in small portions. The resulting yellow-orange 3~ solution was stirred under 1 atm of ethylene for 18 h.
The reaction mixture was then concentrated, and the viscous product extracted with - 300 mL of petroleum ether. The yellow filtrate was concentrated to m ieeTt~ t~r~ ct~LCT fRl II F 9R1 WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96l01282 3ryness, and extracted a second time with - 15D mL
petroleum ether. - 500 mL of methanol was added to the filtrate; the copolymer precipitated as an oil which adhered to the sides of the flask, and was isolated by decanting off the petroleum ether/ methanol mixture.
The copolymer was dried, affording 1.33 g of a slightly viscous oil. Upon standing for several hours, an additional 0.70 g of copolymer precipitated from the petroleum ether/ methanol mixture. By 1H NMR
10 integration, it was determined that the acrylate content of this material was 4.2 mole%, and that it contained 26 ester and 87 methyl-ended branches per 1000 methylenes. GPC analysis in tetrahydrofuran (vs.
a PMMA standard) gave Mn = 30,400, MW = 40,200. 1H NMR.
/J (CDC13) d 4.36 (t, CH2CH2C02CH2CH2Rg), 2.45 (mult, CH~CH2C02CHZCHZRf), 2.31 (t, CH2CHzC02CH~CH2Rf), 1.62 (mult, CH2CH2C02CH2CH2Rgi, 1.23 (mint, other methylenes and methines), 0.85 (mult, methyls). 13C NMR gave branching per 1000 CH2: Total methyls (91.3), Methyl 20 ;32.8), Ethyl(20), Propyl (2.2), Butyl (7.7), Amyl (2.2), >_Hex and end of chains (22.1). GPC analysis in THF gave Mn = 30,400, Mw = 40,200 vs. PMMA.
Example 74 A 100 mL autoclave was charged with ;Pd(CH3CH2CN)4](BF4)2 (0.058 g, 0.12 mmol) and chloroform (4o mL). To this was added a solution of (2,6-i-PrPh)2DABMe2 (0.070 g, 0.17 mmoi) dissolved in 0 mL of chloroform under ethylene pressure (2.1 MPa).
'~he pressure was maintained at 2.1 MPa for 1.5 h, 30 during which time the temperature inside the reactor increased from 22 to 35°C. The ethylene pressure was then vented and the reaction mixture removed from the =-eactor. The reactor was washed with 3 x 50 mL of chloroform, the washings added to the reaction mixture, 3~ and volatiles removed from the resulting solution in vacuo to afford 9.77 g of a viscous oil. 1H NMR of this material showed it to be branched polyethylene with 96 methyl-ended branches per 1000 methylenes.

m ioc~Tl tTG CNGGT fRi I) F 9R1 Exaynle 75 A 100 mL autoclave was charged with [Pd(CH3CN)4J(BF4)2 (0.053 g, 0.12 mmol) and chloroform (50 mL). To this was added a solution of (2,6-i-PrPh)2DABMe2 (0.070 a, 0.17 mmol) dissolved in 10 mL of chloroform under ethylene pressure (2.1 MPa). The pressure was maintained at 2.1 MPa for 3.0 h, during which time the temperature inside the reactor increased from 23 to 52°C. The ethylene pressure was then vented 10 and the reaction mixture removed from the reactor. The reactor was washed with 3 x 50 mL of chloroform, the washings added to the reaction mixture, and volatiles removed from the resulting solution in vacuo to afford 25.98 g of a viscous oil. 1H NMR of this material 1~ showed it to be branched polyethylene with 103 methyl-ended branches per 1000 methylenes. GPC analysis in trichlorobenzene gave Mn = 10,800, Mw = 21,200 vs.
linear polyethylene.
xample 76 ?0 A mixture of 20 mg (0.034 mmol) of [(2,6-i-PrPh)DABH~)NiBr2 and 60 mL dry, deaerated toluene was magnetically-stirred under nitrogen in a 200-mL three-necked flask with a gas inlet tube, a thermometer, and a gas exit tube which vented through a mineral oil bubbler. To this mixture, 0.75 mL (65 eq) of 3M
poly(methylalumoxane) (PMAO) in toluene was added via syringe. The resulting deep blue-black catalyst solution was stirred as ethylene was bubbled through at about 5 ml and 1 atm for 2 hr. The temperature of the 30 mixture rose to 60°C in the first 15 min and then dropped to room temperature over the course of the reaction.
The product sclution was worked up by blending with methanol; the resulting white polymer was washed 3~ with 2N HC1, water, and methanol to yield after drying (50°C/vacuum/nitrogen purge) 5.69g (6000 catalyst turnovers) of polyethylene which was easily-soluble in hot chlorobenzene. Differential scanning calorimetry 17~
c~ ~acTiTi tTF SHFFT fRIILE 261 WO 96/23010 ~ 02338526 2001-03-O1 pC'f/US96/01282 xhibited a broad melting point at 107°C (67 J/g). Ge' permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory):
Mn=22,300; Mw=102,000; MW/Mn=4.56. 13C NMR analysis:
branching per 1000 CH2: total Methyls (60), Methyl (41), Ethyl (5.8), Propyl (2.5), Butyl (2.4), Amyl (1.2), ?Hexyl and end of chain (5); chemical shifts were referenced to the solvent: the high field carbon 10 of 1,2,4-trichlorobenzene (127.8 ppm). A film of polymer (pressed at 200°C) was strong and could be stretched and drawn without elastic recovery.
Example 77 F
In a Parry 600-mL stirred autoclave under l~ nitrogen was combined 23 mg (0.039 mmol) of [(2,6-i-PrPh)DABH2)NiBr2, 60 mL of dry toluene, and 0.75 mL of poly(methylalumoxane) at 28°C. The mixture was stirred, flushed with ethylene, and pressurized to 414 kPa with ethylene. The reaction was stirred at 414 kPa ?0 for 1 hr; the internal temperature rose to 31°C over this time. After 1 hr, the ethylene was vented and 200 mL of methanol was added with stirring to the autoclave. The resulting polymer slurry was filtered;
the polymer adhering to the autoclave walls and impeller was scraped off and added to the filtered polymer. The product was washed with methanol and acetone and dried (80°C/vacuum/nitrogen purge) to yield S.lOg (4700 catalyst turnovers) of polyethylene.
Differential scanning calorimetry exhibited a melting 3~ point at 127°C (170 J/g). Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=49,300; MW=123,000;
MW/Mn=2.51. Intrinsic viscosity (trichlorobenzene, 3~ 135°C): 1.925 dL/g. Absolute molecular weight averages corrected for branching: Mn=47,400; MW=134,000;
MW/Mn=2.83. 13C NMR analysis; branching per 1000 CHZ:
total Methyls (10.5), Methyl (8.4), Ethyl (0.9), Propyl e~ iec~rrTt ~r curt? roi n C 9R1 WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96/01282 (0), Butyl (0), >_Butyl and end of chain (1.1); chemical shifts were referenced to the solvent: the high field carbon of 1,2,4-trichlorobenzene (127.8 ppm). A film of polymer (pressed at 200°C) was strong and stiff and could be stretched and drawn without elastic recovery.
This polyethylene is much more crystalline and linear than the polymer of Example 76. This example shows that only a modest pressure increase from 1 atm to 414 kPa allows propagation to successfully compete with rearrangement and isomerization of the polymer chain by this catalyst, thus giving a less-branched, more-crystalline polyethylene.
Example 78 A mixture of 12 mg (0.020 mmol) of [(2,6-1-1 ~ PrPh) DABZ=] NiBrz and 40 mL .dry, deaerated toluene was magnetically-stirred under nitrogen at 15°C in a 100-mL
three-necked flask with an addition funnel, a thermometer, and a nitrogen inlet tube which vented through a mineral oil bubbler. To this mixture, 0.5 mL
?0 of poiy(methylalumoxane) in toluene was added via syringe; the resulting burgundy catalyst solution was stirred for 5 min and allowed to warm to room temperature. Into the addition funnel was condensed (via a Dry Ice condenser on the top of the funnel) 15 ~~ mL (about 10g) of cis-2-butene. The catalyst solution was stirred as the cis-2-butene was added as a liquid all at once, and the mixture was stirred for 16 hr.
The product solution was treated with 1 mL of methanol and was filtered through diatomaceous earth; rotary 30 evaporation yielded 0.35g (300 catalyst turnovers) of a light yellow grease, poly-2-butene. 13C NMR analysis;
branching per 1000 CH2: total Methyls (365), Methyl (285), Ethyl (72), >_Butyl and end of chain (8);
chemical shifts were referenced to the solvent >> chloroform-dl (77 ppm).
Listed below are the 13C NMR data upon which the above analysis is based.

SUBSTITUTE SHEET (RULE 26) 13C ~ Data CDC13, RT, 0.05M CnAcAc Freq ppm Intensity 41.6071 11.2954 41.1471 13.7193 38.6816 3.55568 37.18D5 7.07882 36.8657 33.8859 36.7366 35.1101 36.6196 33.8905 36.2645 12.1006 35.9094 13.3271 35.8004 11.8845 35.5785 4.20104 34.7351 24.9682 34.4325 39.3436 34.3114 59.2878 34.1177 125.698 33.9886 121.887 33.8837 120.233 33.5326 49.8058 33.004 132.842 32.7377 51.2221 32.657 55.6128 32.3705 18.1589 31.5876 9.27643 31.3818 16.409 31.0066 15.1861 30.0946 41.098 29.9736 42.8009 29.7D72 106.314 29.3602 60.0884 29.2512 35.0694 29.114 26.6437 28.9769 29.1226 27.9358 3.57351 27.7501 3.56527 27.0682 14.6121 26.7333 81.0769 26.3257 14.4591 26.015 11.8399 25.3008 8.17451 25.0627 5.98833 22.4801 3.60955 284 22.3308 10.4951 2B5+, EOC

19.6192 90.3272 1B1 19.9618 154.354 1B1 19.3085 102.085 181 18.9937 34.7667 1B1 18.8525 38.7651 1B1 13.7721 11.2148 184+, EOC, 1B3 11.0484 54.8771 1B2 10.4552 10.8437 1B2 10.1283 11.0735 1B2 9.99921 9.36226 1B2 SUBSTITUTE SHEET (RULE 26) Example 79 A mixture of 10 mg (0.017 mmol) of [(2,6-i-PrPh)DABH~)NiBr2 and 40 mL dry, deaerated toluene was magnetically-stirred under nitrogen at 5°C in a 100-mL
three-necked flask with an addition funnel, a thermometer, and a nitrogen inlet tube which vented through a mineral oil bubbles. To this mixture, 0.5 mL
of 3M poly(methylalumoxane) in toluene was added via 10 syringe; the resulting burgundy catalyst solution was stirred at 5°C for 40 min. Into the addition funnel was condensed (via a Dry Ice condenser on the top of the funnel) 20 mL (about 15 g) of 1-butene. The catalyst solution was stirred as the 1-butene was added l~ as a liquid ail at once. .The reaction temperature rose to 50°C over 30 min and then dropped to room temperature as the mixture was stirred for 4 hr. The product solution was treated with 1 mL of methanol and was filtered through diatomaceous earth; rotary 20 evaporation yielded 6.17 g (1640 catalyst turnovers) of clear, tacky poly-1-butene rubber. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=64,700; Mw=115,000;
~~ MW/Mn=1.77. 13C NMR analysis; branching per 1000 CHI:
total Methyls (399), Methyl (86), Ethyl (272), >_Butyl and end of chain (41); chemical shifts were referenced to the solvent chloroform-dl (77 ppm). This example demonstrates the polymerization of an alpha-olefin and 30 shows the differences in branching between a polymer derived from a 1-olefin (this example) and a polymer derived from a 2-olefin (Example 78). This difference shows that the internal olefin of Example 78 is not first isomerized to an alpha-olefin before 3~ polymerizing; thus this catalyst is truly able to polymerize internal olefins.
Listed below are the 13C NMR data upon which the above analysis is based.

~11RCTITI IT'E SHEET (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 13C ~R Data CDC13, RT, CrAcAc 0.05M

Freq Intensity ppm 43.8708 6.42901 41.5304 11.1597 41.0825 16.1036 38.7623 103.647 38.1247 50.3288 37.3338 24.6017 36.8173 30.0925 35.756 55.378 35.0337 22.3563 34.1419 64.8431 33.8514 55.3508 33.4116 90.2438 33.0645 154.939 32.7094 51.3245 32.431 23.0013 385 30.946 12.8866 386+

30.1551 26.1216 29.7516 54.6262 29.4248 40.7879 27.6008 8.64277 27.2417 20.1564 27.1207 21.9735 26.7777 45.0824 26.0755 66.0697 25.6599 77.1097 24.3807 8.9175 23.4809 32.0249 284, 285+, 2EOC

22.8393 8.06774 22.1372 16.4732 19.4981 57.7003 181 19.3609 70.588 181 15.132 17.2402 1B4+

13.8448 7.9343 184+

12.2509 27.8653 12.037 27.0118 11.0766 6.61931 1B2 10.2938 98.0101 1B2 10.1364 104.811 182 Examrle 80 A 22-ma (0.037-mmol) sample of [(2,6-i-PrPh)DABH~JNiBr, was introduced into a 600-mL stirred ParrO autoclave under nitrogen. The autoclave was , sealed and ?S mL of dry, deaerated toluene was .
introduced into the autoclave via gas tight syringe 10 through a port on the autoclave head. Then 0.6 mL of ' 3M poly(methylalumoxane) was added via syringe and stirring was begun. The autoclave was pressurized with e~ ~ce~Tt tT~ cu~FT (Rt II E 26) w:ropyiene to 414 kPa and stirred with continuous propylene feed. There was no external cooling. The internal temperature quickly rose to 33°C upon initial propylene addition but gradually dropped back to 24°C
~ over the course of the polymerization. After about 7 min, the propylene feed was shut off and stirring was continued; over a total polymerization time of 1.1 hr, the pressure dropped from 448 kPa to 358 kPa. The propylene was vented and the product, a thin, honey-10 colored solution, was rotary evaporated to yield 1.65g of a very thick, brown semi-solid. This was dissolved in chloroform and filtered through diatomaceous earth;
concentration yielded 1.3 g (835 catalyst turnovers) of tacky, yellow polypropylene rubber. Gel permeation 1~ chromatography (trichlorobenzene, i35°C, polystyrene reference, results calculated as polypropylene using universal calibration theory): Mn=7,940; Mw=93,500;
M,,,~ / Mn=11 . 7 8 .
Example 81 20 A mixture of 34 mg (0.057 mmol) of [(2,6-i-PrPh)DABH2]NiBr2 and 20 mL dry, deaerated toluene was magnetically-stirred under nitrogen at 5°C in a 100-mL
three-necked flask with a thermometer and a nitrogen inlet tube which vented through a mineral oil bubbler.
?~ To this mixture, 0.7 mL of 3M poly(methylalumoxane) in toluene was added via syringe and the resulting deep blue-black solution was stirred for 30 min at 5°C. To this catalyst solution was added 35 mL of dry, deaerated cyclopentene, and the mixture was stirred and 30 allowed to warm to room temperature over 23 hr. The blue-black mixture was filtered through alumina to remove dark blue-green solids (oxidized aluminum compounds from PMAO); the filtrate was rotary evaporated to yield 1.2 g (310 catalyst turnovers) of 35 clear liquid cyclopentene oligomers.
$xamnlP 82 A 20-mg (0.032 mmol) sample of [(2,6-i-PrPh)DABMe~]NiBr2 was placed in Parr~ 600-mL stirred SUBSTITUTE SHEET (RULE 26) autoclave under nitrogen. The autoclave was sealed and 100 mL of dry, deaerated toluene and 0.6 mL of 3M
poly(methylalumoxane) were injected into the autoclave through the head port, and mixture was stirred under nitrogen at 20°C for 50 min. The autoclave body was immersed in a flowing water bath and the autoclave was then pressurized with ethylene to 2.8 MPa with stirring as the internal temperature rose to 53°C. The autoclave was stirred at 2.8 MPa (continuous ethylene 10 feed) for 10 min as the temperature dropped to 29°C, and the ethylene was then vented. The mixture stood at 1 atm for 10 min; vacuum was applied to the autoclave for a few minutes and then the autoclave was opened.
The product was a stiff, swollen polymer mass is whic:l was scraped out, cut. up, and fed in portions to 500 mL methanol in a blender. The polymer was then boiled with a mixture of methanol (200 mL) and trifluoroacetic acid (10 mL), and finally dried under high vacuum overnight to yield 16.88 (18,700 catalyst 20 turnovers) of polyethylene. The polymer was somewhat heterogeneous with respect to crystallinity, as can be seen from the differential scanning calorimetry data below; amorphous and crystalline pieces of polymer could be picked out of the product. Crystalline polyethylene was found in the interior of the polymer mass; amorphous polyethylene was on the outside. The crystalline polyethylene was formed initially when the ethylene had good access to the catalyst; as the polymer formed limited mass transfer, the catalyst 30 became ethylene-starved and began to make amorphous polymer. Differential scanning calorimetry:
(crystalline piece of polymer): mp: 130°C (150J/g);
(amor:.hous piece of polymer): -48°C (Tg); mp: 42°C
(3J/a!, 96°C (11J/g). Gel permeation chromatography (tric::iorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=163,000; MW=534,000;
MW/Mr=3.27. This example demonstrates the effect of SUBSTITUTE SHEET (RULE 26) WO 96/23010 CA 02338526 2001-03-O1 PC"T/US96/01282 ethylene mass transfer on the polymerization andVshows that the same catalyst can make both amorphous and crystalline polyethylene. The bulk of the polymer was crystalline: a film pressed at 200°C was tough and ~ stiff .
Example 83 A 29-mg (0.047 mmol) sample of [(2,6-i-PrPh)DABMez]NiBrz was placed in ParrO 600-mL stirred autoclave under nitrogen. The autoclave was sealed and 10 100 mL of dry, deaerated toluene and 0.85 mL of 3M
poly(methylalumoxane) were injected into the autoclave through the head port. The mixture was stirred under nitrogen at 23°C for 30 min. The autoclave body was immersed in a flowing water bath and the autoclave was 1~ pressurized with ethylene .to 620 kPa with stirring.
The internal temperature peaked at 38°C within 2 min.
The autoclave was stirred at 620 kPa (continuous ethylene feed) for 5 min as the temperature dropped to 32°C. The ethylene was then vented, the regulator was 20 readjusted, and the autoclave was pressurized to 34.5 kPa (gauge) and stirred for t0 min (continuous ethylene feed) as the internal temperature dropped to 22°C. In the middle of this 20 min period, the ethylene feed was temporarily shut off for 1 min, during which time the ~ autoclave pressure dropped from 34.5 kPa (gauge) to 13.8 kPa; the pressure was then restored to 34.5 kPa.
After stirring 20 min at 34.5 kPa, the autoclave was once again pressurized to 620 kPa for 5 min; the internal temperature rose from 22°C to 34°C. The 30 ethylene feed was shut off for about 30 sec before venting; the autoclave pressure dropped to about 586 kPa.
The ethylene was vented; the product was a dark, thick liquid. Methanol (200 mL) was added to the 35 autoclave and the mixture was stirred for 2 hr. The polymer, swollen with toluene, had balled up on the stirrer, and the walls and bottom of the autoclave were coated with white, fibrous rubbery polymer. The s«a~rr~l~ sHEEf rRULE 261 WO 96123010 ~ 02338526 2001-03-O1 pCT/US96/01282 .aolymer was scraped out, cut up, and blended with methanol in a blender and then stirred with fresh boiling methanol for 1 hr. The white rubber was dried under high vacuum for 3 days to yield 9.6 g (7270 catalyst turnovers) of rubbery polyethylene. 1H NMR
analysis (CDC13): 95 methyl carbons per 1000 methylene carbons.
Differential scanning calorimetry: -51°C (Tg); mp:
3°.5°C (4J/g); mp: 76.4°C (7J/g). Gel permeation 10 chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=223,000; Mw=487,000;
Mw/Mn=2.19.
The polyethylene of Example 83 could be cast from l~ :~:ot chlorobenzene or pressed at 200°C to give a strong, stretchy, hazy, transparent film with good recovery.
It was not easily chloroform-soluble. This example demonstrates the use of the catalyst's ability (see Example 82) to make both amorphous and crystalline ?0 polymer, and to make both types of polymer within the same polymer chain due to the catalyst's low propensity to chain transfer. with crystalline blocks (due to higher ethylene pressure) on both ends and an amorphous region (due to lower- pressure, mass transfer-limited polymerization) in the center of each chain, this polymer is a thermoplastic elastomer.
Example 84 A Schlenk flask containing 147 mg (0.100 mmol) of C (2, 6-i-PrPh) DABMe2] PdMe (OEt2) }BAF was cooled to -30 78°C, evacuated, and placed under an ethylene atmosphere. Methylene chloride (100 ml) was added to the flask and the solution was then allowed to warm to room temperature and stirred. The reactio_~_ vessel was warm during the first several hours of mix=ng and the 3~ solution became viscous. After being stirred for 17.4 h, the reaction mixture was added to -600 mL of MeOH in order to precipitate the polymer. Next, the MeOH was decanted off of the sticky polymer, which was then c~ mc~m r~ cuFFT !RI 1l E 261 dissolved in -.600 mL of petroleum ether. After being filtered through plugs of neutral alumina and silica gel, the solution appeared clear and almost colorless.
The solvent was then removed and the viscous oil (45.31 g) was dried in vacuo for several days: 1H NMR (CDC13, 400 MHz) c~ 1.24 (CH2, CH), 0.82 (m, CH3); Branching:
-128 CH3 per 1000 CH2; DSC: Tg = -67.7°C. GPC: Mn =
29,000; Mw = 112,000.
Examine 85 Following the procedure of Example 84 {[(2,6-i-PrPh)DABMe2]PdMe(OEtz)}BAF (164 mg, 0.112 mmol) catalyzed the polymerization of ethylene for 24 h in 50 mL cf CH2C12 to give 30.16 g of polymer as a viscous of 1. iH NMR (C5D6) d 1.41 (CH2, CH) , 0. 94 (CH3) ;
l~ Branc~~inJ: -.ii5 CH3 per 1000 CHz; GPC Analysis (THF, PMMA standards, RI Detector): MW = 262,000; Mn =
121,000; PDI = 2.2; DSC: Tg = -66.8°C.
Examcle 86 The procedure of Example 84 was followed using 144 ?0 mg (0.100 mmol) of { [ (2, 6-i-PrPh)DABH2] PdMe (OEt2) }BAF
in 50 mL of CH2C12 and a 24 h reaction time. Polymer (9.68 g) was obtained as a free-flowing oil. 1H NMR
(CDCIz, 400 MHz) c5 5.36 (m, RHC=CHR'), 5.08 (br s, RR'C=CHR " ), 4.67 (br s, H2C=CRR'), 1.98 (m, allylic ~~ H), 1.25 (CH2, CH), 0.83 (m, CH3); Branching: -149 CH3 per 1000 CH2; DSC: Tg = -84.6°C.
E~nle 87 A 30-mg (0.042-mmol) sample of [(2,6-i-PrPhiDABAn]NiBr2 was placed in ParrO 600-mL stirred 30 autoclave under nitrogen. The autoclave was sealed and 150 mL of dry toluene and 0.6 mL of 3M
polymethylalumoxane were injected into the autoclave throuch the head port. The autoclave body was immersed in a flowing water bath and the mixture was stirred 3~ under nitrogen at 20°C for 1 hr. The autoclave was then pressurized with ethylene to 1.31 MPa with stirrir_a for 5 min as the internal temperature peaked at 30°C. The ethylene was then vented to 41.4 kPa SUBSTITUTE SHEET (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 p~'/Z7S96/01282 v gauge) and the mixture was stirred and fed ethylene at 41.4 kPa for 1.5 hr as the internal temperature dropped to 19°C. At the end of this time, the autcciave was again pressurized to 1.34 MPa and stirred for 7 min as the internal temperature rose to 35°C.
The ethylene was vented and the autoclave was briefly evacuated; the product was a stiff, solvent-swollen gel. The polymer was cut up, blended with 500 mL methanol in a blender, and then stirred overnight 10 with 500 mL methanol containing 10 mL of 6N HC1. The stirred suspension in methanol/HC1 was then boiled for 4 hr, filtered, and dried under high vacuum overnight to yield 26.1 g (22,300 catalyst turnovers) of polyethylene. Differential scanning calorimetry: -49°C
1~ (Tg); mp: 115°C (42J/g). The melting transition was very broad and appeared to begin around room temperature. Although the melting point temperature is higher in this Example than in Example 76, the area under the melting endotherm is less in this example, 20 implying that the polymer of this Example is less crystalline overall, but the crystallites that do exist are more ordered. This indicates that the desired block structure was obtained. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=123,000; M~,,=601,000;
MW/Mn=4.87. The polyethylene of this example could be pressed at 200°C to give a strong, tough, stretchy, hazy film with ~.artial elastic recovery. When the 30 stretched film was plunged into boiling water; it completely relaxed to its original dimensions.
Example 88 A 6.7-mg (0.011-mmol) sample of [(2,6-i-PrPh)DABMez]NiBr2 was magnetically-stirred under nitrogen in a 50-mL Schlenk flask with 25 mL of dry, deaerated toluene as 0.3 mL of 3M poly(methylalumoxane) was injected via syringe. The mixture was stirred at 23°C for 40 min to give a deep blue-green solution of ci mc~nr~ t~ ~NF~ rRt 1E 261 atalyst. Dry, deaerated cyciopentene (10 mL) was injected and the mixture was stirred for 5 min. The flask was then pressurized with ethylene at 20.7 MPa and stirred for 22 hr. The resulting viscous solution was poured into a stirred mixture of 200 mL methanol and 10 mL 6N HC1. The methanol was decanted off and replaced with fresh methanol, and the polymer was stirred in boiling methanol for 3 hr. The tough, stretchy rubber was pressed between paper towels and dried under vacuum to yield 1.0g of poly(ethylene/cyclopentene). 8y 1H NMR
analysis(CDC13): 100 methyl carbons per 1000 methylene carbons. Comparison of the peaks attributable to cyclopentene (0.65 ppm and 1.75 ppm> with the standard I~ polyethylene peaks (0.9 ppm and 1.3 ppm) indicates about a 10 mol% cyclopentene incorporation. This polymer yield and composition represent about 2900 catalyst turnovers. Differential scanning calorimetry:
-44°C (Tg). Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=122,000; Mw=241,000;
Mw/Mn=1.97.
Listed below are the 13C NMR data upon which the above analysis is based.
13C ~R data TCB, 120C, 0.05M CrAcAc Freq ppm Intensity 50.9168 5.96663 46.3865 3.27366 l cme and/or 1,3 ccmcc 40.7527 40.5963 2 eme 40.567 41.9953 1,3 eme 40.3336 45.8477 1,3 eme 37.1985 60.1003 36.6998 41.2041 36.0579 11.2879 35.607 25.169 34.4771 19.0834 34.0845 22.8886 33.1243 20.1138 32.8962 27.6778 31.8406 75.2391 30.0263 76.2755 Ig~
cllACTtTIfTF ~HFFT fRl II F ~Rl WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96I01282 29.6921 170.41 28.9494 18.8754 28.647 25.8032 27.4588 22.2397 27.1086 48.0806 24.3236 3.31441 22.5783 4.64411 285+, 2 EOC

19.6712 43.1867 1B1 17.5546 1.41279 end group 14.3399 1.74854 183 13.8518 5.88699 1B4+, lEOC

10.9182 2.17785 281 Rxamp~,8~
A 7.5-mg (0.013-mmol) sample of [(2,6-t-BuPh)DABMe~]NiBr2 was magnetically stirred under nitrogen in a 50-mL Schlenk flask with 40 mL of dry, deaerated toluene as 0.5 mL of 3M poly(methylalumoxane).
was injected via syringe. The mixture was stirred at 23°C for 1 hr to give a deep blue-green solution of catalyst. The flask was pressurized with ethylene at 10 20.7 kPa (gauge) and stirred for 20 hr. The solution, which had become a reddish-brown suspension, was poured into a stirred mixture of 200 mL methanol and 10 mL 6N
HC1 and was stirred at reflux for 1 hr. The methanol was decanted off and replaced with fresh methanol, and 15 the white polymer was stirred in boiling methanol for 1 hr. The stiff, stretchy rubber was pressed between paper towels and then dried under vacuum to yield 1.25 g (3380 catalyst turnovers) of polyethylene. 1H-1 NMR
analysis (C6D6): 63 methyl carbons per 1000 methylene 20 carbons. Differential scanning calorimetry: -34°C
(Tg); mp: 44°C (31J/g); mp: 101°C (23J/g).
xa nle 90 A 5.5 mg (0.0066 mmol) sample of {[(2,6-i-PrPh)2DABMe2]PdMe(Et~O)}SbF6 was allowed to stand at room temperaLUre in air for 24 hr. A 100-mL three-neck flask with a magnetic stirrer and a gas inlet dip tube was charged with 40 mL of reagent methylene chloride and ethylene gas was bubbled through with stirring to saturate the solvent with ethylene. The sample of 30 { [ (2, 6-i-PrPh) ~DABMe2] PdMe (Et20) ~SbF6 was then rinsed et tceTrTt tTC cNtcT IRI 11 F X61 ,into the flask with 5 mL of methylene chloride~ana ethylene was bubbled through with stirring for 5 hr.
The clear yellow solution was rotary evaporated to yield 0.20 g (1080 catalyst turnovers) of a thick yellow liquid polyethylene.
Fxamye 91_ A 600-mL stirred Parr° autoclave was sealed and flushed with nitrogen, and 100 mL of dry, deaerated toluene was introduced into the autoclave via gas tight syringe through ~ port on the autoclave head. The autoclave was purged with propylene gas to saturate the solvent with propylene. Then 45 mg (0.054 mmol) of [(2,6-i-PrPh)ZDABMeZ]PdMe(EtzO))SbF6 was introduced into the autoclave in the following manner: a 2.5-mL
l~ gas tight syringe with a syringe valve was loaded with 45 mg of~[(2,6-i-PrPh)2DABMe2]PdMe (Et20)}SbF6 under nitrogen in a glove box; then 1-2 mL of dry, deaerated methylene chloride was drawn up into the syringe and the contents were quickly injected into the autoclave ?0 through a head port. This method avoids having the catalyst in solution with no stabilizing ligands.
The autoclave was pressurized with propylene to 414 MPa and stirred for 2.5 hr, starting with continuous propylene feed. The autoclave was cooled in a running tap water bath at 22°C. The internal temperature quickly rose to 30°C upon initial propylene addition but soon dropped back to 22°C. After 0.5 hr, the propylene feed was shut off and stirring was continued. Over 2 hr, the pressure dropped from 41.4 s0 MPa to 38.6 MPa. The propylene was then vented. The product was a thin, honey-colored solution. Rotary evaporation yielded 2.3 g (1010 catalyst turnovers) of very thick, dark-brown liquid polypropylene which was almost eiastomeric when cool. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polypropylene using universal calibration theory): Mn=8,300; Mw=15,300;
Mw/Mn=1.84. 13C NMR analysis; branching per 1000 CH2:

RI IR~TITI iTF SNFFT (RULE 261 WO 96/23010 CA 02338526 2001-03-O1 pCT/US96101282 total Methyls (545), Propyl (1.3), >Butw~ and end cf chain (9.2); chemical shifts. The polymer exhibited a glass transition temperature of -44°C by differential scanning calorimetry.
Listed below are the 13C NMR data upon which the above analysis is based.
13C ~R data CDC13, RT, 0.05M CrAcAc Freq ppm Intensity 46.4978 13.2699 Methylenes 45.8683 11.9947 Methylenes 45.3639 10.959 Methvlenes 45.1783 11.3339 Methylenes 44.5568 8.41708 Methylenes 44.4398 7.69019 Methylenes 44.3026 6.29108 Methylenes 44.1372 6.73541 Methylenes 43.5036 5.49837 Methylenes 42.4262 5.03113 Methylenes 41.6918 3.72552 Methylenes 39.1537 4.23147 Methines and Methvlenes 38.7179 25.2596 Methines and Methylenes 37.8664 10.0979 Methines and Methylenes 37.6727 14.3755 Methines and Methylenes 37.0755 17.623 Methines and Methylenes 36.781 42.0719 Methines and Methylenes 36.559 10.0773 Methines and Methylenes 34.5495 5.34388 Methines and Methvlenes 34.3195 7.48969 Methines and Methylenes 33.5488 12.6148 Methines and Methylenes 33.351 20.5271 Methines and Methylenes 32.7982 4.10612 Methines and Methylenes 32.4108 22.781 Methines and Methylenes 31.8701 5.90488 Methines and Methvlenes 31.5957 10.6988 Methines and Methylenes 29.8364 44.4935 Methines and Methylenes 29.7072 103.844 Methines and Methylenes 29.3925 152.645 Methines and Methvlenes 29.0293 6.71341 Methines and Methylenes 27.6089 38.7993 Methines and Methylenes 27.4193 10.3543 Methines and Methylenes 27.0763 66.8261 Methines and Methylenes 26.9552 92.859 Methines and Methylenes 26.7615 55.7233 Methines and Methylenes 26.3661 20.1674 Methines and Methv_lenes 24.8529 16.9056 Methine Carbon of XXVIII

23.1217 12.5439 Methine carbons of XX'III
and XXIX, 284+, EOC

22.6779 13.0147 Methine carbons of XXVIIT_ and XXIX, 284+, EOC , 22.5245 9.16236 Methine carbons of XXVIII
and XXIX, 2B4+, EOC

ct iac~ tT~ SNF~T lRIILE 261 WO 96/23010 CA 02338526 2001-03-O1 PCTlUS96/01282 22.3389 77.3342 Methine carbons of XX'JIII and XXIX, 284+, EOC
21.9757 9.85242 Methine carbons of XXVT_II and XXIX, 284+, EOC
21.1405 10.0445 Methyls 20.4182 8.49663 Methyls 19.9743 25.8085 Methyls 19.825 31.4787 Methyls 19.3811 44.9986 Methyls 19.1995 31.3058 Methyls 13.8569 6.37761 Methyls 13.8004 7.67292 Methyls 137.452 22.0529 Methvls 128.675 44.6993 Methyls 127.88 43.8939 Methyls 124.959 22.4025 Methyls 122.989 3.3312 Methyls Exam, 1 a 9 2 A 600-mL stirred Parr= autoclave was sealed, flushed with nitrogen, and heated to 60°C in a water bath. Fifty mL (48 g; 0.56 mol) of dry, deaerated methyl acrylate was introduced into the autoclave via gas tight syringe through a port on the autoclave head and ethylene gas was passed through the autoclave at a low rate to saturate the solvent with ethylene before catalyst addition. Then 60 mg (0.07 mmol) of {[(2,6-1-10 PrPh)2DABMe2JPdMe(Et20))SbF6 was introduced into the autoclave in the following manner: a 2.5-mL gas tight syringe with a syringe valve was loaded with 60 mg of {[(2,6-i-PrPh)2DABMe2]PdMe(Et20)}SbF6 under nitrogen in a glove box; then 1 mL of dry, deaerated methyiene 1~ chloride was drawn up into the syringe and the contents were quickly injected into the autoclave through a head port. This method avoids having the catalyst in solution with no stabilizing ligands.
The autoclave was pressurized with ethylene to 689 20 kPa and continuously fed ethylene with stirring for 4.5 hr; the internal temperature was very steady at 60°C.
The ethylene was vented and the product, a clear yellow solution, was rinsed out of the autoclave with chiorcform, rotary evaporated, and held under high 2s vacuum overnight to yield 1.56 g of thin light-brown liquid ethylene/methyl acrylate copolymer. The SI IRRT1T11TF SHFFT (RULE 261 infrared spectrum of the product exhibited a stroncr ester carbonyl stretch at 1740 cm-1. 1H-1 NMR analysis (CDC13): 61 methyl carbons per 1000 methylene carbons.
Comparison of the integrals of the ester methoxy (3.67ppm) and ester methylene (~2COOMe; 2.30ppm) peaks with the integrals of the carbon chain methyls (0.8-0.9ppm) and methylenes (1.2-l.3ppm) indicated a methyl acrylate content of 16.6 molo (37.9 wto). This product yield and composition represent 480 ethylene turnovers 10 and 96 methyl acrylate turnovers. 13C NMR analysis;
branching per 1000 CH2: total methyls (48.3), Methyl (20.8), Ethyl (10.5), Propyl (1), Butyl (8), _,Amyl and End of Chair. (18.1), methyl acrylate (94.4); ester-bearina -CH(CH2)nCO~CH~ branches as a o of total ester:
l~ n>_5 (JS.~i, n=4 (14.3), n=i,2,3 (29.5), n=0 (20.3);
chemical shifts were referenced to the solvent: the high field carbon of 1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography (tetrahydrofuran, 30°C, polymethylmethacrylate reference, results 20 calculated as polymethylmethacrylate using universal calibration theory): Mn=3,370; Mw=5,450; Mw/Mn=1.62.
Listed below are the 1'C NMR data upon which the above analysis is based.

~11RSTITI ITF SHEET (RULE 261 C NMR data TCB 120C, 0.05M CrAcAc Freq ppm Intensity 53.7443 2.19635 CH2C12 solvent impurity 50.9115 8.84408 50.641 132.93 45.5165 7.55996 MEBO 43.8 ppm :2 adjacent MEBO

39.69.7 2.71676 39.2886 7.91933 38.1639 13.843 37.7926 26.6353 37.1666 20.6759 36.6733 8.65855 34.6256 17.6899 34.4612 16.7388 34.1429 85.624 33.9095 124.997 lEB4+

33.676 40.0271 Contributions from EB

33.2888 11.4719 Contributions from EB

32.8644 14.4963 Contributions from EB

3 .3498 17.5883 . Contributionsfrom EB

32.04'?5 9.83096 Contributions from EB

31.8459 30.9676 Contributions from EB

31.7079 12.7737 Contributions from EB

31.5912 13.8792 Contributions from EB

31.0873 19.6266 Contributions from EB

30.6258 10.5512 30.1324 58.6101 29.6497 169.398 29.4322 48.5318 29.1934 95.4948 27.8619 8.70181 27.4269 32.9529 26.9283 78.0563 26.5145 27.0608 26.3554 14.0683 25.9588 21.9081 2E84 (tent) 25.33_5 9.04646 2E84 (tent) 24.9761 64.2333 2EB5+

24.2069 10.771 BBB (beta-beta-B) 23.0451 9.50073 2B4 22.9337 6.90528 284 22.5518 30.0427 285+, EOC

19.9842 1.87415 283 19.6288 17.125 1B1 19.1673 6.0427 1B1 16.7695 2.23642 14.3 - 183 13.7882 34.0749 1b4+, EOC

1i . 07'%4 4 . 50599 1B2 10.E705 10.8817 182 189.989 1.04646 EBO Carbonyl 175.687 3.33867 EBO Carbonyl 175.406 14.4124 EBO Carbonyl 175.22 5.43832 EBO Carbonyl 175.061 3.53125 EHO Carbonyl RI IR~T1T11TF SHFFT (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96101282 172.859 11.2356 EB1+ Carbonyl 172.605 102.342 EH1+ Carbonyl 172.09 7.83303 EB1+ Carbonyl 170.944 3.294 EB1+ Carbonyl Examt~le 93 A 45-mg (0.048-mmol) sample of ~[(2,6-i-PrPh)~DABAn]PdMe(Et20)}SbF6 was placed in a 600-mL Parr ~ stirred autoclave under nitrogen. To this was added 50 mL of dry, deaerated methylene chloride, and the autoclave was pressurized to 414 kPa with ethylene.
Ethylene was continuously fed at 414 kPa with stirring at 23-25°C for 3 hr; then the feed was shut off and the 10 reaction was stirred for 12 hr more. At the end of this time, the autoclave was under 89.6 kPa (absolute).
The autoclave was repressurized to 345 kPa with ethylene and stirred for 2 hr more as the pressure dropped to 255 kPa, showing that the catalyst was still 1~ active; the ethylene was then vented. The brown solution in the autoclave was rotary evaporated, taken up in chloroform, filtered through alumina to remove catalyst, and rotary evaporated and then held under high vacuum to yield 7.35 g of thick, yellow liquid ?0 polyethylene. 1H NMR analysis (CDC13): 131 methyl carbons per 1000 methylene carbons. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=10,300; Mw=18,100;
Mw/Mn=1.76.
Example 94 A 79-mg (0.085-mmol) sample of ([(2,6-i-PrPh)2DABAnJPdMe(Et~O)}SbF6 was placed in a 600-mL Parr ~ stirred autoclave under nitrogen. To this was added 30 50 mL of dry, deaerated methyl acrylate, and the autoclave was pressurized to 689 kPa with ethylene.
The autoclave was warmed to 50°C and the reaction was stirred at 689 kPa for 70 hr; the ethylene was then vented. The clear yellow solution in the autoclave was filtered through alumina to remove catalyst, rotary c1 tacTtTt 1TF SHFFT IR1 i1 F 261 WO 96/23010 CA 02338526 2001-03-O1 pCT/US96/01282 evaporated, and held under high vacuum to yield C.2T g of liquid ethylene/methyl acrylate copolymer. The infrared spectrum of the product exhibited a strong ester carbonyl stretch at 1740cm-1. 1H NMR analysis (CDC13): 70 methyl carbons per 1000 methylene carbons;
13.5 molo (32 wto) methyl acrylate. This yield and composition represent 12 methyl acrylate turnovers and 75 ethylene turnovers.
Exam A 67-mg (0.089-mmol) of { [(2,4,6-MePh) zDABMe~] PdMe (Et20) }SbF6 was placed in a 200-mL
glass centrifuge bottle with a magnetic stir bar under nitrogen. To this was added 40 mL of dry, deaerated methyiene chloride. The bottle was immediately I~ pressurized to 207 kPa with ethylene. Ethylene was continuously fed at 207 kPa with stirring at 23-25°C
for 4 hr. After 4 hr, the ethylene feed was shut off and the reaction was stirred for 12 hr more. At the end of this time, the bottle was under zero pressure 20 (gauge). The brown solution was rotary evaporated and held under high vacuum to yield 5.15 g of thick, brown liquid polyethylene. 1H NMR analysis (CDC13): 127 methyl carbons per 1000 methylene carbons. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory):
Mn=20,200; Mw=32,100; Mw/Mn=1.59.
Exam 1~6 A 56-mg (0.066-mmol) sample of {[(2,6-1-30 PrPh) 2DABMe~] PdCH2CH2C (0) CH3) }SbF6 was placed in a 600-mL Parr~ stirred autoclave under nitrogen. To this was added 30 mL of dry, deaerated perfluoro(propyltetrahydrofuran). The autoclave was stirred and pressurized to 5.9 MPa with ethylene. The 3~ internal temperature peaked at 29°C; a cool water bath was placed around the autoclave body. The reaction was stirred for 16 hr at 23°C and 5.9 MPa and the ethylene was then vented. The autoclave contained a light' 19~
e~ ~ocr~ rTC cuc~T ioi n G 9W

WO 96/23010 ~ 02338526 2001-03-O1 ,yellow granular rubber; this was scraped out cf the autoclave and held under high vacuum to yield 29.0 g (15,700 catalyst turnovers) of spongy, non-tacky, rubbery polyethylene which had. good elastic recovery and was very strong; it was soluble in chloroform or chlorobenzene.
The polyethylene was amorphous at room temperature: it exhibited a glass transition temperature of -57°C and a melting endotherm of -16°C
10 (35J/g) by diffeYential scanning calorimetry. On cooling, there was a crystallization exotherm with a maximum at 1°C (35J/g). Upon remelting and recooling the melting endotherm and crystallization exotherm persisted, as did the glass transition. Dynamic 1~ mechanical analysis at lHz showed a tan 8 peak at -51°C
and a peak in the loss modulus E" at -65°C; dielectric analysis at 1000 Hz showed a tan d peak at -35°C. 1H
NMR analysis (CDC13): 86 methyl carbons per 1000 methylene carbons. 13C NMR analysis: branching per 20 1000 CH2: total Methyls (89.3), Methyl (37.2), Ethyl (14), Propyl (6.4), Butyl (6.9), ~m and End Of Chair.
(23.8); chemical shifts were referenced to the solvent:
the high field carbon of 1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography (trichlorcbenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory):
Mn=137,000; Mw=289,000; Mw/Mn=2.10. Intrinsic viscosity (trichlorobenzene, 135°C): 2.565 dL/g.
Absolute molecular weight averages corrected for 30 branching: Mn=196,000; Mw=425,000; Mw/Mn=2.77. Density (determined at room temperature with a helium gas displacement pycnometer): 0.8546 ~ 0.0007 g/cc.
Exarr~le 97 A 49-mg (0.058 mmol) sample of {[(2,6-i-3~ PrPh)2DABMe,]PdCH2CH2C(O)CH3)SbF6 was placed in a 600-mL
Parr~ stirred autoclave under nitrogen. To this was added 30 mL of dry, deaerated hexane. The autoclave was stirred and pressurized to 5.9 MPa with ethylene.

m icerTi r~ cuG~ gal II F 9R1 The internal temperature peaked briefly at 34°C; a cool water bath was placed around the autoclave body. The reaction was stirred for 16 hr at 23°C. At 14 hr, the ethylene feed was shut off; the autoclave pressure 5 dropped to 5.8 MPa over 2 hr; the ethylene was then vented. The autoclave contained a light yellow, gooey rubber swollen with hexane, which was scraped out of the autoclave and held under high vacuum to yield 28.2 g (17,200 catalyst turnovers) of spongy, non-tacky, 10 rubbery polyethylene which had good elastic recovery and which was very strong.
The polyethylene was amorphous at room temperature: it exhibited a glass transition temperature of -61°C and a melting endotherm of -12°C
l~ (27J/g) by differential scanning calorimetry. Dynamic mechanical analysis at 1Hz showed a tan d peak at -52°C
and a peak in the loss modulus E" at -70°C; dielectric analysis at 1000 Hz showed a tan d peak at -37°C. 1H
NMR analysis (CDC13): 93 methyl carbons per 1000 ?0 methylene carbons. 13C NMR analysis: branching per 1000 CH2: total Methyls (95.4), Methyl (33.3), Ethyl (17.2), Propyl (5.2), Butyl (10.8), Amyl (3.7), >_Hex and End Of Chain (27.4); chemical shifts were referenced to the solvent: the high field carbon of s 1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=149,000; Mw=347,000;
Mw/Mn=2.33. Density (determined at room temperature 30 with a helium gas displacement pycnometer): 0.8544 ~
0.0007 g/cc.
Example 98 Approximately 10-mesh silica granules were dried at 200°C and were impregnated with a methylene chloride 3~ solution of { [ (2 , 6-i-PrPh) ZDABMez] PdCH2CHzC (O) CH3 } SbFE
to give a 10 wt% loading of the catalyst on silica.
A 0.53-g (0.063 mmol) sample of silica gel containing 10 wt% {[(2,6-i-e~i ~enn~ ~e ~ueeT !C71 II G ~R1 WO 96/23010 ~ 02338526 2001-03-O1 p~/pg96/01282 PrPh) zDABMe~) PdCH2CH2C (O) CH3 } SbFS was placed in a 600-mL
ParrO stirred autoclave under nitrogen. To this was added 40 mL of dry, deaerated hexane. The autoclave was stirred and pressurized to 5.5 MPa with ethylene;
the ethylene feed was then turned off. The internal temperature peaked briefly at 31°C. The reaction was stirred for 14 hr at 23°C as the pressure dropped to 5.3 MPa; the ethylene was then vented. The autoclave contained a clear, yellow, gooey rubber swollen with 10 hexane. The product was dissolved in 200 mL
chloroform, filtered through glass wool, rotary evaporated, and held under high vacuum to yield 7.95 g (4500 catalyst turnovers) of gummy, rubbery polyethylene. 1H NMR analysis (CDC13): 96 methyl 1~ carbons per 1000 methylene carbons. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=6,900; Mw=118,000;
Mw/Mn=17.08.
20 Example 99 A 108-mg (0.073 mmol) sample of {[(2,6-i-PrPh)zDABMe2]PdCHzCH2C(O)CH3?BAF was placed in a 600-mL
Parr~ stirred autoclave under nitrogen. To this was added via syringe 75 mL of deaerated reagent grade methyl acrylate containing 100 ppm hydroquinone monomethyl ether and 100 ppm of phenothiazine. The autoclave was pressurized to 5.5 MPa with ethylene and was stirred at 35°C as ethylene was continuously fed for 90 hr; the ethylene was then vented. The product 30 consisted of a swollen clear foam wrapped around the impeller; 40 mL of unreacted methyl acrylate was poured off the polymer. The polymer was stripped off the impeller and was held under high vacuum to yield 38.2 g e~ clear, grayish, somewhat-tacky rubber. 1H NMR
3~ analysis (CDC13): 99 methyl carbons per 1000 methylene carbons. Comparison of the integrals of the ester methoxy (3.67ppm) and ester methylene (~i2COOMe;
2.30ppm) peaks with the integrals of the carbon chain r.r m,r.~m, rrr euerT rm n c ~C~

oethyls (0.8-0.9ppm) and methylenes (1.2-l.3ppm) indicated a methyl acrylate content of 0.9 mol% (2.6 wt%). This product yield and composition represent 18,400 ethylene turnovers and.158 methyl acrylate turnovers. 13C NMR analysis: branching per 1000 CH2:
total Methyls (105.7), Methyl (36.3), Ethyl (22), Propyl (4.9), Butyl (10.6), Amyl (4), >_Hex and End Of Chain (27.8), methyl acrylate (3.4); ester-bearing -CH(CH2)nC02CH3 branches as a % of total ester: n>_5 (40.6), n=1,2,3 (2.7), n=0 (56.7); chemical shifts were referenced to the solvent: the high field carbon of 1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography (tetrahydrofuran, 30°C, polymethylmethacrylate reference, results calculated as l~ polymethyimethacrylate using universal calibration theory): Mn=151,000; Mw=272,000; Mw/Mn=1.81.
Example 100 A 62-mg (0.074-mmol) sample of {[(2,6-i-PrPh)2DABMe2jPdMe(Et20)~SbF6 was placed in a 600-mL Parr~ stirred autoclave under nitrogen with 200 mL of deaerated aqueous 10% (v/v) n-butanol. The autoclave was pressurized to 2.8 MPa with ethylene and was stirred for 16 hr. The ethylene was vented and the polymer suspension was filtered. The product consisted of a fine gray powdery polymer along with some larger particles of sticky black polymer; the polymer was washed with acetone and dried to yield 0.60 g (290 catalyst turnovers) of polyethylene. The gray polyethylene powder was insoluble in chloroform at RT;
it was soluble in hot tetrachloroethane, but formed a gel on cooling to RT. 1H NMR analysis (tetrachloroethane-d2; 100°C): 43 methyl carbons per 1000 methylene carbons. Differential scanning calorimetry exhibited a melting point at 89°C (78J/g) with a shoulder at 70°C; there was no apparent glass transition.

ct tacTtTt tTF ~HFFT lRl 1l E 261 WO 96123010 ~ 02338526 2001-03-O1 pCT/US96/01282 A 78-mg (0.053-mmol) sample of ([(2,6-i-PrPh)~DABMez]PdCHzCH2C(O)CH3}BAF was placed in a 600-mL
ParrO stirred autoclave under nitrogen. To this was added 40 mL of dry, deaerated t-butyl acrylate containing 100 ppm hydroquinone monomethyl ether. The autoclave was pressurized with ethylene to 2.8 MPa and was stirred and heated at 35°C as ethylene was continuously fed at 2.8 MPa for 24 hr; the ethylene was then vented. The product consisted of a yellow, gooey 10 polymer which was dried under high vacuum to yield 6.1 g of clear, yellow, rubbery ethylene/t-butyl acrylate copolymer which was quite tacky. 1H NMR analysis (CDC13): 102 methyl carbons per 1000 methylene carbons.
Comparison of the integral of the ester t-butoxy (1.44 Is ppm) peak with the integrals of the carbon chain methyls (0.8-o.9ppm) and methylenes (1.2-l.3ppm) indicated a t-butyl acrylate content of 0.7 mol% (3.3 wta). This yield and composition represent 3960 ethylene turnovers and 30 t-butyl acrylate turnovers.
20 Gel permeation chromatography (tetrahydrofuran, 30°C, polymethylmethacrylate reference, results calculated as polymethylmethacrylate using universal calibration theory): Mn=112,000; Mw=179,000; Mw/Mn=1.60.
EX~~n 1 a 10 2 2~ A 19-mg (0.022-mmol) sample of [ (2, 6-i-PrPh) 2DABMe2] PdCH~CH2C(O) CH3}SbF6 was placed in a 600-mL ParrO stirred autoclave under nitrogen. The autoclave was pressurized to 5.2 MPa with ethylene and was stirred for 2 hr; the ethylene feed was then shut 30 off. The autoclave was stirred for 16 hr more as the ethylene pressure dropped to 5.0 MPa; the ethylene was then vented. The autoclave contained a light yellow, granular sponge rubber growing all over the walls and head of the autoclave; this was scraped out to yield 3~ 13.4 g (21,800 catalyst turnovers) of spongy, non-tacky, rubbery polyethylene which was very strong and -elastic. 1H NMR analysis (CDC13): 90 methyl carbons per 1000 methylene carbons.

m ~ec~~ tTC cN~CT rCti 11 F 9R1 WO 96123010 CA 02338526 2001-03-O1 PCT/i;~S96!01'_82 Ciz=erent_a'_ scar...~.i~J cal orimetry ex:.ibiteo a class transit_o~ at -50°C. Gel permeation ,...romatography (tric'.~.lcrobenzene, 135°C, polystyre:~e reference, resul_s calculated as polyethyle_~.e using un_ve=sa= c.1 i.,_~:.ic.. tspry) : h'; =i75, OCC; h~w=4 70', C~,~, bi~"r,~ M;, = 2 . 7 2 .
--, '. ° - ~ 7 . A 70-mg (0.047-mmoi) sample of (((2,6-i-=rPh) ~O."~~.~"e_) ?dC:i_C:i~C (O) C~3 ~BF~~' was placed in a 600--_ _ ~_r0 s=irred au=cc'_ave under r:itroge::. To this was a~dea 70 mL o~ deaerated reagent grade methyl acrylat~
contai::ing lOC ppm each hydroquinone monomethyl ether a.~.pa~ot:.iazine and 0.7 mL (I wt%; 4.7 mol%) d=a~ra~e~, deior.ized water. The autoclave was stirs=
1~ Gt 35°C ~s ethylene was continuously fed at 4.8 M?a ..._ 16 hr; tae ethylene was then vented. The product consisted of a clear solution. Rotary evaporation yielcec 1.45 g o. ethylene/methyl acrylate copolymer as a clear oil. T::e i.~.frared spectrum of the product ex'.~.=b=ted a strong ester carbonyl stretch at 1740cm-'-.
:T uMR analysis (CDC13): 1I8 methyl carbons per 1000 metl:yle.~.e carbons. Comparison o~ the intecrals c. th=_ es ter me thoxy ( 3 . 67ppm) and ester methyl ene (;~ 2COO~:e ;
2.30pp-:i Deaks with the integrals of the carbon chaff.-.
~~ met'.'_~_v_s ;0.8-0.9ppm) and methvienes (1.2-~..3ppm) ..~.~ica~ec a methyl acryiate content of 0.7 moi% (2.2 wto). _..is product yield and composition represent 1090 et'.~.yle.~.e turnovers and a methyl acrylate t~,:rnovers. Gel permeation chromatography ,__ic::_orobenze.~.e, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory): Mn=362; Mw=908; Mw/Mn=2.51.
=.X3',.~.a _° ~ ~G
?, =_-mg (C.C3o-mmol) sample cf (((2,6-.
~~ ?r?h) _D~-3:fe~J ?dC'.-'_ ::2C (O) Ca3)BTyR was piace3 in a 6G0-rL
?arrU stirred autoclave under nitrogen. To this was added 100 mL o~ cry, deaerated methylene chloride. The a~tOCl atle w3S :i,'..~,'.erSed =r. a Cool water bail: and Stlrre.~.

r."..~T,~r, rr- cu~tT roi ii C ~~1 . , . , , .. " ,.
as it was pressurized to 4.8 MPa with ethyhene.
Ethylene was continuously fed with stirring at 4.8 MPa and 23°C for 23 hr; the ethylene then was vented. The product consisted of a clear rubber, slightly swollen with methylene chloride. The polymer was dried under high vacuum at room temperature to yield 34.5 g (34,100 Catalyst turnovers) of clear rubbery polyethylene. 1H
NMR analysis (CDC13): 110 methyl carbons per 1000 methylene carbons. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : Mn=243, 000; M~"~=676, 000;
Mw/Mri=2.78.
Example 104A
A 83-mg (0.056-mmol) sample of {((2,6-i-PrPh) 2DABMe2) PdCH2CH2C (O) CH3}BAF was placed in a 600-mL
Parr~ stirred autoclave under nitrogen. To this was added 70 mL of dry, deaerated, ethanol-free chloroform.
The autoclave was immersed in a cool water bath and stirred as it was pressurized to 4.7 MPa with ethylene.
Ethylene was continuously fed with stirring at 4.7 MPa and 23°C for 21 hr; the ethylene then was vented. The product consisted of a pink, rubbery, foamed polyethylene, slightly swollen with chloroform. The polymer was dried under vacuum at 40°C to yield 70.2 g '-(94,400 catalyst turnovers) of pink, rubbery polyethylene which was slightly tacky. 1H NMR analysis (CDC13): 111 methyl carbons per 1000 methylene carbons.
Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory):
Mn=213,000; Mw=728,000; Mw/Mn=3.41.
Example 105 A 44-mg (0.052-mmol) sample of {[(2,6-1-PrPh) 2DABMe2] PdCHZCHZC (O) CH3}SbF6 was magnetically stirred under nitrogen in a 50-mL Schlenk flask with 20 mL of dry, deaerated methylene chloride. To this was added 5 mL (5.25 g; 73 mmol) of freshly distilled AMENDED SHEET

WO 96/23010 CA 02338526 2001-03-O1 PCT'/US96/01282 ,acrylic acid (contains a few ppm of phenothiazine as a radical polymerization inhibitor) via syringe and the mixture was immediately pressurized with ethylene at 5.52 kPa and stirred for 40 hr. The dark yellow solution was rotary evaporated and the residue was stirred with 50 mL water for 15 min to extract any acrylic acid homopolymer. The water was drawn off with a pipette and rotary evaporated to yield 50 mg of dark residue. The polymer which had been water-extracted was heated under- high vacuum to yield 1.30 g of ethylene/acrylic acid copolymer as a dark brown oil.
The infrared spectrum showed strong COOH absorbances at 3400-2500 and at 1705cm-1, as well as strong methylene absorbances at 3000-2900 and 1470cm-1.
A 0.2-g sample of the. ethylene/acrylic acid copclymer was treated with diazomethane in ether to esterify the COON groups and produce an ethyiene/methyl acrylate copolymer. The infrared spectrum of the esterified copolymer showed a strong ester carbonyl abscrbance at 1750cm'l; the COOH absorbances were gone.
1H NMR analysis (CDC13): 87 methyl carbons per 1000 methylene carbons. Comparison of the integrals of the ester methoxy (3.67ppm) and ester methylene (.~2COOMe;
2.30ppm) peaks with the integrals of the carbon chain methyis (0.8-0.9ppm) and methylenes (1.2-l.3ppm) indicated a methyl acrylate content of 5.3 molo (14.7 wt% methyl acrylate => 12.3 wt% acrylic acid in the original copolymer). This product yield and composition represent 780 ethylene turnovers and 43 acrylic acid turnovers. Gel permeation chromatography (tetrahydrofuran, 30°C, polymethylmethacrylate reference, results calculated as polymethylmethacrylate usir.~ universal calibration theory): Mn=25,000;
Mw°e2,800; Mw/Mn=1.71.
Listed below are the 13C NMR data upon which the above analysis is based.
13C ~ Data CDC13, 0.05M CrAcAc, 30C
Freq ppm Intensity SUBSTITUTE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96101282 51.0145 24.9141 45.434 1.11477 MEBo 38.8925 2.29147 38.5156 6.51271 37.3899 10.7484 37.0713 17.3903 36.7634 17.6341 36.4182 3.57537 36.2961 6.0822 34.459 2.158 34.0289 9.49713 33.7369 34.4456 33.3705 49.2646 32.8926 18.2918 32.3935 10.5014 32.0271 3.5697 3B5 31.5705 30.6837 3B6+, 3EOC

31.1723 1.54526 29.813 46.4503 29.3511 117.987 29.1387 21.034 28.9953 30.6D3 28.613 7.18386 27.2007 8.02265 26.744 23.8731 26.3777 46.8498 26.006 5.42389 25.5547 8.13592 25.0609 5.46013 2 EB4(tentative) 24.9175 2.30355 2 EB4(tentative) 24.6042 15.7434 2 EB5+

23.7547 2.78914 23.3777 5.63727 22.7936 8.07071 2B4 22.6768 3.78032 284 22.3211 33.1603 285+, 2EOC

19.3477 15.4369 1B1 18.8645 5.97477 1B1 14.1814 1.99297 1B3 13.7407 38.5361 1B4+, lEOC

11.0274 6.19758 182 10.5124 10.4707 1B2 176.567 9.61122 EBp carbonyl 174.05 9.03673 EB1+ carbonyl 173.779 85.D21 EB1+ carbonyl Fxam~ 106 A 25-mg (0.029-mmol) sample of {[(2,6-i-PrPh)ZDABMe2]PdCH2CHzC(O)CH3}SbF6 was magnetically stirred under 55.2 kPa of ethylene in a 50-mL Schlenk flask with 20 mL of dry methylene chloride and 5 mL
(4.5 g; 39 mmol) of methyl 4-pentenoate for 40 hr at room temperature. The yellow solution was rotary enacm~ tTF RHFFT (Rt 1LE 261 evaporated to yield 3.41 g of ethylene/methyl 4-pentenoate copolymer as a yellow oil. The infrared spectrum of the copolymer showed a strong ester carbonyl absorbance at 1750cm-1. 1H NMR analysis (CDC13): 84 methyl carbons per 1000 methylene carbons.
Comparison of the integrals of the ester methoxy (3.67ppm) and ester methylene (~2COOMe; 2.30ppm) peaks with the integrals of the carbon chain methyls (0.8-0.9ppm) and methylenes (1.2-l.3ppm) indicated a methyl 4-pentenoate content of 6 mol% (20 wt%). This yield and composition represent about 3400 ethylene turnovers and 200 methyl 4-pentenoate turnovers. 13C NMR
auantitative analysis: branching per 1000 CH2: total Methyis (93.3), Methyl (37.7), Ethyl(18.7), Propyl (2), 1~ Butyl (8.6), ?Am and end of chains (26.6), >_Bu and end of chains (34.8); ester-bearing branches -CH(CH2)nCOzCH3 as a % of total ester: n>_5 (38.9), n=4 (8.3), n=1,2,3 (46.8), n=0 (6); chemical shifts were referenced to the solvent: chloroform-dl (77 ppm). Gel permeation chromatography (tetrahydrofuran, 30°C, polymethylmethacrylate reference, results calculated as polymethylmethacrylate using universal calibration theory): Mn=32,400; Mw=52,500; Mw/Mn=1.62.
Example 107 A 21-mg (0.025-mmol) sample of ~[(2,6-i-PrPh) ZDABMe~] PdCH~CH~C (O) CH3 ~SbF6 was magnetically stirred under nitrogen in a 50-mL Schlenk flask with 5 mL of dry methylene chloride and 5 mL (4.5 g; 39 mmol) of methyl 4-pentenoate for 74 hr. The yellow solution was rotary evaporated to yield 0.09 g of a yellow oil, poly[methyl 4-pentenoate). The infrared spectrum showed a strong ester carbonyl absorbance at 1750cm-1.
The 1H NMR (CDC13) spectrum showed olefinic protons at 5.4-5.5ppm; comparing the olefin integral with the 3~ integral of the ester methoxy at 3.67ppm indicates an average degree of polymerization of 4 to 5. This example demonstrates the ability of this catalyst to StJBSTtTtJTE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 PCTIUS96/01282 '~omopoiymerize alpha olefins bearing pol~~'~Pictlonal groups not conjugated to the carbon-carbon double bond.
Example 108 A 53-ma (0.063-mmol) sample of {[(2,6-i-PrPh)2DABMe-]PdCH2CH2C(O)CH3}SbF6 was placed in a 600-mL
Parr~ stirred autoclave under nitrogen. To this was .' added 25 mL of dry, deaerated toluene and 25 mL (26 g;
0.36 mol) cf freshly distilled acrylic acid containing about 1~0 npm phenothiazine. The autoclave was 10 pressurized to 2.1 MPa with ethylene and was stirred for 68 hr Gt 23°C; the ethylene was then vented. The autoclave contained a colorless, hazy solution. The solution was rotary evaporated and the concentrate was taken up in 50 mL of chloroform, filtered through 1~ diatomaceous earth, rotary. evaporated, and then held under high vacuum to yield 2.23 g of light brown, very viscous liquid ethylene/acrylic acid copolymer. The infrared spectrum showed strong COOH absorbances at 3400-2500 and at 1705cm-1, as well as strong methylene 20 absorbances at 3000-2900 and 1470cm-1.
A 0.3-g sample of the ethylene/acrylic acid copolymer was treated with diazomethane in ether to esterify the COOH groups and produce an ethylene/methyl acrylate copolymer. The infrared spectrum showed a strong ester carbonyl absorbance at 1750cm-1; the COOH
absorbances were gone. 1H NMR analysis (CDC13): 96 methyl carbons per 1000 methylene carbons. Comparison of the integrals of the ester methoxy (3.67ppm) and ester methylene (~i2COOMe; 2.30ppm) peaks with the 30 integrals of the carbon chain methyls (0.8-0.9ppm) and methylenes (1.2-l.3ppm) indicated a methyl acrylate content of 1.8 mol% (5.4 wt% methyl acrylate => 4.5 wto acrylic acid in the original copolymer). This product yield and composition represent 1200 ethylene turnovers 35 and 22 acrylic acid turnovers. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using ~1 iR~TtTt 1TE SHEET (RULE 26) sniversal calibration theory): Mn=5,330; fiW=i~,000;
Mw/Mn=2.82.
Exam~lA 10 A 600-mL stirred Parr~ autoclave was sealed and S flushed with nitrogen. Fifty mL (48 g; 0.56 mel) of dry, deaerated methyl acrylate was introduced into the autoclave via gas tight syringe through a port on the autoclave head. Then 60 mg (0.07 mmol) of {((2,6-i-PrPh)~DABMe~)PdMe(Et20)}BAF was introduced into the autoclave in the following manner: a 2.5-mL gas tight syringe with a syringe valve was loaded with 60 mg of ([(2,6-i-PrPh):DABMe2)PdMe(EtzO)}BAF under nitrogen in a glove box; then 1 mL of dry, deaerated methviene chloride was drawn up into the syringe and the contents I~ were quickly infected into. the autoclave through a head port. This method avoids having the catalyst in solution with no stabilizing ligands.
The autoclave body was immersed in a running tap water bath; the internal temperature was very steady at 22°C. The autoclave was pressurized with ethvlene to 2.8 MPa and continuously fed ethylene with stirring for 4.5 hr. The ethylene was then vented and the product, a mixture of methyl acrylate and yellow gooey polymer, was rinsed out of the autoclave with chloroform, rotary evaporated, and held under high vacuum overnia_ht to yield 4.2 g of thick, light-brown liquid ethylene/methyl acrylate copolymer. The infrared spectrum of the product exhibited a strong ester carbonyl stretch at 1740cm-1. 1H NMR analysis (CDC13):
82 methyl carbons per 1000 methylene carbons.
Comparison of the integrals of the ester methoxy (3.67ppm) and ester methylene (~2COOMe; 2.30ppm) peaks with the integrals of the carbon chain methyls (0.8-0.9ppm) and methylenes (1.2-_.3ppm) indicated a methyl 3S acrylate content of 1.5 m01% (4.4 wto). This product yield and composition represent 2000 ethylene turnovers and 31 methyl acrylate turnovers. 13C NMR analysis:
branching per 1000 CH2: total Methyls (84.6), Methyl SI IRSTITI tTE SHEET (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 pCT/US96101282 ( 2 8 . 7 ) , Ethyl ( 15 . 5 ) , Propyl ( 3 . 3 ) , Butyl ( 8 .-2 ) , ?riex and End Of Chain (23.9), methyl acrylate (13.9). Ester-bearing -CH(CH2)nC02CH3 branches as a % of total ester:
n?5 (34.4), n=4 (6.2), n=1,2,3 (13), n=0 (46.4). Molex:
ethylene (97.6), methyl acrylate (2.4); chemical shifts were referenced to the solvent: the high field carbon of 1,2,4-trichlorobenzene (127.8 ppm). Gel permeation chromatography (tetrahydrofuran, 30°C, polymethylmethacrylate reference, results.calculated as 10 polymethylmethacrylate using universal calibration theory): Mn=22,000; Mw=45,500; Mw/Mn=2.07.
A mixture of 1.45 g of this ethylene/methyl acrylate copolymer, 20 mL dioxane, 2 mL water, and 1 mL of 50% aqueous NaOH was magnetically stirred a~
l~ reflux under nitrogen for 4.5 hr. The liquid was then decanted away from the swollen polymer and the polymer was stirred several hours with three changes of bciling water. The polymer was filtered, washed with water and methanol, and dried under vacuum (80°C/nitrogen purge) 20 to yield 1.2 g soft of ionomer rubber, insoluble in hot chloroform. The FTIR-ATR spectrum of a pressed film (pressed at 125°C/6.9 MPa) showed a strong ionomer peak at 1570cm-1 and virtually no ester carbonyl at 1750cm-1. The pressed film was a soft, slightly tacky rubber with about a 50°s elongation to break. This example demonstrates the preparation of an ionomer from this ethylene/methyl acrylate polymer.
Example 110 The complex [(2,6-i-PrPh)2DAHMe2]PdMeCl (0.020 g, 30 0.036 mnol) was weighed into a vial and dissolved in 6 ml CH2C12. NaBAF (0.032g, 0.036 mmol) was rinsed into the stirring mixture with 4 ml of CH2C12. There was an immediate color change from orange to yellow. The solution was stirred under 6.2 MPa ethylene in a Fisher 3, Porter tube with temperature control at 19°C. The internal temperature rose to 22°C during the first 15 minutes. The temperature controller was raised tc 30°C. After 35 minutes, the reaction was consuming ci ~aeTt~ tT~ ~HFFT (RULE 261 :thylene slowly. After a total reactior.~ tifie oz about 20 h, there was no longer detectable ethylene consumption, but the liquid level in the tube was noticeably higher. Workup by addition to excess MeOH
5 gave a viscous liquid precipitate. The precipitate was redissolved in CH2C12, filtered through a 0:5 micron PTFE filter and reprecipitated by addition to excess MeOH to give 7.208 g dark brown viscous oil (718C
equivalents of ethylene per Pd). 1H NMR (CDC13) 0.8-10 1.0 (m, CH3); 1.0-1.5 (m, CH and CH2). Integration allows calculation of branching: 118 methyl carbons per 1000 methylene carbons. GPC in THF vs. PMMA standard:
Mn=12,700, Mw=28,800, Mw/Mn=2.26.
Example 111 1~ The solid complex {[(2,6-i-PrPh)~DABMe2]PdMe(Et~O)?SbF6 (0.080 g, 0.096 mmol) was placed in a Schlenk flask which was evacuated and refilled with ethylene twice. Under one atm of ethylene, black spots formed in the center of the solid 20 complex and grew outward as ethylene was polymerized in the solid state and the resulting exotherm destroyed the complex. Solid continued to form on the solid catalyst that had not been destroyed by the exotherm, and the next day the flask contained considerable solid '~ and the reaction was still slowly consuming ethylene.
The ethylene was disconnected and 1.808 g of light gray elastic solid was removed from the flask (644 equivalents ethylene per Pd). The 1H NMR in CDC13 was similar to example 110 with 101 methyl carbons per 1000 30 methylene carbons. Differential Scanning Calorimetry (DSC): first heat 25 to 150°C, 15°C/min, no events;
second heat -150 to 150°C, Tg = -53°C with an endothermic peak centered at -20°C; third heat -15o to 275°C, Tg = -51°C with an endothermic peak centered at 3~ -20°C. GPC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory): Mn=13,000 Mw=313,000 Mw/Mn=24.

c1 iee~r tTC cu~~T rW n F X61 WO 96123010 ~ 02338526 2001-03-O1 pCT/US96/01282 Example ~1 The complex { [ (2, 6-i-PrPh) ZDABMe~] PdMe (Et20) }SbF6 (0.084 g, 0.100 mmol) was loaded into a Schlenk flask in the drybox followed by 40 ml of dry dioxane. The septum-capped flask was connected to a Schlenk line and the flask was then briefly evacuated and refilled with ethylene. The light orange mixture was stirred under an ethylene atmosphere at slightly above 1 atm by using a mercury bubbler. There was rapid uptake of ethylene.
10 A room temperature water bath was used to control the temperature of the reaction. After 20 h, the reaction was worked up by removing the solvent in vacuo to give 10.9 g of a highly viscous fluid (3870 equivalents of ethylene per Pd). Dioxane is a solvent for the Pd 1~ complex and a non-solvent.for the polymer product. 1H
NMR (CDC13) 0.8-1.0 (m, CH3); 1.0-1.5 (m, CH and CH2).
Integration allows calculation of branching: 100 methyl carbons per 1000 methylene carbons. GPC
(trichlorobenzene, 135°C, polystyrene reference, 20 results calculated as linear polyethylene using universal calibration theory): Partially resolved trimodal distribution with Mn=16300, Mw=151000 Mw/Mn=9.25. DSC (second heat,-150°C to 150°C, 15°C/min) Tg=-63°C, endothermic peak centered at -30°C.
Example ~~
Polymerization of ethylene was carried out according to example 112, using pentane as solvent.
Pentane is a non-solvent for the Pd complex and a 30 solvent for the polymer product. The reaction gave 7.47 g of dark highly viscous fluid (2664 equivalents of ethylene per Pd). 1H NMR analysis (CDC13): 126 methyl carbons per 1000 methylene carbons. 13C NMR
analysis, branching per 1000 CH2: Total methyls (128.8), Methyl (37.8), Ethyl (27.2), Propyl l3.5), Butyl l14.5), Amyl (2.5), ?Hexyl and end of chain (44.7), average number of carbon atoms for ?Hexyl branches = 16.6 (calculated from intrinsic viscosity Sl)BSTiTLITE SHEET (RULE 26) and GPC molecular weight data). Quantitation of the -CH2CH(CH3)CH2CH3 structure per 1000 CH2's: 8.3. These side chains are counted as a Methyl branch and an Ethyl branch in the quantitative branching analysis. GPC
(trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory): Mn=9,800, Mw=16,100, Mw/Mn=1.64. Intrinsic viscosity (trichlorobenzene, 135°C) - 0.125 g/dL. Absolute molecular weights calculated by GPC (trichlorobenzene, 135°C, polystyrene reference, corrected for branching using measured intrinsic viscosity): Mn=34,900, Mw=58,800, Mw/Mn=1.68.
DSC (second heat, -150°C to 150°C, 15°C/min) Tg = -71°C, endothermic peak centered at -43 °C.
1J Rxamn~e 114 Polymerization of ethylene was carried out according to example 112, using distilled degassed water as the medium. Water is a non-solvent for both the Pd complex and the polymer product. The mixture was worked up by decanting the water from the product which was then dried in vacuo to give 0.427 g of dark sticky solid (152 equivalents of ethylene per Pd). 1H
NMR analysis (CDC13): 97 methyl carbons per 1000 methylene carbons. GPC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory):
Mn=25,100, Mw=208,000, Mw/Mn=8.31.
ample 115 Polymerization of ethylene was carried out according to example 112, using 2-ethylhexanol as the solvent. The Pd complex is sparingly soluble in this solvent and the polymer product is insoluble. The polymer product formed small dark particles of high viscosity liquid suspended in the 2-ethylhexanol. The solve~.t was decanted and the polymer was dissolved in CHC13 and reprecipitated by addition of excess MeOH.
The solvent was decanted, and the reprecipitated polymer was dried in vacuo to give 1.66 g of a dark cttacTt~ rr~ cN~cT SRI II F ?61 WO 96/23010 ~ 02338526 2001-03-O1 pCT/US9G/01282 ;.ighly viscous fluid (591 equivalents of ethylene per Pd). 1H NMR analysis (CDC13): 122 methyl carbons per 1000 methylene carbons. GPC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear 5 polyethylene using universal calibration theory):
Mn=7,890, Mw=21,600, Mw/Mn=2.74.
$xample 116 The solid complex {[(2,6-i-PrPh) zDABMe~] PdMe (EtzO) )SbF6 (0.084 g, 0.100 mmol) was 10 loaded into a Schlenk flask in the drybox. The flask was connected to a Schlenk line under 1 atm of ethylene, and cooled to -78°C. Solvent,(CH2C12, 40 ml) was added by syringe and after equilibrating at -78°C
under ethylene, the mixture was warmed to room I~ Temperature under ethylene: The mixture was shirred under an ethylene atmosphere at slightly above 1 atm by using a mercury bubbler. There was rapid uptake of ethylene. A room temperature water bath was used to control the temperature of the reaction. After 24 h, 20 the reaction was worked up by removing the solvent in vacuo to give 24.5 g of a highly viscous fluid (8730 equivalents of ethylene per Pd). CH2C12 is a good solvent for both the Pd complex and the polymer product. The polymer was dissolved in CH2C12, and reprecipitated by addition to excess MeOH in a tared flask. The solvent was decanted, and the reprecipitated polymer was dried in vacuo to give 21.3 g of a dark highly viscous fluid. 1H NMR analysis (CDC13): 105 methyl carbons per 1000 methylene carbons.
30 C-13 NMR analysis, branching per 1000 CH2: Total methyls (118.6), Methyl (36.2), Ethyl (25.9), Propyl (2.9), Butyl (11.9), Amyl (1.7), ?Hexyl and end of chains (34.4), average number of carbon atoms for >_ Hexyl branches = 22.5 (calculated from intrinsic 3~ viscosity and GPC molecular weight data). Quantitation of the -CH2CH(CH3)CH2CH3 structure per 1000 CHz's: 8.1.
These side chains also counted as a Methyl branch and an Ethyl branch in the quantitative branching analysis.
?12 et rneTtTl tTC CNCCT IRI II F ~Rl WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96l01282 3PC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory): Mn=25,800, Mw=45,900, Mw/Mn=1.78. Intrinsic viscosity (trichlorobenzene, 5 135°C) - 0.24 g/dL. Absolute molecular weights calculated by GPC (trichlorobenzene, 135°C, polystyrene reference, corrected for branching using measured intrinsic viscosity): Mn=104,000, Mw=188,000, Mw/Mn=1.81.
10 Listed below are the 1'C NMR data upon which the above analysis is based.

SI IRRTIT11TE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 13C ~R
Data TCB, 120C, 6M CrAcAc 0.0 Freq ppm Intensity 39.7233 5.12305 39.318 17.6892 MB2 38.2022 17.9361 MB3+

37.8369 32.3419 MB3+

37.2469 43.1136 a81, 383 36.8335 10.1653 aBl, 383 36.7452 14.674 a81, 383 34.9592 10.3554 ay+B, (484, etc.) 585, 34.6702 24.015 ay+B, (4B4, etc.) 5B5, 34.5257 39.9342 ay+B, (4B4, etc.) 585, 34.2006 109.158 ay+B, (484, etc.) 5B5, 33.723 36.1658 ay+B, (4B4, etc.) 5B5, 33.3136 12.0398 MB1 32.9323 20.7242 MB1 32.4266 6.47794 3B5 31.9409 96.9874 3B6+, 3EOC

31.359 15.2429 y+y+B, 384 31.09E1 19.2981 ,i+y+B, 3B4 30.6606 15.8689 y+y+B, 3B4 30.2271 96.7986 -f+y+B, 384 30.1188 54.949 y+y+B, 3B4 29.7455 307.576 y+y+B, 3B4 29.5809 36.2391 y+y+B, 384 29.3361 79.3542 y+y+B, 384 29.2157 23.0783 y+y+B, 3B4 27.6424 24.2024 py+B, 282,(485,etc.) 27.526 29.8995 py+B, 2B2,(485,etc.) 27.3534 23.1626 py+B, 2B2,(4B5,etc.) 27.1607 70.8066 ~iy+B, 282,(4B5,etc.) 27.0042 109.892 py+B, 2B2,(4B5,etc.) 26.5908 7.13232 ~iy+B, 2B2,(4B5,etc.) 26.3941 23.945 py+B, 2B2,(485,etc.) 25.9446 4.45077 py+B, 2B2,(4B5,etc.) 24.4034 9.52585 p~3B

24.2428 11.1161 ppB

23.139. 21.2608 284 23.0227 11.2909 2B4 22.6494 103.069 2B5+, 2EOC

20.0526 5.13224 2B3 19.7355 37.8832 181 19.2017 14.8043 181, Structure XXVII

14.4175 4.50604 1B3 13.9118 116.163 1B4+, lEOC

11.1986 18.5867 182, Structure XXVII

10.9617 32.3855 1B2 c~ ~ocTt~ rrF ~N~~T IRlILE 261 Fxamola ~
Polymerization of ethylene was carried out according to example 116, at a reaction temperature of 0°C and reaction time of several hours. The polymer product formed a separate fluid phase on the top of the mixture. The reaction was quenched by adding 2 ml acrylonitrile. The product was moderately v=scous fluid, 4.5 g (1600 equivalents of ethylene per Pd). 1H
NMR analysis (CDC13): 108 methyl carbons.per 1000 methylene carbons. 13C NMR analysis, branching per 1000 CH2: Total methyls (115.7), Methyl (35.?), Ethyl (24.7), Propyl (2.6), Butyl (11.2), Amyl (3.2), >_Hexyl and end of chain (37.1). Quantitation of the -CHZCH(CH3)CH2CH3 structure per 1000 CH2's: 7.~. These I~ side chains are counted as a Methyl branch and an Ethyl branch in the quantitative branching analysis. GPC
(trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory: Mn=15,200, Mw=23,700, Mw/Mn=1.56.
Rxay?1 a ~ ~ 8 The Pd complex ([(2,6-i-PrPh) zDABMe2] PdCH2CH2CH2C (O) OCH~ } SbF6 ( 0 . 084 g, 0 . 100 mmol) was loaded into a Schlenk flask in the drybox, and 40 ml of FC-75 was added. ~'he septum-capped flask was connected to a Schlenk line and the flask was then briefly evacuated and refilled with ethylene from the Schlenk line. The mixture was stirred under an ethylene atmosphere at slightly above 1 atm by using a mercury bubbler. Both the Pd initiator and the polymer are insoluble in FC-75. After 15 days, the reaction flask contained a large amount of gray elastic solid.
The FC-75 was decanted, and the solid polymer was then dissolved in CHC13 and precipitated by addition of the solution to excess MeOH. The polymer was dried in vacuo, and then dissolved in o-dichlorobenzene at 100°C. The hot solution was filtered through a 10 ~m FTFE filter. The filtered polymer solution was shaken 21~
CIIRCTtTItTF RHFFT fR111 F 261 WO 96123010 cA 02338526 2001-03-O1 p~'/US96101282 ,~n a separatory funnel with concentrated sulfuric acid, followed by distilled water, followed by 5% NaHC03 solution, followed by two water washes. The polymer appeared to be a milky suspension in the organic layer during this treatment. After washing, the polymer was precipitated by addition to excess MeOH in a blender and dried at room temperature in vacuo to give 19.6 g light gray elastic polymer fluff (6980 equivalents of ethylene per Pd). 1H NMR analysis (CDC13): 112 methyl 10 carbons per 100D methylene carbons. 13C NMR analysis, branching per 1000 CH2: Total methyls (114.2), Methyl (42.1), Ethyl (24.8), Propyl (5.1), Butyl (10.2), Amyl (4), >_Hexyl and end of chain (30.3), average number cf carbon atoms for >_Hexyl branches = 14.4 (calculated 1~ from intrinsic viscosity and GPC molecular weight data). GPC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory: Mn=110,000, Mw=265,000, Mw/Mn=2.40. Intrinsic viscosity 20 (trichlorobenzene, 135°C) - 1.75 g/dL. Absolute molecular weights calculated by GPC (trichlorobenzene, 135°C, polystyrene reference, corrected for branching using measured intrinsic viscosity): Mn=214,000, Mw=535,000, Mw/Mn=2.51.
Example 119 Polymerization of ethylene was carried out according to example 112, using the complex {[(2,6-i-PrPh) ~DABMe2] PdCHzCH2CH~C (O) OCH3 } SbF6 l0 . 084 g, 0 . 100 mmol) as the initiator and CHC13 as the solvent. The 30 reaction gave 28.4 g of dark viscous fluid (10,140 equivalents of ethylene per Pd). 1H NMR analysis (CDC13): 108 methyl carbons per 100D methylene carbons.
13C NMR analysis, branching per 1000 CH2: Total methyls (119.5), Methyl (36.9), Ethyl (25.9), Propyl (2.1), 3~ Butyl (11), Amyl (1.9), ?Hexyl and end of chair.
(38.9). GPC (.trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene c~ mc~Tl tTF ~HFFT fRlILE 261 ;.sing universal calibration theory): Mn=10,800, Mw=26,800, Mw/Mn=2.47.
Examt~
Polymerization of ethylene was carried out according to example 112, using the complex [(2,6-i-PrPh) ZDABMe~] PdMe (OSO~CFj) (0. 068g, 0.10 mmol) as the initiator and CHC13 as the solvent. The reaction gave 5.98 g of low viscosity fluid (2130 equivalents of ethylene per Pd). 1H NMR (CDC13) 0.8-1.0 (m, CH3);
10 1.0-1.5 (m, CH and CH2); 1.5-1.7 (m, C~3CH=CH- ); 1.9-2.1 (broad, -C$2CH=CHCj~2- ); 5.3-5.5 (m, -CH=CH- ).
Integration of the olefin end groups assuming one olefin per chain gives Mn = 630 (DP = 24). A linear polymer with this molecular weight and methyl groups at I~ both ends should have 46 methyl carbons per 1000 methylene carbons. The value measured by integration is 161, thus this polymer is highly branched.
Example 12~
Polymerization of ethylene was carried out 20 according to example 112, using the complex {[(2,6-i-PrPh) ~DABHZ] PdCH~CHzCH2C (O) OCH3 } SbF6 ( 0 . 082 g, 0 . 10 mmol ) as the initiator and CHC13 as the solvent. The reaction gave 4.47 g of low viscosity fluid (1600 equivalents of ethylene per Pd). 1H NMR (CDC13) is similar to example 120. Integration of the olefin end groups assuming one olefin per chain gives Mn = 880 (DP
- 31). A linear polymer with this molecular weight and methyl groups at both ends should have 34 methyl carbons per 1000 methylene carbons. The value measured 30 by integration is 156, thus this polymer is highly branched.
Example 122 Polymerization of ethylene was carried out according to example 112, using the complex {[(2,6-i-3~ PrPh) 2DABMe2] PdCH~CH2CH~C (O) OCH3 )BC1 (C6F5) 3 (0 . 116 g, 0.10 mmol) as the initiator and CHC13 as the solvent.
The reaction gave 0.278 g of low viscosity fluid, after correcting for the catalyst residue this is 0.160 g (57 ?l7 SUBSTITUTE SHEET (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 PCT/IJS96I01282 equivalents of ethylene per Pd). Mn estimatea~~
integration of olefin end groups is 300.
Example X23 The complex [(2,6-i-PrPh)zDABMe2]PdMeCl (0.056 g, 0.10 mmol) was loaded into a Schlenk flask in the drybox followed by 40 ml of dry toluene. A solution of ethyl aluminum dichloride (1.37 ml of 0.08 M solution in o-dichlorobenzene) was added while stirring.
Polymerization of ethylene was carried out using this 10 solution according to example 112. The reaction gave 0.255 g of low viscosity fluid, after correcting for the catalyst residue this is 0.200 g (71 equivalents of ethylene per Pd). Mn estimated by integration of olefin end groups is 1300.
1~ Example X24 Methyl acrylate was sparged with argon, dried over activated 4A sieves, passed through activity 1 alumina B in the drybox, and inhibited by addition of 20 ppm phenothiazine. The solid complex {[(2,6-1-20 PrPh) 2DABMez] PdMe (EtzO) }SbFs (0.084 g, 0.100 mmol) was loaded into a Schlenk flask in the drybox. The flask was connected to a Schlenk line under 1 atm of ethylene, and cooled to -78°C. Forty ml of CH2C12 was added by syringe and after equilibrating at -78°C under ethylene, 5 ml of methyl acrylate was added by syringe and the mixture was warmed to room temperature under ethylene. After 40 h, the reaction was worked up by removing the solvent in vacuo to give 3.90 g of moderately viscous fluid. Integration of the 1H NMR
30 spectrum showed that this copolymer contained 6.9 mole % methyl acrylate. No poly(methyl acryiate) homopolymer could be detected in this sample by 1H NMR.
1H NMR shows that a significant fraction of the ester groups are located at the ends of hydrocarbon branches:
35 3.65(s, -C02CH3, area=4.5), 2.3(t, -C$2C02CH3, ester ended branches, area=3), 1.6(m, -C$2CH2C02CH3, ester ended branches, area=3), 0.95-1.55(m, CH and other CH2, area=73), 0.8-0.95(m, CH3, ends of branches or ends of e~ ~acTm m: cu~cT lAl II F 7R1 =hains, area=9.5) This is confirmed by the~i3C NMR
quantitative analysis: Molex: ethylene (93.1), methyl acrylate (6.9), Branching per 1000 CH2: Total methyls (80.2), Methyl (30.1), Ethyl (16.8), Propyl (1.6), Butyl (6.8), Amyl (1.3), >_Hexyl and end of chain (20.1), methyl acrylate (41.3), Ester branches CH(CH2)nCO2CH3 as a o of total ester: n?5 (47.8), n=4 (17.4), n=1,2,3 (26.8), n=0 (8).
GPC of this sample was done in THF vs. PMMA
standards using a dual UV/RI detector. The outputs of the two detectors were very similar. Since the UV
detector is only sensitive to the ester functionality, and the RI detector is a relatively nonselective mass detector, the matching of the two detector outputs 1~ shows that the ester functionality of the methyl acrylate is distributed throughout the entire molecular weight range of the polymer, consistent with a true copolymer of methyl acrylate and ethylene.
A 0.503 g sample of the copolymer was fractionated by dissolving in benzene and precipitating partially by slow addition of MeOH. This type of fractionation experiment is a particularly sensitive method for detecting a low molecular weight methyl acrylate rich component since it should be the most soluble material under the precipitation conditions.
The precipitate 0.349 g, (69°s) contained 6.9 mole o methyl acrylate by 1H NMR integration, GPC (THF, PMMA
standard, RI detector): Mn=19,600, Mw=29,500, Mw/Mn=1.51. The soluble fraction 0.180g (36a) contained 8.3 mole-o methyl acrylate by 1H NMR
integration, GPC (THF, PMMA standard, RI detector):
Mn=11,700, Mw=19,800, Mw/Mn=1.70. The characterization of the two fractions shows that the acrylate content is only slightly higher at lower molecular weights. These results are also consistent with a true copolymer of the methyl acrylate with ethylene.

c~ iacTlTi 1TF ~NFFT !Rl 1l E 26) WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96J01282 Exan~le 125 Methyl acrylate was sparged with argon, dried over activated 4A sieves, passed through activity 1 alumina B in the drybox, and inhibited by addition of 20 ppm phenothiazine. The complex [(2,6-i-PrPh) ZDABMe2] PdMe (OS02CF3) (0.068 g, 0.10 mmol) was loaded into a Schlenk flask in the drybox, and 40 ml of CHC13 was added followed by 5 ml of methyl acrylate..
The septum capped flask was connected to a Schlenk line 10 and the flask was then briefly evacuated and refilled with ethylene from the Schlenk line. The light orange mixture was stirred under an ethylene atmosphere at slightly above 1 atm by using a mercury bubbler. After 20 h, the reaction was worked up by removing the l~ solvent and unreacted methyl acrylate in vacuo to give 1.75 g of a low viscosity Copolymer.
13C NMR quantitative analysis: Molex: ethylene (93), methyl acrylate (7), Branching per 1000 CH2:
Total methyls (100.9), Methyl (33.8), Ethyl (19.8), 20 Propyl (1.9), Butyl (10.1), Amyl (7.3), ?Fiexyl and end of chains (28.4), methyl acrylate (41.8). This sample is low molecular weight - total methyls does not . include end of chain methyls. Ester branches -CH(CH2)nC02CH3 as a % of total ester: n?5 (51.3), n=4 (18.4), n=1,2,3 (24), n=0 ( 6.3).
Example 126 Ethylene and methyl acrylate were copolymerized according to example 125 with catalyst {[(2,6-i-PrPh)~DABMe~)PdCH~CHzCH2C(O)OCH3}BAF (0.136 g, 0.10 30 mmol) in CH2C12 solvent with a reaction time of 72 hours to give 4.93 g of copolymer.
Example 127 Ethylene and methyl acrylate were copolymerized .
according to example 125 with catalyst {[(2,6-i-3~ PrPh) 2DABMe,] PdCHzCHzCH2C (O) OCH3 ) SbF6 ( 0 . 084 g, 0 . 10 mmol) with a reaction time of 72 hours to give 8.19 g of copolymer.
?20 ~~ ~RCTITt ITF ~HFFT (RULE 261 WO 96123010 CA 02338526 2001-03-O1 PCT'IUS96/01282 ~'xamnie 128 Ethylene and methyl acrylate were copolymerized according to example 125 with catalyst {[(2,6-i-PrPh)ZDABHZ]PdCH2CH2CH2C(O)OCH3}SbF6 (0.082 g, 0.10 mmol) to give 1.97 g of copolymer.
Exanlnle Ethylene and methyl acrylate were copolymerized according to example 125 with catalyst {[(2,6-i-PrPh) 2DABMe2] PdMe (CH3CN) } SbF6~ ( 0 . 080 g, 0 . 10 mmol ) to 10 give 3.42 g of copolymer. The 1H NMR shows primarily copolymer, but there is also a small amount of poly(methyl acrylate) homopolymer.
Example i30 Ethylene and methyl acrylate (20 ml) were 1~ copolymerized in 20 ml of CHCl3 according to example 125 using catalyst {((2,6-i-PrPh) 2DABMe2] PdCHzCH2CH2C (O) OCH3 } SbF6 (0. 339 g, 0 .40 mmol) to give 2.17 g of copolymer after a reaction time of 72 hours. 13C NMR quantitative analysis: Mole%:
20 ethylene (76.3), methyl acrylate (23.7). Branching per 1000 CH2: Total methyls (28.7), Methyl (20.5), Ethyl (3.8), Propyl (0), Butyl (11), ?Amyl and end of chains (13.6), methyl acrylate (138.1). Ester branches -CH(CH2)nC02CH3 as a % of total ester: n>_5 (38.8), n=4 (20), n=1,2,3 (15.7), n=0 (25.4).
Example 131 Ethylene and methyl acrylate (20 ml) were copolymerized in 20 ml of CHC13 at SO°C for 20 hours according to example 125 using catalyst {((2,6-1-30 PrPh)~DABMe2]PdCH~CHzCHZC(O)OCH3}SbF6 (0.339 g, 0.40 mmol) to give 0.795 g of copolymer. DSC (two heats, 150 to +150°C, 15°C/min) shows Tg= -48°C.
Exams a 132 A solution of the ligand (2,6-i-PrPh)2DAB(Me2) 3~ (0.045 g, 0.11 mmol) dissolved in 2 ml of CHC13 was added to a solution of the complex [PdMe(CH3CN)(1,5-cyclooctadiene)]+SbF6- (0.051 g, 0.10 mmol) in 2 ml of CHC13. This mixture was combined with 35 ml of of ~nn~r~ rrc euccT ~Qt 11 C 9R1 additional CHC13 and 5 ml cf methyl acrylate in a Schlenk flask in a drybox, and then a copolymerization with ethylene was carried out according to example 125 to give 1.94 g of copolymer.
Examx~ 1 a 13 3 Methyl acrylate (S ml) was added to the solid catalyst ([(2,6-i-PrPh)zDABMe2)PdMe(Et20)~BF9 (0.0698, 0.10 mmol) followed by 40 ml of CHC13. The addition of methyl acryiate before the CHC13 is often.important to 10 avoid deactivation of the catalyst. A copolymerization with ethylene was carried out according to example 125 to give 2.87 g of copolymer.
Cha_racteYi zat i on of x~olv ( ethylene-co-methyl acry ~ a P ) 1 ~ ~~H NMR
NMR spectra in CDC13 were integrated and the polymer compositions and branching ratios were calculated. See example 124 for chemical shifts and assignments.

Example Yield(g) methyl acrylateCH3 per C02CH3 per (mole %) 1000 CH2 l 124 3.9 6.9 BO 42 125 1.75 7.1 104 45 126 4.93 5.6 87 34 127 8.19 6.1 87 37 128 1.97 7.3 159 50 129 3.42 9.5 86 59 130 2.17 22.8 29 137 131 0.795 41 14 262 132 1.94 6.1 BO 36 133 2.87 8.2 70 49 Molecular Weight Characterization GPC was done in THF using PMMA standards and an RI
detector except for example 133 which was done in '_'S trichlorobenzene at 135°C vs. polystyrene reference m ~nn~ me ~utcT I~I 11 C ~R1 with results calculated as linear polyethylene using universal calibration theory. When polymer er_~d groups could be detected by 1H NMR (5.4 ppm, multipiet, -CH=CH-, internal double bond), Mn was calculated assuming two olefinic protons per chain.
Example Mr MW MW/Mn Mn (1H NMR) 124 15,500 26,400 1.70 125 1,540 2,190 1.92 850 126 32,500 49,900 1.54 127 12,300 22,500 1.83 128 555 595 1.07 360 129 16.100 24,906 1.55 136 800 3,180 3.98 ~ 1,800 131 x,100 132 15,200 26,000 1.71 133 5,010 8,790 1.75 Example 134 Ethylene and t-butyl acrylate (20 ml) were 10 copolymerized according to example 130 to give 2.039 g of viscous fluid. 1H NMR of the crude product showed the desired copolymer along with residual unreacted t-butyl acrylate. The weight of polymer corrected for monomer was 1.84 g. The sample was reprecipitated to 15 remove residual monomer by slow addition of excess MeOH
to a CHC13 solution. The reprecipitated polymer was dried in vacuo. '-H NMR (CDC13): 2.2(t, -CH2C02C(CH3)3, ester ended branches), 1.6(m, -C$2CH2C02C(CH3)3, ester ended branches), 1.45(s, -C(CH3)3), 0.95-1.45(m, CH and 20 other CH2), 0.75-0.95(m, CH3, ends of hydrocarbon branches or ends of chains). This spectrum shows that the esters are primarily located at the ends of hydrocarbon branches; integration gave 6.7 mole % t-butyl acrylate. 13C NMR quantitative analysis, branching per 1000 CH2: Total methyls (74.8), Methyl (27.7), Ethyl (15.3), Propyl (1.5), Butyl (8.6), amyl ''?3 m ~ewn~ m cucCT IRI ii F 9R1 WO 96/23010 ~ 02338526 2001-03-O1 :nd end of chains (30.8), -C02C(CH3)3 ester (43.2).
Ester branches -CH(CH2)nC02C(CH3)3 as a o of total ester: n>_5 (44.3), n=1,2,3,4 (37.2), n=0 (18.5). GPC
(THF, PMMA standard): Mn=6000 Mw=8310 Mw/Mn = 1.39.
S ]~,~cample 135 Glycidyl acrylate was vacuum distilled and inhibited with 50 ppm phenothiazine. Ethylene and glycidyl acrylate (5 ml) were copolymerized according to Example 125 using catalyst ([(2,6-1-10 PrPh)zDABMe2]PdCH2CH2CH2C(O)OCH3}SbF6 (0.084 g, 0.10 mmol). The reaction mixture was filtered through a fritted glass filter to remove chloroform insolubles, and the chloroform was removed in vacuo to give 14.1 g viscous yellow oil which still contained residual I~ unreacted glycidyl acrylate. The sample was reprecipitated to remove residual monomer by slow addition of excess acetone to a CHC13 solution. The reprecipitated polymer was dried in vacuo to give 9.92 g of copolymer containing 1.8 mole % glycidyl acrylate.
20 1H NMR (CDC13): 4.4, 3.9, 3.2, 2.85, 2.65 (multiplets, 1 H each -CH2CH[ CHZ 1 ) 2.35 (t, -CH2C02CH2CHCH20, ester ended branches), 1.65(m, L-J
-CH2CH2C02CH2CHCH20, ester ended branches), 0.95-1.5(m.CH
(~
and other CH2), 0.75-0.95(m, CH3, ends of hydrocarbon branches or ends of chains). This spectrum shows that the epoxide ring is intact, and that the glycidyl ester groups are primarily located at the ends of hydrocarbon branches. GPC (THF, PMMA standard): Mn=63,100 Mw=179,000 Mw/Mn = 2.85.
30 13C NMR quantitative analysis, branching pe= 1000 CH2: Total methyls (101.7), Methyl (32.5), Ethyi , (21.3), Propyl (2.4), Butyl (9.5), Amyl (1.4), >_Hexyl and end of chains (29.3), Ester branches -CH(C.'-'.2)nC02R
as a % of total ester: n?5 (39.7), n=4 (small amount), 3~ n=1,2,3 (50.7), n=0 (9.6).

c~ roert~ tTC cN~CT IR1 II F 261 A 3.24-g sample of the copolymer was dissolved in 50 mL of refluxing methylene chloride. A solution of 0.18 g oxalic acid dihydrate in 5 mL of 1:1 chloroform-acetone was added to the solution of copolymer and the solvent was evaporated off on a hot plate. The thick liquid was allowed to stand in an aluminum pan at room.
temperature overnight; the pan was then placed in an oven at 70°C for 1.5 hr followed by 110°C/vacuum for 5 hr. The cured polymer was a dark, non-tacky soft 10 rubber which tore easily (it had a very short elongation to break despite its rubberiness).
Examnl_e ~'~6 1-Pentene (20 ml) and methyl acrylate (5 ml) were copolymerized in 20 ml chloroform for 96 hours using I~ catalyst ( [ (2, 6-i-PrPh) 2DABMe2] PdCH2CH2CHzC (O) OCH~ }SbFE
(0.084 g, 0.10 mmol). The solvent and unreacted monomers were removed in vacuo to give 0.303 g copolymer (0.219 g after correcting for catalyst residue). The 1H NMR spectrum was similar to the 20 ethylene/methyl acrylate copolymer of example 124 suggesting that many of the ester groups are located at the ends of hydrocarbon branches. Integration shows that the product contains 21 mole o methyl acrylate.
There are 65 acrylates and 96 methyls per 1000 25 methylene carbons. GPC (THF, PMMA standard): Mn=6400 Mw=11200 Mw/Mn = 1.76.
Exam i37 Benzyl acrylate was passed through activity 1 alumina B, inhibited with 50 ppm phenothiazine, and 30 stored over activated 4A molecular sieves. Ethylene and benzyl acrylate (5 ml) were copolymerized according to example 135 to give 11.32 g of viscous fluid. 1H
NMR of the crude product showed a mixture of copolymer and unreacted benzyl acrylate (35 wt ~) The residual 3~ benzyl acrylate was removed by two reprecitations, the first by addition of excess MeOH to a chloroform solution, and the second by addition of excess acetone to a chloroform solution. 1H NMR (CDC13): 7.35 (broad ci ~acTlTi T'fF SHFFT f RI II F 961 ~,_ -CH2C6~j5), 5.1(s, -C~2C6H5), 2.35(t, -C~2C02CH2C6H5, ester ended branches), 1.6(m, -C~i2CH2C02CH2C6H5, ester ended branches), 0.95-1.5(m, CH and other CH2), 0.75-0.95(m, CH3, ends of hydrocarbon branches or ends of chains). Integration shows that the product contains 3.7 mole % benzyl acrylate. There are 21 acrylates and 93 methyls per 1000 methylene carbons. GPC (THF, PMMA
standard): Mn=46,200 Mw=73,600 Mw/Mn = 1.59.
13C ~R quantitative analysis, Branching per 1000 10 CH2: Total methyls (97.2), Methyl (32.9), Ethyl (20.3), Propyl (2.4), Butyl (9.7), Amyl (2.9), >_Hexyl and end of chains (35.2), benzyl acrylate (17.9), Ester branches -CH(CHz)nC02R as a o of total ester: n?5 (44.5), n=4 (7.21, n=1,2,3 (42.3), n=0 (6) Examnie 138 1-Pentene (10 ml) and ethylene (1 atm) were copolymerized in 30 ml chloroform according to example 125 using catalyst {[(2,6-i-PrPh)~DABMe~]PdCH2CH2CH2C(O)OCH3~SbF6 (0.084 g, 0.10 20 mmol) to give 9.11 g highly viscous yellow oil The 1H
NMR spectrum was similar to the polyethylene) of example 110 with 113 methyl carbons per 1000 methylene carbons. 13C NMR quantitative analysis, branching per 1000 CH2: Total methyls (119.5), Methyl (54.7), Ethyl (16.9), Propyl (8.4), Butyl (7.7), Amyl (7.2), ?Hexyl and end of chains (30.9). GPC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory): Mn=25,000, Mw=44,900, Mw/Mn=1.79.
30 Listed below are the 13C NMR data upon which the above analysis is based.

C ~ Data TCB, 120C, 0.05M
CrAcAc Freq Intensity ppm 39.60125.53532 39.43136.33425 MB2 38.30048.71403 MB3+

37.944617.7325 MB3+

37.280936.416 aBl, 36.76595.10586 aBl, c> >ee~T~ rTC cuGrT rRl 11 F 261 WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96/01282 34.3181 56.1758 ay+B

33.8243 15.6271 ay+B

33.3942 8.09189 t~~

32.9854 20.3523 MB1 32.6721 4.35239 MB1 32.327 4.06305 3B5 31.9394 27.137 3B6+, 3 EOC

31.4031 9.62823 y+y+B, 384 30.235 52.8904 y+y+B, 3B4 29.7518 162.791 y+y+B, 384 29.3164 26.506 y+y+B, 3g4 27.5695 15.4471 By+B, 282 27.1341 59.1216 By+B, 2B2 26.4811 8.58222 By+B, 2B2 24.4475 5.93996 ~i(3B

23.12 5.05181 284 22.6369 29.7047 2B5+, 2 EOC

20.1626 6.29481 2B3 19.7378 31.9342 1B1 19.2068 3.93019 1B1 14.2582 5.59441 1B3 13.8706 36.3938 184+, .
EOC

10.9768 9.89028 1B~

Examp 13 1-Pentene (20 ml) was polymerized in 20 ml chloroform according to example 138 to give 2.59 g of viscous fluid (369 equivalents 1-pentene per Pd).
Integration of the 1H NMR spectrum showed 118 methyl carbons per 1000 methylene carbons. DSC (two heats, -I50 to +150°C, 15°C/min) shows Tg= -58°C and a low temperature melting endotherm from -50°C to 30°C (32 J/g).
13C NMR quantitative analysis, branching per 1000 CH2: Total methyls (118), Methyl (85.3), Ethyl (none detected), Propyl (15.6), Butyl (non detected), _>Amyl and end of chains (17.1). GPC (trichlorobenzene, 1~ 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory): Mn=22,500, Mw=43,800, Mw/Mn=1.94.
Listed below are the 13C NMR data upon which the above analysis is based.
~27 SUBSTITUTE SHEET (RULE 26) WO 96/23010 CA 02338526 2001-03-O1 pCTlUS96/01282 13C ~ data TCB, 120C, O.OSMCrAcAc Frees t it I

~~m n 42.6277 ens as for Me & Et+
v 4.69744 39.5428 9.5323 3rd carbon of a 6+ carbon side chain that has a methv_1 branch at the 4 position 38.1357 3.59535 37.8384 13.9563 MB3+

37.5888 28.4579 37.2224 54.6811 aB1,3B3 35.5287 6.51708 35.2419 3.55603 34.6366 7.35366 34.2437 22.3787 32.911 45.2064 MB1 32.5977 10.5375 32.38 4.02878 31.8809 14.1607 3B6+, 3EOC

30.6916 8.44427 y+y+B

30.0703 63.1613 y+y+B

29.6987 248 ~ y+y+B

29.2633 17.9013 y+y+B

28.8916 3.60422 27.1182 66.2971 py+B, (485, etc.) 24.5324 16.8854 22.5784 16.0395 2B5+, 2EOC

20.1041 13.2742 19.6952 54.3903 181, 2B3 14.2104 12.2831 13.8281 16.8199 184+,EOC,1B3 Integration of the CH2 peaks due to the structure -CH(R)CH2CH(R')- , where R is an alkyl group, and R' is an alkyl group with two or more carbons showed that in 690 of these structures, R = Me. The region integrated for the structure where both R and R' are >_Ethyl was 39.7 ppm to 41.9 ppm to avoid including an interference 10 from another type of methylene carbon on a side chain.
Example 140 [(2,6-i-PrPh)ZDABMe,]PdMeCl (0.020 g, 0.036 mmol) was dissolved in 4 ml CH2C12 and methyl acrylate 15 (0.162 g, 0.38 mmol, inhibited with 50 ppm phenothiazine) was added while stirring. This sclution was added to a stirred suspension of NaBAF (0.033 g, 0.038 mmol) in 4 ml of CH2C12. After stirring for 1 ~~g SUBSTITUTE SHEET f RULE 26) 'our, the mixture was filtered through a 0.5~~m PTFE
membrane filter to remove a flocculant gray precipitate. The solvent was removed from the filtrate in vacuo to give a solid which was recrystallized from a CH2C12/pentane mixture at -40°C to give 0.39 g (750 yield) of orange crystalline {[(2,6-i-PrPh)2DABMe~)PdCH~CH~CH2C(O)OCH3}BAF . 1H NMR (CDC13) 0.65(m, CH2, 2H); 1.15-1.45(four sets of doublets for -CH(C~3)2 and multiplet at 1.4 for a CH2,.total area =
26H); 2.19,2.21 (s, s, CH3 of ligand backbone, 6H);
2.40(m, CH2, 2H); 2.90 (m, -C$(CH3)2, 4H); 3.05(s, -C02CH3, 3H); 7.25-7.75(m, aromatic H of ligand and counterior., 19H).
All GPC data reported for examples 141-170, 177, 1~ and 204-212 were run in trichlorobenzene vs.
polyethylene standards unless otherwise indicated. All DSC data reported for examples 141-170, 177, and 204-212 (second heat, -150°C to 150°, 10 or 15°C/min).
ExamR, a 141 ?0 A Schlenk flask containing {[(2,6-i-PrPh)2DABH2)NiMe(Et20)~BAF (1.3 mg, 8.3 x 10-~ mol) under an argon atmosphere was cooled to -78°C. Upon cooling, the argon was evacuated and the flask backfilled with ethylene (1 atm). Toluene (75 mL) was added via syringe. The polymerization mixture was then warmed to 0°C. The solution was stirred for 30 minutes Polymer began to precipitate from the solution within minutes. After 30 minutes, the polymerization was terminated upon exposing the catalyst to air. The 30 polymer was precipitated from acetone, collected by filtration and washed with 6 M HC1, water, and acetone.
The polymer was dried in vacuo. The polymerization yielded 1.53 g of polyethylene (1.3 x 105 TO). Mn =
91,900; M,a = 279,000; MW/Mn = 3.03; Tm = 129°C. 1H NMR
(CED5C1, 142°C) 0.6 methyls per 100 carbons.
Exa~r~le 142 The reaction was done in the same way as in Example 141 using 1.3 mg of {[(2,6-1-c~ iacTm r~ cuc~T IRi II F ~R1 WO 96123010 ~ 02338526 2001-03-O1 p~~7g96/01282 _-rPh)ZDABMe;]NiMe(Et20) }BAF l8.3 x 10-7 mol) . The polymer was isolated as a white solid (0.1 g).
Fxamr~l es 4 48 General procedure for the polymerization of ethylene by the methylaluminoxane (MAO) activation of nickel complexes containing bidentate diimine ligands:
Polymerization at 0°C: The bisimine nickel dihalide complex (1.7 x 10-5 mol) was combined with toluene (100 mL) in a flame dried Schlenk flask under 1 atmosphere l0 ethylene pressure. The polymerization was cooled to 0°C in an ire-water bath. The mixture was stirred at 0°C for 15 ~;.inutes prior to activation with MAO.
Subseauent__,~, 1.5 mL of a loo MAO (100 eq) solution in toluene was added onto the nickel dihalide suspension.
The solutic~ was stirred at 0°C for 10, 30, or 60 minutes. Within minutes increased viscosity and/or precipitation of polyethylene was observed. The polymerization was quenched and the polymer precipitated from acetone. The polymer was collected 20 by suction filtration and dried under vacuum for 24 hours. See Table I for a detailed descritition of molecular weight and catalyst activity data.
Example No. Catalyst 143 [(2,6-i-PrPh)2DABH~]NiBrz ?5 144 [(2,6-i-PrPh)ZDABMez]NiBr2 145 [(2,6-MePh)~DABH2]NiBr~
146 [(2,6-i-PrPh)2DABAn]NiBr2 147 [(2,6-MePh)~DABAn]NiBr2 148 [ (2, 6-MePh) zDABMe~] NiBrz Exam. Condi- Yield TO/ Mn MW MW/Mn Thermal tionsl ~ (g) hr-mol Analysis catalyst ('C) 143 0'C.30m 5.3 22,700 80,900 231,0002.85 119 (Tm~

144 0'C.30 3.8 16,300 403,000 795,0001.97 115 (Tm) m 145' 0'C.30m 3.4 14,300 42,900 107,0002.49 131 (Tm) 146' 0'C..iUm7.0 29,900 168,000 389,0002.31 107 (Tm;

147 0''C 3 .7 47, 500 125, 362, 2 . 122 (Tm) .10 000 000 89 m 148 0'C.IOm 5.1 65,400 171,000 440,0002.58 115 (Tm) m rocnTi rrC cNCCT lCtl II F ~Rl 1 Polymerization reactions run at 1 atmosphere ethylene pressure.
2 Branching Analysis by 13C NMR per 1000 CH2:
Ex. 144: Total methyls (54.3), Methyl (43.4), Ethyl (3.3), Propyl (2), Butyl (1.3), ?Butyl and end of chains ( 5 . 7 ) .
Ex. 146: Total methyls (90.9), Methyl (65.3), Ethyl (7.2), Propyl (4.5), Butyl (3.5), Amyl (4.5), >_ Hexyi and end of chains (10.2).
3 Ex. 145: '1H NMR (CEDSCl) , 142°C) 0.1 methyl per 100 carbon atoms.
F_'xamples 149-154 Polymerization at Ambient Temperature The general procedure described for the MAO
1~ activation of the diimine~nickel dihalides was followed in the polymerizations detailed below, except all polymerizations were run between 25-30°C.
Example No. Catalyst 149 [ (2, 6-i-PrPh) zDABH2] NiBr~

150 [ (2, 6-i-PrPh) 2DABMe~] NiBr2 151 [ ( 2 , 6 -MePh) ZDABH~ ] NiBr~

152 [(2,6-i-PrPh)~DABAn]NiBr2 153 [(2,6-MePh)zDABAn]NiBr2 2~ 154 [(2,6-MePh)ZDABMez]NiBr~

Exam. Condi- Yield TO/ Mn MW MW/Mn Thermal tionsl (g) hr~mol ~ Analysis catalyst (C) 149 30C.30 2.5 12,200 15,500 34,900 2.25 --m 150' 25C.~O 3.4 14,500 173,000248,00G 1.44 -51 (Tg) m 151' 25C.30 7.2 30,800 13,900 39,900 2.88 90,112 m (Tm) 152' 25C.30 4.2 18,000' 82,300 175,000 2.80 39 (Tm) m 153 25C,10 4.9 62,900 14,000 25,800 1.85 --m 154 25C.10 3.7 47,500 20,000 36,000 1.83 --m ~r rR~rnlTE SHEET (RULE 261 WO 96/23010 ~ 02338526 2001-03-O1 p~/pS96/01282 1 Polymerization reactions run at 1 atmosphere ethylene pressure.
2 Branching Analysis by 13C NMR per 1000 CH2:
Ex. 150: Total methyls (116.3), Methyl (93.5), Ethyl (6.2), Propyl (3.2), Butyl (2.9), Am (6.6), ?Hex and end of chains (11.2).
Ex. 152: Total methyls (141.9), Methyl (98.1), Ethyl (15.9), Propyl (5.6), Butyl (6.8), Amyl (4.1), Hex and end of chains (10.7). Quantitation of the -10 CH2CH(CH3)CH2CH3 structure per 1000 CH2's: 8.
3 Ex. 151: 1H NMR (C6DSC1) , 142°C) 3 methyl per 100 carbon atoms.
Example 155 A standard solution of [(2,6-i-PrPh)~DABAn]NiBr~
1~ was prepared as follows: 1,2-difluorobenzene (10 mL) was added to 6.0 mg of [(2,6-i-PrPh)2DABAn]NiBr2 (8.4 x 10-6 mol) in a 10 mL volumetric flask. The standard solution was transferred to a Kontes flask and stored under an argon atmosphere.
?0 The standard catalyst solution (1.0 mL, 8.4 x 10-~ mol catalyst) was added to a Schlenk flask which contained 100 mL toluene, and was under 1 atmosphere ethylene pressure. The solution was cooled to 0°C, and 1.5 mL of a loo solution of MAO (>_1000 eq) was added.
The solution was stirred for 30 minutes. Polymer began to precipitate within minutes. The polymerization was quenched and the polymer precipitated from acetone.
The resulting polymer was dried in vacuo (2.15 g, 1.84 x 105 TO) . Mn = 489, 000; M,, = 1, 200, 000; M,,,,/Mn = 2.47 30 Example 156 The polymerization of ethylene at 25°C was accomplished in an identical manner to that described in Example 155. The polymerization yielded 1.8 g of polyethylene (1.53 x 105 TO). Mn = 190,000; MW =
3~ 410,000; MW/Mn = 2.16; 1H NMR (C6D5C1, 142°C) 7 methyls per 100 carbons.

c1 lacTtTI tTF RNFFT fRl 1l E 261 WO 96123010 CA 02338526 2001-03-O1 PC'T/US96I01282 A standard solution of [(2,6-MePh)ZDABAn]NiBr~ was prepared in the same way as described for the complex in Example 155 using 5.0 mg of [(2,6-MePh)2DABAn]NiBr~
( 8 . 4 x 10'6 mol ) .
5 Toluene (100 mL) and 1.0 mL of the standard solution of complex 5 (8.3 x 10-~ mol catalyst) were combined in a Schlenk flask under 1 atmosphere ethylene pressure. The solution was cooled to 0°C, and 1.5 mL
of a 10% solution of MAO(>_1000 eq) was added. The 10 polymerization mixture was stirred for 30 minutes. The polymerization was terminated and the polymer precipitated from acetone. The reaction yielded 1.60 g of polyethylene (1.4 x 105 TO). Mn = 590,000; Mw =
1,350,000; Mw/Mn = 2.29.
1~ Example 158 Toluene (200 mL) and 1.0 mL of a standard solution of [(2,6-i-PrPh)2DABAn]NiBr2 (8.3 x 10-~ mol catalyst) were combined in a Fisher-Porter pressure vessel. The resulting solution was cooled to 0°C, and 1.0 mL of a 20 10% MAO (>_1000 eq) solution in toluene was added to activate the polymerization. Subsequent to the MAO
addition, the reactor was rapidly pressurized to 276 kPa. The solution was stirred for 30 minutes at 0°C.
After 30 minutes, the reaction was quenched and polymer precipitated from acetone. The resulting polymer was dried under reduced pressure. The polymerization yielded 2.13 g of white polyethylene (1.82 x 105 TO).
Mn = 611,000; MW = 1,400,000; M,,r/Mn = 2.29; Tt,, = 123°C;
1H NMR (C6D5C1, 142°C) 0.5 methyls per 100 carbons.
30 Fxampl_es 159-160 Polymerization of Propylene The diimine nickel dihalide complex (1.7x10-5 mol) was combined with toluene (100 mL) in a Schlenk flask under 1 atmosphere propylene pressure. The 35 polymerization was cooled to 0°C, and 1.5 mL of a l0%
MAO (100 eq) solution in toluene was added. The solution was stirred for 2 hours. The polymerization ?33 ct tacTtTt ITF SHEET (RULE 26) WO 96123010 CA 02338526 2001-03-O1 pCT/US96101282 ~as quenched and the polymer precipitated from a~Ctone.
The polymer was dried under vacuum.
Example No. Catalyst 159 [ (2, 6-i-PrPh) ~DABHZ] NiBr~
160 [(2,6-i-PrPh)~DABAn]NiBrz Exam.Condi- Yield TO/ Mn MW M,,,,/MnThermal tionsl (g) hr~mol Analysis catalyst (C) 159 0C.2h 1.3 900 131,000 226,000 1.72 -20 (Tg) a 160 0C.2h 4.3 2,900 147,000 235,000 1.60 -78, (T ) aGPC (toluene, polystyrene standard) Ex. 159: 'H NMR (CaD~CI), 142°C) 30 methyls per 100 carbon atoms.
10 Ex. 160: 1H NMR (CEDSC1), 142°C) 29 methyls per 100 carbon atoms. Quantitative 13C NMR analysis, branching per 1000 CH2: Total methyls (699). Based on the total methyls, the fraction of 1,3-enchainment is 130.
Analysis of backbone carbons (per 1000 CH2): ~+ (53), 1~ 8'/y (0.98) .
Listed below are the 13C NMR data upon which the above analysis is based.

C NMR Data TCB, 140C, 0.05M CrAcAc Freq ppm Intensity 47.3161 53.1767 46.9816 89.3849 46.4188 82.4488 45.84 23.1784 38.4702 12.8395 38.0985 29.2643 37.472 18.6544 37.2915 24.8559 35.3747 15.6971 34.5623 14.6353 33.3145 14.2876 32.996 12.2954 30.9464 24.2132 30.6703 57.4826 30.081 30.122 y to single branch ci n~Tm t~ SNFFT rRtILE 261 29.6987 29.2186 b+ to branch 28.3659 298.691 27.4792 33.2539 27.1235 29.7384 24.5324 9.45408 21.1554 20.0541 20.6244 110.077 19.9926 135.356 16.9342 8.67216 16.4829 8.81404 14.9962 8.38097 Examj~1_e ~ 6~
[(2,6-i-PrPh)~DABH2]NiBrz (10 mg, 1.7 x 10-5 m01) was combined with toluene (40 mL) under a N2 atmosphere. A 10% solution of MAO (1.5 mL, 100 eq) was added to the solution. After 30 minutes, the Schlenk flask was backfilled with propylene. The reaction was stirred at room temperature for 5.5 hours. The polymerization was quenched, and the resulting polymer dried under vacuum (670 mg, 213 TO/h). Mn = 176,000;
MW = 299,000; Mw/Mn = 1.70. Quantitative 13C NMR
analysis, branching per 1000 CH2: Total methyls (626), Methyl (501), Ethyl (1), >_Butyl and end of chain (7).
Based on the total methyls, the fraction of 1,3-enchainment is 22%. Analysis of backbone carbons (per 1000 CH2) : 8+ (31) , 8+/y (0.76) .
Examl, l 62-~ 65 ~he diimine nickel dihalide catalyst precursor (1.7x10-5 m01) was combined with toluene (40 mL) and 1-hexene (10 mL) under a N2 atmosphere. Polymerization '_0 reactions of 1-hexene were run at both 0°C and room temperature. A 10% solution of MAO (1.5 mL, 100 eq) in toluene was added. Typically the polymerization reactions were stirred for 1-2 hours. The polymer was precipitated from acetone and collected by suction filtration. The resulting polymer was dried under vacuum.

S11RSTITlITE SHEET (RULE 267 WO 96/23010 ~ 02338526 2001-03-O1 pC'1'/j7g96/01282 Ex. No. Catalyst 162 [ (2, 6-i-PrPh) 2DABH2] NiBr=

163 [(2,6-i-PrPh)ZDABAn)NiBr~

164 [ (2, 6-i-PrPh) 2DABH2] NiBr 165 [(2,6-i-PrPh)2DABAn]NiBr~

Exam.Condi- Yield TO/ Mna MW MW/Mn Thermal tionsl (g) hr~mol Analysis catalyst (C) 162 25C.Ih 3.0 2100 173,000318,000 1.84 -48 (T
) 163 25C.Ih 1.2 860 314,000642,000 2.05 -54 (Tg) -19 (Tm) 164 0C.2h 3.0 1100 70,800 128,000 1.80 -45 (TQ) 165 0C.?h 1.5 540 91,700 142,000 1.55 -49 (T~) aGPC (toluene, polystyrene standards).
Branching Analysis Ex. 162: by 13C NMR per 1000 10 Total methyls (157.2), Methyl (47), Ethyl (1.9), Propyl (4.5), Butyl (101.7), ?Am and end of chain (4.3) .

ci ~ac~~ rrF SNF~ rRtJLE 261 13C ~ data (Example 162) TCB, 120C, 0.05M CrAcAc Frees t nom I
i n y 42.8364 ens Methine t 7.99519 41.3129 27.5914 as to tw o h+ branches Et 40.5759 19.6201 as to tw o h+ branches Et 37.8831 14.7864 Methines andMethylenes 37.2984 93.6984 Methines andMethylenes 36.6684 6.99225 Methines andMethylenes 35.5773 36.067 Methines andMethylenes 34.655 55.825 Methines andMethylenes 34.3091 63.3862 Methines andMethylenes 33.8356 24.1992 Methines andMethylenes 33.428 53.7439 Methines andMethylenes 32.9957 51.1648 Methines andMethylenes 31.9169 17.4373 Methines andMethylenes 31.5546 14.008 Methines andMethylenes 31.1552 10.6667 Methines andMethylenes 30.5993 34.6931 Methines andMethylenes 30.274 56.8489 Methines andMethylenes.

30.1258 42.1332 Methines andMethylenes 29.747 97.9715 Methines andMethylenes 29.1047 47.1924 Methines andMethylenes 28.8823 64.5807 Methines andMethylenes 28.1289 13.6645 Methines andMethylenes 27.5648 61.3977 Methines andMethylenes 27.1777 50.9087 Methines andMethylenes 27.0213 31.6159 Methines andMethylenes 26.9142 31.9306 Methines andMethylenes 26.4572 4.715666 Methines andMethylenes 23.2085 154.844 2B4 22.6074 12.0719 2B5+,EOC

20.0669 8.41495 1B1 19.6963 57.6935 1B1 15.9494 17.7108 14.3477 8.98123 13.8742 248 1B4+,EOC

Examnla 166 ((2,6-i-PrPh)2DABMe2)NiBr2 (10.4 mg, 1.7 x 10'5 mol) was combined with toluene (15 mL) and 1-hexene (40 mL) under 1 atmosphere ethylene pressure. The solution was cooled to 0°C, and 1.5 mL of a 10% MAO (100 eq) solution in toluene was added. The reaction was stirred at 0°C for 2.5 hours. The polymerization was quenched and the polymer precipitated from acetone.
The resulting polymer was dried under reduced pressure (1.4g). Mn = 299,000; Mw = 632,000; Mw/Mn = 2.12.

cnacr~ rt~c cu~~ rR111E 261 WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96/01282 Branching Analysis by 13C NMR per 1000 CH2: Total methyls (101.3), Methyl (36.3), Ethyl (1.3), Propyl (6.8), Butyl (47.7), ?Amyl and end of chains (11.5).
Example 167 [(2,6-i-PrPh)2DABH~]NiBr2 (10 mg, 1.7 x 10-5 mol) was added to a solution which contained toluene (30 mL) and 1-octene (20 mL) under 1 atm ethylene. A l00 solution of MAO (1.5 mL, 100 eq) in toluene was added.
The resulting purple solution was allowed to stir for 4 10 hours at room temperature. Solution viscosity increased over the duration of the polymerization. The polymer was precipitated from acetone and dried under vacuum resulting in 5.3 g of copolymer. Mn = 15,200, MW = 29,100, Mn/Mw = 1.92.
xample X68 [(2,6-i-PrPh)zDABAn]NiBr, (12 mg, 1.7x10-5 mol) was combined with toluene (75 mL) in a Schlenk flask under 1 atmosphere ethylene pressure. The mixture was cooled to 0°C, and 0.09 mL of a 1.8 M solution in toluene of 20 Et2A1C1 (10 eq) was added. The resulting purple solution was stirred for 30 minutes at 0°C. The polymerization was quenched and the polymer precipitated from acetone. The resulting polymer was dried under reduced pressure (6.6 g, 2.8 x 104 TO). Mn - 105,OvQ; M~,, = 232,000; M,"r/Mn = 2.21 Example 159 [(2,6-i-PrPh)~DABAn]NiBrz (12 mg, 1.7x10-5 mol) was combined with toluene (75 mL) under 1 atmosphere propylene pressure. The solution was cooled to 0°C and 30 0.1 mL of Et2A1C1 (>_10 eq~ was added. The reaction was stirred at 0°C for 2 hours. The polymerization was quenched and the polymer precipitated from acetone.
The resulting polymer was dried under reduced pressure (3.97 c 2800 TO).
>> xa nle 170 [(2,6-i-PrPh)2DABAn]NiBr2 (12 mg, 1.7x10-5 mol) was combined with toluene (50 mL) and 1-hexene (25 mL) under a N~ atmosphere. EtzAlC1 (0.01 mL, 10 eq) was S~IRSTiTtITF SHEET (RULE 261 WO 96/23010 CA 02338526 2001-03-O1 PCT/US96i01282 added to the polymerization mixture. T'h~- Z-esu°'~ifrg purple solution was allowed to stir for 4 hours. After 4 hours the polymerization was quenched and the polymer precipitated from acetone. The polymerization yielded 1.95 g poly(1-hexene) (348 TO/h). Mn = 373,000; MW =
680,000; MW/Mn = 1.81.
Rxam~
1-Tetradecene (20 ml) was polymerized in methylene chloride (10 ml) for 20 hr using catalyst ~[(2,6-i-PrPh) zDABMe2] PdCH2CH2CH2C (O) OCH3 ) SbF6 ( 0 . 04 g, 0 . 05 mmol). The solvent and reacted monomer were removed in vacuo. The polymer was precipitated to remove unreacted monomer, by the addition of acetone to a chloroform solution. The precipitated polymer was 1~ dried in vacuo to give a 10.2 g yield. '3C NMR
(trichlorobenzene, 120°C) integrated to give the following branching analysis per 1000 methylene carbons: Total methyls (69.9), methyl (24.5), ethyl (11.4), propyl (3.7), butyl (2.3) amyl (0.3), ?Hexyl and end of chain (24.2). Thermal analysis showed Tg =
-42.7°C, and Tm = 33.7°C (15.2 J/g).
Listed below are the 13C NMR data upon which the above analysis is based.

enacts rrc cuccT rRl II F ~Rl WO 96/23010 PCTlUS96101282 C NMR Data TCB, 120C, O.DSM
CrAcAc Freq ppm Intensity 39.3416 7.78511 MB2 38.2329 5.03571 MB3+

37.8616 9.01667 MB3+

37.5857 3.33517 MB3+

37.2462 31.8174 aBl, 383 36.6415 2.92585 a81, 3B3 34.668 5.10337 ay+B

34.2384 38.7927 ay+B

33.7397 16.9614 3B5 33.3471 3.23743 3B6+, 3EOC

32.9387 16.0951 y+y+B, 3B4 31.9148 27.6457 Y+y+B, 384 31.1297 6.03301 Y+y+B. 384 30.212 59.4286 Y+y+B, 384 29.7398 317.201 y+y+B, 3B4 29.3101 32.1392 y+y+B, 384 27.1511 46.0554 py+B, 282 27.0185 53.103 _ py+B, 2B2 26.419 9.8189 ~iy'B, 2B2 24.244 2.46963 ppB

22.6207 28.924 285+, 2EOC

20.0479 3.22712 2B3 19.7084 18.5679 1B1 14.3929 3.44368 1B3 13.8677 30.6056 1B4+, lEOC

10.9448 9.43801 182 Example 172 4-Methyl-1-pentene (20 ml) was polymerized in methylene chloride (10 ml) for 19 hr using catalyst ( [ (2, 6-i-PrPh) ~DABMe2] PdCH,CHzCH2C(O)OCH3}SbF6 (0.04 g, 0.05 mmol). The solvent and unreacted monomer were removed ~n vacuo. The polymer was precipitated tc 10 remove residual monomer by addition of excess acetone to a chloroform solution. The precipitated polymer was dried in vacuo to rive a 5.7 g yield. 13C NMR
(trichlorobenzene, 120°C) integrated to give 518 methyls per 1000 methylene carbon atoms. Thermal l~ analysis showed Tg -30.3°C.
Listed below are the 13C NMR data upon which ~he above analysis is based.

.."~r.~rr ~r suet? yet n C 9R1 13C ~R Data TCB, 1200, 0.05M CrAcAc Freq ppm Intensity 47.8896 13.3323 47.4011 8.54293 45.7127 26.142 45.1392 17.4909 43.9658 13.9892 43.1375 12.7089 42.6171 11.5396 41.8207 9.00437 39.203 64.9357 37.9712 24.4318 37.3075 87.438 35.4862 16.3581 34.9553 24.5286 34.35 31.8827 33.3624 25.7696 33.0226 42.2982 31.4403 25.3221 30.6226 38.7083 28.504 26.8149 27.989 81.8147 27.7341 78.3801 27.5802 94.6195 27.458 75.8356 27.0864 35.5524 25.6103 97.0113 23.4333 59.6829 23.0563 41.5712 22.536 154.144 21.9944 5.33517 20.7307 16.294 20.4971 34.7892 20.2953 29.9359 19.7378 62.0082 Example 173 1-Eicosene (19.0 g) was polymerized in methylene chloride (15 ml) for 24 hr using catalyst {[(2,6-i-PrPh)2DABMe~)PdCH2CH2CHzC(O)OCH3}SbF6 (0.047 g, 0.05 mmol). The solvent and unreacted monomer were removed in vacuo. The polymer was precipitated to remove residual monomer by addition of excess acetone to a chloroform solution of the polymer. The solution was 10 filtered to collect the polymer. The precipitated polymer was dried in vacuo to give a 5.0 g yield. 13C
NMR quantitative analysis, branching per 1000 CH2:
Total methyls (27), Methyl (14.3), Ethyl (0), Propyl ~I IRSTITlITE SHEET (RULE 26) WO 96/23010 CA 02338526 2001-03-O1 p~y1TS96101282 ,,0.2), Butyl (0.6), Amyl (0.4), ?Hexyl and end of chains (12.4).
Integration of the CH2 peaks due to the structure -CH(R)CH2CH(R')- , where R is an alkyl group, and R' is 5 an alkyl group with two or more carbons showed that in 820 of these structures, R = Me.
Listed below are the '3C NMR data upon which the above analysis is based.
13C NMR data TCB, 120C, 0.05M CrAcAc 37.7853 13.978 MB~+

37.1428 52.1332 CcH

34.1588 41.067 czB4+

32.826 26.6707 MB1 31.8066 24.9262 3B6+,3EOC

30.0703 96.4154 Y+y+B,3B4 29.6243 1239.8 y+Y+8,384 27.0013 78.7094 By+B, (485, etc.) 22.5041 23.2209 2B5+,2EOC

19.605 30.1221 1B1 13.759 23.5115 1B4+,EOC

Example 174 The complex [(2,6-i-PrPh)zDABH2]PdMeCl (0.010 1~ g, 0.019 mmol) and norbornene (0.882 g, 9.37 mmol) were weighed into a vial and dissolved in 2 ml CH2C12.
NaBAF (0.0328, 0.036 mmol) was rinsed into the stirring mixture with 2 ml of CH2C12 After stirring about 5 minutes, there was sudden formation of a solid 20 precipitate. Four ml of o-dichlorobenzene was added and the solution became homogenous and slightly viscous. After stirring for 3 days, the homogeneous orange solution was moderately viscous. The polymer was precipitated by addition of the solution to excess MeOH, isolated by filtration, and dried in vacuo to give 0.285 g (160 equivalents norbornene per Pd) bright orange glassy solid. DSC (two heats, 15°C/min) showed no thermal events from -50 to 300°C. This is consistent with addition type poly(norbornene). Ring-30 opening polymerization of norbornene is known to ~i nom ~ s~~~ rRW E 2s) WO 96/23010 ~ 02338526 2001-03-O1 PCTIUS96/01282 _produce an amorphous polymer with a glass transiticr.
temperature of about 30-55°C.
Rxamnle 175 The solid complex {[(2,6-1-PrPh) ~DABHz] PdMe (Et~O) }SbFs (0.080 g, 0.10 mmol) was added as a solid to a stirring solution of norbornene (1.865 g) in 20 ml of o-dichlorobenzene in the drybox.
About 30 min after the start of the reaction, there was slight viscosity (foam on shaking) and the homogeneous mixture was dark orange/red. After stirring for 20 h, the solvent and unreacted norbornene were removed in vacuo to give 0.508 g orange-red glassy solid (54 equivalents norbornene/Pd). 1H NMR (CDC13): broad featureless peaks from 0.8-2.4 ppm, no peaks in the 1~ olefi~ic region. This spectrum is consistent with addition type poly(norbornene). GPC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory): Mn=566 Mw=1640 Mw/Mn=2.90.
Fxamni ~,'t 76 4-Methyl-1-pentene (10 ml) and ethylene (1 atm) were copolymerized in 30 ml of chloroform according to example 125 using catalyst {[(2,6-i-PrPh) ~DABMe~] PdCH2CHzCH2C (O) OCH3ySbF6 (0. 084 g, 0.10 mmol) to give 23.29 g highly viscous yellow oil. The 1H NMR spectrum was similar to the polyethylene) of example 110 with 117 methyl carbons per 1000 methylene carbons. 13C NMR quantitative analysis, branching per 1000 CH2: Total methyls (117.1), Methyl (41.5), Ethyl (22.7), Propyl (3.3), Butyl (13), Amyl (1.2), ?Hexyl and end of chains (33.1), ?Amyl and end of chains (42.31, By 13C NMR this sample contains two identifiable branches at low levels attributable to 4-methyl-1-pentene. The Bu and >amyl peaks contain small 3~ contributions from isopropyl ended branch structures.
Example 177 CoCl2 (500 mg, 3.85 mmol) and (2,6-i-PrPh)2DABAn (2.0 g, 4.0 mmol) were combined as solids and dissolved SUBSTITUTE SHEET (RULE 26) WO 96/23010 ~ 02338526 2001-03-O1 PCT/US96/01282 Ln 50 mL of THF. The brown solution was stirred for hours at 25°C. The solvent was removed under reduced pressure resulting in a brown solid (1.97 g, 820 yield) .
A portion of the brown solid (12 mg) was immediately transferred to another Schlenk flask and dissolved in 50 mL of toluene under 1 atmosphere of ethylene. The solution was cooled to 0°C, and 1.5 mL
of a 10% MAO solution in toluene was added. The 10 resulting purple solution was warmed to 25°C and stirred for 12 hours. The polymerization was quenched and the polymer precipitated from acetone. The white polymer (200 mg) was collected by filtration and dried under reduced pressure. Mn = 225,000, M,,~ = 519,000, Mw/Mn = 2.31, Tg = -42°, Tm = 52°C and 99.7°C.
Example 178 Ethyl 10-undecenoate (10 ml) and ethylene (1 atm) were copolymerized in 30 ml of CH2C12 according to example 125 using catalyst {I(2,6-i-20 PrPh) 2DABMe2] PdCHZCH2CH2C (O) OCH3 } SbF6 ( 0 . 084 g, 0 . 10 mmol). The copolymer was precipitated by removing most of the CH2C12 in vacuo, followed by addition of excess acetone. The solution was decanted and the copolymer was dried in vacuo to give 1.35 g viscous fluid. 1H
NMR (CDC13): 0.75-0.95lm, CH3); 0.95-1.5(m, C(O)OCH2C~3, CH2, CH); 1.5-1.7(m, -C~2CH2C(O)OCH2CH3);
1.9-2.0(m, -CI32CH=CH-); 2.3(t, -CH2C~2C(O)OCH2CH3);
4.15(q, -CH2CH2C(O)OCH2CH3); 5.40(m, -CH=CH-). The olefinic and allylic peaks are due to isomerized ethyl 30 10-undecenoate which has coprecipitated with the copolymer. Adjusting for this, the actual weight of copolymer in this sample is 1.18 g. The copolymer was reprecipitated by addition of excess acetone to a chloroform solution. 1H NMR of the reprecipitated 35 polymer is similar except there are no peaks due to isomerized ethyl 10-undecenoate at 1.9-2.0 and 5.40 ppm. Based on integration, the reprecipitated copolymer contains 7.4 mole o ethyl l0-undecenoate, and ~t n~iT~ 1TE SHEET (RULE 26) ,~.3 methyl carbons per 1000 methylene carbons. 13C NMR
quantitative analysis, branching per 1000 CH2: Total methyls (84.5), Methyl (31.7), Ethyl( 16.9), Propyl (1.5), Butyl (7.8), Amyl (4.4), ?Hexyl and end of 5 chains (22.3). GPC (THF, PMMA standard): Mn=20,300 Mw=26,300 Mw/Mn = 1.30. 13C NMR quantitative analysis, branching per 1000 CH2: ethyl ester (37.8), Ester branches -CH(CH2)nC02CH2CH3 as a % of total ester: r.>_5 (65.8), n=4 (6.5), n=1,2,3 (26.5), n=0 (1.2) . ' Listed below are the 1'C NMR data upon which the above analysis is based.

~t lBSTtTIITE SHEET (RULE 26) WO 96/23010 cA 02338526 2001-03-O1 pCT/US96/01282 13~ ~R Data Freq ppm Intensity 59.5337 53.217 39.7234 2.57361 39.3145 7.80953 38.2207 11.9395 37.8437 20.3066 37.2225 29.7808 36.7181 5.22075 34.6792 17.6322 34.265 107.55 33.7181 21.9369 33.3093 8.22574 32.9164 15.0995 32.396 8.52655 32.0828 5.79098 31.9075 37.468 31.127 13.8003 30.6757 8.38026 30.2084 52.5908 29.9961 27.3761 29.72 151.164 29.5076 39.2815 29.2899 69.7714 28.727 6.50082 27.5164 20.4174 26.9908 64.4298 26.5713 9.18236 26.3749 11.8136 25.5519 4.52152 25.0528 43.7554 24.2457 7.9589 23.1094 10.0537 22.9926 4.71618 22.6156 37.2966 20.0245 2.4263 19.6847 25.9312 19.1643 5.33693 17.5183 2.20778 14.2954 66.1759 13.8653 43.8215 13.414 2.52882 11.1521 5.9183 10.9237 14.9294 174.945 3.27848 172.184 125.486 171.695 4.57235 Example 179 The solid complex {[(2,6-i-PrPh) ZDABHz] PdMe (Et20) )SbF6 (0.080 g, 0.10 mmol) was added as a solid to a stirring solution of cyclopentene (1.35 g, 20 mmol) in 20 ml of dichlorobenzene in the suasTm~TE SHEET (RULE 26) drybox. After stirring 20 h, the sligYi~r~ viscous solution was worked up by removing the solvent in vacuo to give 1.05 g sticky solid (156 equivalents of cyclopentene per Pd). 1H NMR (CDC13): complex spectrum from 0.6-2.6 ppm with maxima at 0.75, 1.05, 1.20, 1.55, 1.65, 1.85, 2.10, 2.25, and 2.50. There is also a multiplet for internal olefin at 5.25-5.35. This is consistent with a trisubstituted cyclopentenyl end group with a single proton (W. M. Kelly et. al., Macromolecules 1994, 27, 4477-4485.) Integration assuming one olefinic proton per polymer chain gives DP=8.0 and Mn=540. IR (Thin film between NaCl plates, cm-1): 3048 (vw, olefinic end group, CH stretch), 1646(vw, olefinic end group, R2C=CHR trisubstituted double bond stretch), 1464(vs), 1447(vs), 1364(m), 1332 (m) , 1257 (w) , 1035 (w) , 946 (m) , 895 (w) , 882 (w) , 803(m, cyclopentenyl end group, R2C=CHR trisubstituted double bond, CH bend), 721(vw, cyclopentenyl end group, RHC=CHR disubstituted double bond, CH bend). GPC
(trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using universal calibration theory): Mn=138 Mw=246 Mw/Mn=1.79.
$~ple 180 The solid complex {[(2,6-i-PrPh) 2DABMe2] PdCH2CH2CH2C (O) OCH3 ~ SbF6 ( 0 . 084 g, 0 . 10 mmol) was added to a stirring solution of 10.0 ml cyclopentene in 10 ml CHC13 in the drybox. After stirring for 20 h, the mixture appeared to be separated into two phases. The solvent and unreacted monomer were removed in vacuo leaving 2.20 g off-white solid (323 equivalents cyclopentene per Pd). DSC (25 to 300°C, 15°C/min, first heat): Tg = 107°C, Tm (onset) -165 °C, Tm (end) - 260 °C, Heat of fusion = 29 J/g.
Similar results were obtained on the second heat.
GPC (trichlorobenzene, 135°C, polystyrene reference, results calculated as linear polyethylene using SUBSTITUTE SHEET (RULE 26) f f DEMANDES OU BREVETS VOLUMiNEUX
LA PRESF~11TE PART1E DE CETTE DEMANDE OU CE BREVET
COMPREND PLUS D'UN TOME. ~ .-CECt EST LE TOME ~ DE
NOTE: Pour les tomes additionels, veuiilez ca~tacter !e Bureau canadien des brevets JUMBO APPLlCATIONSIPATENTS
THIS SECTION OF THE APPLICATtONIPATENT CONTAINS MORE' THAN ONE VOLUME ' , THIS !S VOLUME ' OF
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Claims (9)

WHAT IS CLAIMED IS:

1. A process for the formation of linear .alpha.-olefins, comprising the step of contacting, at a temperature of about -100°C to about +200, ethylene with a catalyst composition adapted for the oligomerization of ethylene to one or more .alpha.-olefins, wherein the catalyst composition comprises a transition metal complex of the formula (XXXI) wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl;
R3 and R4 are each independently hydrogen, substituted hydrocarbyl, hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
and Q and S are each independently chlorine, bromine, iodine or alkyl; and the catalyst composition further comprises a compound W, which is a neutral Lewis acid capable of abstracting either Q-or S- to :Form WQ- or WS-, provided that the anion formed is a weakly coordinating anion, or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion;
wherein an .alpha.-olefin containing 4 to 40 carbon atoms is produced.

2. The process of claim 1, wherein said compound W is an alkyl aluminum compound.

3. The process of claim 2, wherein said compound W is R9 3Al, R9 2AlCl, R9AlCl2, R9AlO or R9 3Al2Cl3, wherein R9 is alkyl containing 1 to 25 carbon atoms.

4. The process of claim 3, wherein R9 contains 1 to 4 carbon atoms.

5. A process for the formation of linear .alpha.-olefins, comprising the step of contacting, at a temperature of about -100°C to about +200, ethylene with a catalyst composition adapted for the oligomerization of ethylene to one or more .alpha.-olefins, wherein the catalyst composition comprises a transition metal complex of the formula (III) or (XXXIV) wherein:

R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl;
R3 and R4 are each independently hydrogen, substituted hydrocarbyl, hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
T1 is hydrogen or n-alkyl containing up to 38 carbon atoms;
Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6;
U is n-alkyl containing up to 38 carbon atoms; and X is a noncoordinating anion;
and wherein an .alpha.-olefin containing 4 to 40 carbon atoms is produced.

6. A process for the formation of linear .alpha.-olefins, comprising the step of contacting, at a temperature of about -100°C to about +200°C, ethylene with a catalyst composition adapted for the oligomerization of ethylene to one or more .alpha.-olefins, wherein the catalyst composition comprises a Ni{II}
complex of a ligand of the formula (VIII) wherein:
R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;
R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring; and wherein an .alpha.-olefin containing 4 to 40 carbon atoms is produced.

7. The process of any one of claims 1-6, wherein R3 and R4 are hydrogen, methyl or 1,8-naphthylylene.

8. The process of any one of claims 1-6, wherein R2 and R5 are phenyl.

9. The process of any one of claims 1-6, wherein a partial pressure of said ethylene is about atmospheric pressure to about 275 MPa.