US 20020173605A1

( 12) Patent Application Publication ( 10) Pub. N o. : US 2002/ 0173605 A1

( 19 ) United States
Inoue et al. ( 4 3) Pub. D ate: N OV. 21, 2002
( 54 ) PROCESS FOR PROD UCIN G FUN CTION AL
STYREN E COPOLYMER AN D FUN CTION AL
STYREN E COPOLYMER
( 76) Inv entor s : Tets uy a Inoue, Ch iba ( J P) ; Mas anor i
Ser a, Ch iba ( J P)
Cor r es pondence Addr es s :
OBLON SPIVAK MCCLELLAN D MAIER &
N EUSTAD T PC
FOURTH FLOOR
1755 J EFFERSON D AVIS HIGHWAY
ARLIN GTON , VA 22202 ( US)
( 21) Appl. N o. : 09 / 9 26, 78 8
( 22) PCT Filed: Apr . 18 , 2001
( 8 6) PCT N o. : PCT/ J P01/ 03302
( 30) For eig n Application Pr ior ity D ata
Apr . 19 , 2000 ( J P) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2000-1179 4 2
Publication Clas s i? cation
( 51) Int. Cl. 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C08 F 4 / 4 4
( 52) US. Cl. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526/ 160; 526/ 75; 526/ 151;
526/ 153; 526/ 24 0; 526/ 34 7
( 57) ABSTRACT
A pr oces s f or pr oducing a s ty r enic copoly m er h av ing a
f unctional g r oup and th e s y ndiotactic con? g ur ation is pr o
v ided. Th e pr oces s com pr is es br ing ing a m etal com pound
into inter action With a v iny l com pound h av ing a f unctional
g r oup to m as k th e f unctional g r oup and copoly m er iZ ing th e
v iny l com pound h av ing th e m as ked f unctional g r oup With a
s ty r enic com pound in th e pr es ence of a poly m er iz ation
cataly s t com pr is ing ( A) a tr ans ition m etal com pound, ( B) at
leas t one com pound s elected f r om com pounds h av ing ox y
g en and com pounds Wh ich can f or m ionic com plex com
pounds by r eaction With th e tr ans ition m etal com pound and
( C) an or g anom etallic com pound. A s ty r enic copoly m er
Wh ich is a r andom , block or g r af t copoly m er , pr ef er ably a
r andom copoly m er , of a v iny l com pound h av ing a f unctional
g r oup and a s ty r enic com pound and h as th e r epeating units
der iv ed f r om th e s ty r enic com pound h av ing th e s y ndiotactic
con? g ur ation can be pr oduced ef f iciently .
Th e abov e s ty r enic r andom copoly m er ex h ibits ex cellent
ph y s ical pr oper ties s uch as ex cellent adh es ion With v ar ious
adh es iv es and ex cellent com patibility With v ar ious r ubber s
and is adv antag eous ly us ed f or v ar ious applications as
v ar ious ty pes of m olded ar ticles .
US 2002/ 0173605 A1
PROCESS FOR PROD UCIN G FUN CTION AL
STYREN E COPOLYMER AN D FUN CTION AL
STYREN E COPOLYMER
TECHN ICAL FIELD
[ 0001] Th e pr es ent inv ention r elates to a pr oces s f or
pr oducing a s ty r enic copoly m er h av ing a f unctional g r oup
and a s ty r enic copoly m er h av ing a f unctional g r oup. Mor e
par ticular ly , th e pr es ent inv ention r elates to a pr oces s f or
ef ? ciently pr oducing a s ty r enic copoly m er , in par ticular , a
s ty r enic r andom copoly m er , h av ing a f unctional g r oup and
th e s y ndiotactic con? g ur ation and a r andom s ty r enic copoly
m er h av ing a f unctional g r oup and th e s y ndiotactic con? g u
r ation and ex h ibiting im pr ov ed ph y s ical pr oper ties s uch as
adh es ion With adh es iv es and com patibility With v ar ious
r ubber s .
BACKGROUN D ART
[ 0002] Her etof or e, s ty r enic poly m er s pr oduced in accor
dance With th e r adical poly m er iZ ation ar e f or m ed into v ar i
ous s h apes in accor dance With v ar ious m olding pr oces s es
and Widely us ed f or h om e electr ic appliances , bus ines s
eq uipm ents , utens ils , packag ing container s , f ur nitur es , toy s ,
s y nth etic paper s and oth er indus tr ial m ater ials . HoWev er , th e
conv entional s ty r enic poly m er s h av e th e atactic con? g ur a
tion and h av e a dr aWback in th at h eat r es is tance and ch em i
cal r es is tance ar e poor .
[ 0003] To ov er com e th e abov e dr aWback of th e s ty r enic
poly m er s h av ing th e atactic con? g ur ation, th e g r oup of
inv es tig ator s in Wh ich th e pr es ent inv entor s ar e included
s ucceeded in dev eloping s ty r enic poly m er s h av ing a h ig h ly
s y ndiotactic con? g ur ation. Sty r enic copoly m er s of a s ty
r enic m onom er and oth er m onom er s h av ing th e s y ndiotactic
con? g ur ation Wer e als o s ucces s f ully dev eloped. Ex am ples
of s uch poly m er s and copoly m er s include s y ndiotactic
copoly m er s of s ty r ene and s ubs tituted s ty r enes ( J apanes e
Patent Application Laid-Open N o. Sh oWa 63( 19 8 8 )
24 1009 ) and s y ndiotactic copoly m er s of s ty r ene and polar
v iny l m onom er s ( J apanes e Patent Application Laid-Open
N os . Heis ei 2( 19 9 0) -258 8 10, Heis ei 2( 19 9 0) -258 8 05,
Heis ei 2( 19 9 0) -258 8 12, Heis ei 4 ( 19 9 2) -130108 , Heis ei
4 ( 19 9 2) -18 5619 and Heis ei 4 ( 19 9 2) -29 8 512) . Block
copoly m er s of s ty r ene and s ty r enic com pounds h av ing a
h eter oatom Wer e als o dev eloped ( J apanes e Patent Applica
tion Laid-Open N o. Heis ei 5( 19 9 3) -32028 1) .
[ 0004 ] HoWev er , th e abov e pr oces s es f or pr oducing s ty
r ene copoly m er s h av ing th e s y ndiotactic con? g ur ation by
copoly m er iZ ation h av e th e f olloWing dr aWbacks . ( 1) In th e
copoly m er iZ ation With polar v iny l m onom er s , am or ph ous
by pr oducts s oluble in s olv ents ar e occas ionally f or m ed in
g r eat am ounts or th e cr y s talline pr oper ty and h eat r es is tance
Wh ich ar e pr oper ch ar acter is tics of th e s y ndiotactic s ty r ene
r es ins ar e occas ionally adv er s ely af f ected. ( 2) It is des ir able
f or im pr ov ing ph y s ical pr oper ties th at a f unctional g r oup is
unif or m ly dis tr ibuted With in a poly m er . HoWev er , in a block
copoly m er of s ty r ene and a s ty r enic polar com onom er , a
m onom er h av ing th e f unctional g r oup is incor por ated only
into g r oWing end por tions of a poly m er and, th er ef or e, th e
ef f ect of im pr ov ing th e ph y s ical pr oper ties is s m aller th an
th at of r andom copoly m er s in Wh ich th e m onom er units
h av ing a f unctional g r oup ar e dis tr ibuted r andom ly in th e
m olecular ch ain. ( 3) Wh en a polar v iny l m onom er or a
N ov . 21, 2002
s ty r enic com pound h av ing a f unctional g r oup is pr es ent in
th e poly m er iZ ation s y s tem With out any pr etr eatm ents , th e
activ ity of a cataly s t and pr oductiv ity m ar kedly decr eas e due
to th e m onom er or th e com pound.
D ISCLOSURE OF THE IN VEN TION
[ 0005] Under th e abov e cir cum s tances , th e pr es ent inv en
tion h as an obj ect of pr ov iding a pr oces s f or ef ? ciently
pr oducing a s ty r enic copoly m er , in par ticular , a s ty r enic
r andom copoly m er , h av ing a f unctional g r oup and th e s y n
diotactic con? g ur ation and ex h ibiting im pr ov ed ph y s ical
pr oper ties s uch as adh es ion With adh es iv es and com patibil
ity With v ar ious r ubber s .
[ 0006] As th e r es ult of ex tens iv e s tudies by th e pr es ent
inv entor s to ach iev e th e abov e obj ect, it Was f ound th at,
Wh en a v iny l com pound h av ing a f unctional g r oup Was
tr eated With a m etal com pound to m as k th e f unctional g r oup
and copoly m er iZ ed With a s ty r enic com pound in th e pr es
ence of a s peci? c cataly s t, th e decr eas e in th e activ ity of th e
cataly s t Was s uppr es s ed and a s ty r enic copoly m er , in par
ticular , a r andom s ty r enic copoly m er , h av ing th e f unctional
g r oup and th e s y ndiotactic con? g ur ation could be ef ? ciently
obtained and th at th e s ty r enic r andom copoly m er h av ing
s peci? c r epeating units , th e f unctional g r oup and th e s y n
diotactic con? g ur ation Was v er y us ef ul f or im pr ov ing ph y s i
cal pr oper ties s uch as adh es ion With adh es iv es and com pat
ibility With v ar ious r ubber s . Th e pr es ent inv ention h as been
com pleted bas ed on th e knoWledg e.
[ 0007] Th e pr es ent inv ention pr ov ides a pr oces s f or pr o
ducing a s ty r enic copoly m er h av ing a f unctional g r oup and
a s y ndiotactic con? g ur ation, th e pr oces s com pr is ing br ing
ing a m etal com pound into inter action With a v iny l com
pound h av ing a f unctional g r oup to m as k th e f unctional
g r oup and copoly m er iZ ing th e v iny l com pound h av ing th e
m as ked f unctional g r oup With a s ty r enic com pound in a
pr es ence of a poly m er iZ ation cataly s t com pr is ing ( A) a
tr ans ition m etal com pound, ( B) at leas t one com pound
s elected f r om com pounds h av ing ox y g en and com pounds
Wh ich can f or m ionic com plex com pounds by r eaction With
th e tr ans ition m etal com pound and ( C) an or g anom etallic
com pound.
[ 0008 ] Th e pr es ent inv ention als o pr ov ides a r andom
s ty r enic copoly m er h av ing a f unctional g r oup and a s y ndio
tactic con? g ur ation, th e copoly m er com pr is ing :
[ 0009 ] ( a) s ty r enic r epeating units r epr es ented by
g ener al f or m ula ( II) :
( 11)
CH; CH
[ 0010] Wh er ein R8 r epr es ents h y dr og en atom , a h alog en
atom or a s ubs tituent h av ing C, Sn or Si, t r epr es ents an
integ er of 1 to 5 and, Wh en a plur ality of R8 ar e pr es ent, th e
plur ality of R8 m ay r epr es ent a s am e g r oup or dif f er ent
g r oups , and
US 2002/ 0173605 A1
[ 0011] ( b) r epeating units Wh ich ar e der iv ed f r om a
v iny l com pound h av ing a f unctional g r oup and r ep
r es ented by g ener al f or m ula ( III) :
( III)
CH2 CH
( R' ) m
( D ) n
[ 0012] Wh er ein D r epr es ents a s ubs tituent h av ing ORl,
1COR1, CO2R1, CN , N R1R2, SR1 or PR1R2,
R and R2 each r epr es enting h y dr og en atom , an alky l g r oup
h av ing 1 to 20 car bon atom s , an ar y l g r oup h av ing 6 to 20
car bon atom s or an alky ls ily l g r oup h av ing 3 to 20 car bon
atom s ; R r epr es ents a linear or br anch ed h y dr ocar bon g r oup
h av ing 1 to 20 car bon atom s ; Wh en a plur ality of D ar e
pr es ent, th e plur ality of D m ay r epr es ent a s am e g r oup or
dif f er ent g r oups ; n r epr es ents an integ er of 1 to 5; m
r epr es ents an integ er of 0 to 4 ; and n+m 5,
[ 0013] Wh er ein th e copoly m er com pr is es 0. 01 to 50%
by m ole of r epeating unit ( b) and a s ter ic r eg ular ity
of th e copoly m er com pr is ing r epeating unit ( a) and
r epeating unit ( b) is s y ndiotactic.
THE MOST PREFERRED EMBOD IMEN T TO
CARRY OUT THE IN VEN TION
[ 0014 ] In accor dance With th e pr oces s of th e pr es ent
inv ention, a s ty r enic copoly m er , in par ticular , a r andom
s ty r enic copoly m er , h av ing a f unctional g r oup and th e
s y ndiotactic con? g ur ation can be obtained. Block copoly
m er s and g r af t copoly m er s can als o be pr oduced. Sty r enic
block copoly m er s can be pr oduced, f or eX am ple, by apply
ing th e pr oces s of th e pr es ent inv ention to th e tWo-s tep
pr oces s des cr ibed in J apanes e Patent Application Laid-Open
N o. Heis ei 5( 19 9 3) -32028 1. Block, r andom and alter nating
s ty r enic copoly m er s can be obtained by apply ing th e pr oces s
of th e pr es ent inv ention to th e pr oces s des cr ibed in J apanes e
Patent Application Laid-Open N o. Sh oWa 63( 19 8 8 ) -24 1009 .
[ 0015] As th e r aW m ater ial m onom er s in th e pr oces s of th e
pr es ent inv ention, a v iny l com pound h av ing a f unctional
g r oup and a s ty r enic com pound can be us ed.
[ 0016] EX am ples of th e v iny l com pound h av ing a f unc
tional g r oup include s ty r enic com pounds h av ing a f unctional
g r oup Wh ich ar e r epr es ented by g ener al f or m ula ( 1) :
( I)
CH=CH2
[ 0017] Wh er ein X r epr es ents a f unctional g r oup Wh ich can
be m as ked With th e m etal com pound; R0 r epr es ents a h y dr o
N ov . 21, 2002
car bon g r oup; Wh en a plur ality of X ar e pr es ent, th e plur ality
of X m ay r epr es ent th e s am e g r oup or dif f er ent g r oups ; Wh en
a plur ality of R0 ar e pr es ent, th e plur ality of R0 m ay
r epr es ent th e s am e g r oup or dif f er ent g r oups ; n r epr es ents an
integ er of 1 to 5; m r epr es ents an integ er of 0 to 5; and
n+m 5.
[ 0018 ] EX am ples of th e pr ef er able s ty r enic com pound
h av ing a f unctional g r oup Wh ich is r epr es ented by g ener al
f or m ula ( I) include com pounds r epr es ented by g ener al f or
m ula ( I) in Wh ich X r epr es ents a s ubs tituent h av ing ORl,
COR1, CO2R1, CN , N R1R2, SR1 or PRlR2
and R0 r epr es ents a linear or br anch ed h y dr ocar bon g r oup
h av ing 1 to 20 car bon atom s .
[ 0019 ] R1 and R2 each r epr es ent h y dr og en atom , an alky l
g r oup h av ing 1 to 20 car bon atom s , an ar y l g r oup h av ing 6
to 20 car bon atom s or an alky ls ily l g r oup h av ing 3 to 20
car bon atom s . Wh en th e g r oups r epr es ented by R1 and R2 ar e
pr es ent in th e s am e s ubs tituent, th e g r oups r epr es ented by R1
and R2 m ay be th e s am e With or dif f er ent f r om each oth er .
As th e g r oup r epr es ented by R0, linear or br anch ed alky l
g r oups ar e pr ef er able. EX am ples of th e alky l g r oup r epr e
s ented by R0 include m eth y l g r oup, eth y l g r oup, n-pr opy l
g r oup, is opr opy l g r oup, n-buty l g r oup, is obuty l g r oup, ter t
buty l g r oup, n-h eX y l g r oup and n-decy l g r oup.
[ 0020] Speci? c eX am ples of th e abov e s ty r enic com pound
h av ing a f unctional g r oup include h y dr oX y s ty r enes s uch as
o-h y dr oX y s ty r ene, p-h y dr oX y s ty r ene and m -h y dr oX y s ty
r ene; alkoX y s ty r enes and s iloX y s ty r enes s uch as o-m eth oX y
s ty r ene, p-m eth oX y s ty r ene, m -m eth oX y s ty r ene, o-eth oX y
s ty r ene, p-eth oX y s ty r ene, m -eth oX y s ty r ene, 4 -m eth oX y -3
m eth y ls ty r ene, p-pr opoX y s ty r ene, p-ph enoX y s ty r ene, p-t
butoX y s ty r ene, p-tr ity loX y s ty r ene, p-tr im eth y ls iloX y s ty r ene,
p-t-buty ldim eth y ls iloX y s ty r ene, p-tr iis opr opy ls iloX y s ty r ene
and p-acetoX y s ty r ene; eth er s ty r enes s uch as p-v iny lbenZ y l
m eth y l eth er , p-v iny lbenZ y l eth y l eth er , p-v iny lbenZ y l n-pr o
py l eth er , p-v iny lbenZ y l is opr opy l eth er , p-v iny lbenZ y l n-bu
ty l eth er , p-v iny lbenZ y l t-buty l eth er , 1-( 4 -v iny lph eny l) -1, 1
dim eth y lm eth y l m eth y l eth er , 1 -( 4 -v iny lph eny l) -1 , 1 -
dim eth y lm eth y l eth y l eth er , ( 1 -( 4 -v iny lph eny l) -1 , 1 -
dim eth y lm eth y l pr opy l eth er , 1 -( 4 -v iny lph eny l) - 1 , 1 -
dim eth y lm eth y l buty l eth er , 1 -( 4 -v iny lph eny l) - 1 , 1 -
diph eny lm eth y l m eth y l eth er , 1 -( 4 -v iny lph eny l) - 1 , 1 -
diph eny lm eth y l eth y l eth er , 1 -( 4 -v iny lph eny l) - 1 , 1 -
diph eny lm eth y l buty l eth er , 1 -( 4 -v iny lph eny l) - 1 , 1 -
dim eth y lm eth y l tr im eth y ls ily l eth er and 1-( 4 -v iny lph eny l)
1, 1-dim eth y lm eth y l tr ieth y ls ily l eth er ; alcoh ols s uch as
p-v iny lbenZ y l alcoh ol, ( 4 -v iny lph eny l) -1, 1-dim eth y lm eth a
nol, ( 4 -v iny lph eny l) -1, 1-diph eny lm eth anol and 2-( 4 -v i
ny lph eny l) eth anol; am ines s uch as 2-am inos ty r ene, 3-am i
nos ty r ene, 4 -am inos ty r ene, 3, 4 -diam inos ty r ene,
4 -v iny lbenZ y lam ine and 2-( 4 -v iny lph eny l) eth y lam ine; am i
nos ty r enes s ubs tituted With alky l g r oups s uch as m -N , N
dim eth y lam inos ty r ene, p-N , N -dim eth y lam inos ty r ene, p-v i
ny lbenZ y l-N , N -dim eth y lam ine, p-v iny lbenZ y l-N , N
dieth y lam ine, p-v iny lbenZ y l-N , N -di-n-pr opy lam ine,
p-v iny lbenZ y l-N , N -di-n-buty lam ine, p-( N , N -dim eth y lam i
no) s ty r ene, p-( N , N -dieth y lam ino) s ty r ene, p-( N , N -di-n-pr o
py lam ino) s ty r ene, p-( N , N -di-n-buty lam ino) s ty r ene, N -( p
v iny lbenZ y l) -py r r olidine, N -( p-v iny lbenZ y l) piper idine and
N -( p-v iny lbenZ y l) m or ph oline; s ty r enes h av ing car bony l
g r oup s uch as p-v iny lbenZ oic acid, m eth y l p-v iny lbenZ oate,
ph eny l p-v iny lbenZ oate, m eth y l 3-v iny ls alicy late, p-f or m y l
s ty r ene, p-acety ls ty r ene and p-v iny lbenZ oph enone;
US 2002/ 0173605 A1
cy anos ty r enes s uch as o-cy anos ty r ene, m -cy anos ty r ene and
p-cy anos ty r ene; m er captos ty r enes and alky lth ios ty r enes
s uch as o-m er captos ty r ene, m -m er captos ty r ene, p-m er cap
tos ty r ene, o-m eth y lth ios ty r ene, m -m eth y l-th ios ty r ene,
p-m eth y lth ios ty r ene, o-eth y lth ios ty r ene, m -eth y lth ios ty r ene
and p-eth y lth ios ty r ene; p-s ty r y ldiph eny lph os ph ine; 3, 5
dim eth y l-4 -h y dr ox y s ty r ene; 3, 5-dieth y l4 -h y dr ox y s ty r ene;
3, 5-dipr opy l-4 -h y dr ox y s ty r ene; 3, 5-diis opr opy l-4 -h y dr ox y
s ty r ene; 3, 5-di-ter t-buty l4 -h y dr ox y s ty r ene; 3, 5-di-ter t-bu
ty l-4 -am inos ty r ene and 3, 5-di-ter t-buty l-car box y s ty r ene.
[ 0021] Fur th er ex am ples of th e pr ef er able s ty r enic com
pound h av ing a f unctional g r oup include com pounds r epr e
s ented by g ener al f or m ula ( I) in Wh ich X r epr es ents a g r oup
r epr es ented by ( CR3R4 ) PD or Z ( Q R5R6R7) q .
[ 0022] In th e g r oup r epr es ented by ( CR3R4 ) PD , D
r epr es ents a s ubs tituent h av ing ORl, COR1, CO2R1,
CN , N R1R2, SR1 or PR1R2; R3 and R4 each r ep
r es ent an alky l g r oup h av ing 1 to 20 car bon atom s , an ar y l
g r oup h av ing 6 to 20 car bon atom s or an alky ls ily l g r oup
h av ing 3 to 20 car bon atom s ; R1 and R2 ar e as de? ned abov e;
p r epr es ents an integ er of 1 to 10; Wh en a plur ality of
CR R4 ar e pr es ent, th e plur ality of CR3R4 m ay r epr e
s ent th e s am e g r oup or dif f er ent g r oups ; and R3 and R4 m ay
r epr es ent th e s am e g r oup or dif f er ent g r oups .
[ 0023] In th e g r oup r epr es ented by Z ( Q R5R6R7) q , Z
r epr es ents 0, N or S; Q r epr es ents C, Si or Sn; R5 to R7 each
r epr es ent an alky l g r oup h av ing 1 to 20 car bon atom s , an ar y l
g r oup h av ing 6 to 20 car bon atom s or an alky ls ily l g r oup
h av ing 3 to 20 car bon atom s ; q r epr es ents 1 or 2; Wh en q
r epr es ents 2, th e tWo Q RSRGR7 m ay r epr es ent th e s am e
g r oup or dif f er ent g r oups ; and R5 to R7 m ay r epr es ent th e
s am e g r oup or dif f er ent g r oups .
[ 0024 ] Speci? c ex am ples of th e abov e s ty r enic com pound
h av ing a f unctional g r oup include eth er s ty r enes s uch as
1-( 4 -v iny lph eny l) -1, 1-dim eth y lm eth y l m eth y l eth er , 1-( 4
v iny lph eny l) -1, 1-dim eth y lm eth y l eth y l eth er , 1-( 4 -v iny lph e
ny l) -1, 1-dim eth y lm eth y l buty l eth er , 1-( 4 -v iny l-ph eny l) -1,
1-diph eny lm eth y l m eth y l eth er , 1-( 4 -v iny lph eny l) -1, 1
diph eny l-m eth y l eth y l eth er , 1-( 4 -v iny lph eny l) -1, 1
diph eny lm eth y l buty l eth er , 1-( 4 -v iny lph eny l) -1, 1
dim eth y lm eth y l tr im eth y ls ily l eth er and 1-( 4 -v iny lph eny l)
1, 1-dim eth y lm eth y l tr ieth y ls ily l eth er ; alcoh ols s uch as
4 -( v iny lph eny l) -1, 1-dim eth y lm eth anol and 4 -( v iny lph eny l)
1, 1-diph eny l-m eth anol; and oth er eth er s ty r enes s uch as
p-t-butox y s ty r ene, p-tr ity lox y s ty r ene, p-tr im eth y ls ilox y s ty
r ene, p-t-buty ldim eth y ls ilox y s ty r ene and p-tr iis opr opy ls i
lox y s ty r ene.
[ 0025] In th e pr es ent inv ention, th e s ty r enic com pound
h av ing a f unctional g r oup m ay be us ed s ing ly or in com bi
nation of tWo or m or e.
[ 0026] In th e pr oces s of th e pr es ent inv ention, ex am ples of
th e s ty r enic com pound Wh ich is copoly m er iZ ed With th e
abov e s ty r enic com pound h av ing a f unctional g r oup include
com pounds r epr es ented by g ener al f or m ula ( IV) :
N ov . 21, 2002
( IV)
on: CH2
( R8 )
/
[ 0027] Wh er ein R8 r epr es ents h y dr og en atom , a h alog en
atom or a s ubs tituent h av ing C, Sn or Si, t r epr es ents an
integ er of 1 to 5 and, Wh en a plur ality of R8 ar e pr es ent, th e
plur ality of R8 m ay r epr es ent th e s am e g r oup or dif f er ent
g r oups .
[ 0028 ] Ex am ples of th e s ty r enic com pound r epr es ented by
g ener al f or m ula ( IV) include s ty r ene; alky ls ty r enes s uch as
p-m eth y ls ty r ene, m -m eth y ls ty r ene, o-m eth y ls ty r ene, 2, 4
dim eth y ls ty r ene, 2, 5-dim eth y ls ty r ene, 3, 4 -dim eth y ls ty r ene,
3, 5 -dim eth y ls ty r ene, p-eth y ls ty r ene, m -eth y ls ty r ene and p-t
buty ls ty r ene; poly v iny lbenZ enes s uch as p-div iny lbenZ ene,
m -div iny lbenZ ene and tr iv iny lbenZ ene; h alog enated s ty
r enes s uch as p-ch lor os ty r ene, m -ch lor os ty r ene, o-ch lor os ty
r ene, p-br om os ty r ene, m -br om os ty r ene, o-br om os ty r ene,
p-? uor os ty r ene, m -? uor os ty r ene, o-? uor os ty r ene and o-m e
th y l-p-? uor os ty r ene; m -ph eny ls ty r ene; and p-ph eny ls ty
r ene. Th e s ty r enic com pound m ay be us ed s ing ly or in
com bination of tWo or m or e.
[ 0029 ] In th e pr oces s of th e pr es ent inv ention, th e r elativ e
am ounts of th e abov e s ty r enic com pound h av ing a f unc
tional g r oup and th e s ty r enic com pound r epr es ented by
g ener al f or m ula ( IV) ar e not par ticular ly lim ited. In g ener al,
th e r atio of th e am ounts in m ole of th e s ty r enic com pound
h av ing a f unctional g r oup to th e s ty r enic com pound r epr e
s ented by g ener al f or m ula ( IV) is s elected in th e r ang e of
0. 01: 9 9 . 9 9 to 50: 50, pr ef er ably in th e r ang e of 05: 9 9 . 5 to
30: 70 and m or e pr ef er ably in th e r ang e of 1: 9 9 to 20: 8 0.
[ 0030] In th e pr oces s of th e pr es ent inv ention, a m etal
com pound is br oug h t into inter action With th e abov e v iny l
com pound h av ing a f unctional g r oup to m as k th e f unctional
g r oup.
[ 0031] Ex am ples of th e m etal com pound include com
pounds r epr es ented by g ener al f or m ula ( V) :
M( A) I ( V)
[ 0032] Wh er ein M r epr es ents a m etal s elected f r om m etals
of Gr oups 1 to 8 and Gr oups 11 to 14 of th e Per iodic Table,
Ar epr es ents h y dr og en atom , a h alog en atom , an alky l g r oup
h av ing 1 to 20 car bon atom s , an ar y l g r oup h av ing 6 to 20
car bon atom s , an alkox y l g r oup h av ing 1 to 20 car bon atom s
or an ar y lox y l g r oup h av ing 6 to 20 car bon atom s , r
r epr es ents th e v alence of th e m etal r epr es ented by M and,
Wh en a plur ality of A ar e pr es ent, th e plur ality of A m ay
r epr es ent th e s am e g r oup or dif f er ent g r oups .
[ 0033] Speci? c ex am ples of th e m etal r epr es ented by M in
g ener al f or m ula ( V) include Li, N a, K, Be, Mg , Ca, Sr , Ba,
Sc, Y, La, Ti, Z r , Hf , V, N b, Ta, Cr , Mo, Mn, Fe, Ru, Cu, Z n,
Cd, Hg , Al, Ga, Sn and Pb. Am ong th es e m etals , Li, N a, K,
Mg , Ti, Z r , Hf , Cu, Z n, Cd, Hg , Al, Ga, Sn and Pb ar e
pr ef er able and Al is m or e pr ef er able.
US 2002/ 0173605 A1
[ 0034 ] As th e m etal com pound, alum inum com pounds
h av ing alky l g r oups ar e pr ef er able and tr ialky lalum inum and
dialky lalum inum com pounds ar e m or e pr ef er able. Ex am ples
of th e alum inum com pound h av ing alky l g r oups include
tr ialky lalum inum s s uch as tr im eth y lalum inum , tr ieth y lalu
m inum , tr i-n-pr opy lalum inum , tr iis opr opy lalum inum , tr i-n
buty lalum inum , tr iis obuty lalum inum and tr i-t-buty lalum i
num ; dialky lalum inum h alides s uch as dim eth y lalum inum
ch lor ide, dieth y lalum inum ch lor ide, di-n-pr opy lalum inum
ch lor ide, diis opr opy l-alum inum ch lor ide, di-n-buty lalum i
num ch lor ide, diis obuty lalum inum ch lor ide and di-t-buty la
lum inum ch lor ide; dialky lalum inum alkox ides s uch as dim
eth y lalum inum m eth ox ide and dim eth y lalum inum eth ox ide;
and dialky lalum inum h y dr ides s uch as dim eth y lalum inum
h y dr ide, dieth y lalum inum h y dr ide and diis obuty lalum inum
h y dr ide.
[ 0035] In th e pr es ent inv ention, th e m etal com pound m ay
be us ed s ing ly or in com bination of tWo or m or e.
[ 0036] In th e pr oces s of th e pr es ent inv ention, a poly m er
iZ ation cataly s t com pr is ing ( A) a tr ans ition m etal com pound,
( B) at leas t one com pound s elected f r om com pounds h av ing
ox y g en and com pounds Wh ich can f or m ionic com plex
com pounds by r eaction With th e tr ans ition m etal com pound
and ( C) an or g anom etallic com pound is us ed.
[ 0037] Th e abov e com ponents of th e cataly s t Will be
des cr ibed in th e f olloWing .
[ 0038 ] ( A) Tr ans ition Metal Com pound
[ 0039 ] As th e tr ans ition m etal com pound us ed in th e
pr es ent inv ention, v ar ious com pounds can be us ed. Com
pounds of tr ans ition m etals of Gr oups 4 to 6 and Gr oups 8
to 10 of th e Per iodic Table ar e pr ef er ably us ed. Ex am ples of
th e com pounds of tr ans ition m etals of Gr oups 4 to 6 of th e
Per iodic Table include com pounds r epr es ented by g ener al
f or m ulae ( VI) to ( IX ) s h oWn in th e f olloWing . Ex am ples of
th e com pounds of tr ans ition m etals of Gr oups 8 to 10 of th e
Per iodic Table include com pounds r epr es ented by g ener al
f or m ula als o s h oWn in th e f olloWing .
[ 004 0] In th e abov e f or m ulae, Q 1 r epr es ents a bonding
g r oup connecting tWo conj ug ated ? v e-m em ber ed lig ands
Wh ich ar e r epr es ented by ( C5H5_ a_ bR9 b) and ( C5H5_ a_ cR1Oc) ;
Q 2 r epr es ents a bonding g r oup connecting a conj ug ated
? v e-m em ber ed lig and r epr es ented by ( C5H5_ a_ dR11( Q and a
g r oup r epr es ented by Z 1; R9 , R10, R11 and R12 each r epr es ent
a h y dr ocar bon g r oup, a h alog en atom , an alkox y l g r oup, a
h y dr ocar bon g r oup h av ing s ilicon atom , a h y dr ocar bon
g r oup h av ing ph os ph or us atom , a h y dr ocar bon g r oup h av ing
nitr og en atom or a h y dr ocar bon g r oup h av ing bor on atom ;
w h en a plur ality of g r oups r epr es ented by any of R9 , R10,
R and R12 ar e pr es ent, th e plur ality of g r oups m ay be th e
s am e With or dif f er ent f r om each oth er and m ay be bonded
to each oth er to f or m a cy clic s tr uctur e; a r epr es ents 0, 1 or
2; b, c and d each r epr es ent an integ er of 0 to 5 Wh en a=0,
an integ er of 0 to 4 Wh en a=1 and an integ er of 0 to 3 Wh en
a=2; e r epr es ents an integ er of 0 to 5; M1 r epr es ents a
tr ans ition m etal s elected f r om m etals of Gr oups 4 to 6 of th e
N ov . 21, 2002
Per iodic Table; M2 r epr es ents a tr ans ition m etal s elected
f r om m etals of Gr oups 8 to 10 of th e Per iodic Table; L1 and
L2 each r epr es ent a lig and f or m ing a coor dinating bond; X 1,
Y1, Z , W1 and U1 each r epr es ent a lig and f or m ing a
cov alent bond or an ionic bond; and th e lig ands r epr es ented
by L1, L2, X 1, Y1, W1 and U1 m ay be bonded to each oth er
to f or m a cy clic s tr uctur e.
[ 004 1] Ex am ples of th e g r oups r epr es ented by Q 1 and Q 2
in th e abov e g ener al f or m ulae ( VI) and ( VII) include ( 1)
alky lene g r oups h av ing 1 to 4 car bon atom s , cy cloalky lene
g r oups and th es e g r oups s ubs tituted With loWer alky l g r oups
as s ide ch ain g r oups or ph eny l g r oup s uch as m eth y lene
g r oup, eth y lene g r oup, is opr opy lene g r oup, m eth y lph eny l
m eth y lene g r oup, diph eny lm eth y lene g r oup and cy cloh ex y
lene g r oup; ( 2) s ily lene g r oups , olig os ily lene g r oups and
th es e g r oups s ubs tituted With loWer alky l g r oups as s ide
ch ain g r oups or ph eny l g r oup s uch as s ily lene g r oup, dim
eth y ls ily lene g r oup, m eth y lph eny ls ily lene g r oup, diph eny l
s ily lene g r oup, dis ily lene g r oup and tetr am eth y ldis ily lene
g r oup; ( 3) h y dr ocar bon g r oups , s uch as loWer alky l g r oups ,
ph eny l g r oup and h y dr ocar by lox y g r oups Wh ich ar e pr ef er
ably loWer alkox y l g r oups , h av ing g er m anium atom , ph os
ph or us atom , nitr og en atom , bor on atom or alum inum atom
s uch as ( CH3) 2Ge g r oup, ( C6H5) 2Ge g r oup, ( CH3) P g r oup,
( CGHQ P g r oup, ( C4 H9 ) N g r oup, ( CGHQ N g r oup, ( CH3) B
g r oup, ( C4 H9 ) B g r oup, ( C6H5) B g r oup, ( C6H5) Al g r oup and
( CH3O) Al g r oup. Am ong th es e g r oups , alky lene g r oups and
s ily lene g r oups ar e pr ef er able.
[ 004 2] ( C5H5-a-bR9 b) > ( C5H5acR1Oc) and ( C5H5-a-dR11d)
each r epr es ent a conj ug ated ? v e-m em ber ed lig and. In th es e
f or m ulae, R9 , R10 and R11 each r epr es ent a h y dr ocar bon
g r oup, a h alog en atom , an alkox y l g r oup, a h y dr ocar bon
g r oup h av ing s ilicon atom , a h y dr ocar bon g r oup h av ing
ph os ph or us atom , a h y dr ocar bon g r oup h av ing nitr og en
atom or a h y dr ocar bon g r oup h av ing bor on atom ; and a
r epr es ents 0, 1 or 2; and b, c and d each r epr es ent an integ er
of 0 to 5 Wh en a=0, an integ er of 0 to 4 Wh en a=1 and an
integ er of 0 to 3 Wh en a=2. As th e h y dr ocar bon g r oup,
h y dr ocar bon g r oups h av ing 1 to 20 car bon atom s ar e pr ef
er able and h y dr ocar bon g r oups h av ing 1 to 12 car bon atom s
ar e m or e pr ef er able. Th e h y dr ocar bon g r oup m ay be a
m onov alent g r oup bonded to cy clopentadieny l g r oup Wh ich
is a conj ug ated ? v e-m em ber ed g r oup. Wh en a plur ality of
h y dr ocar bon g r oups ar e pr es ent, tWo of th e plur ality of
h y dr ocar bon g r oups m ay be bonded to each oth er to f or m a
cy clic s tr uctur e in com bination With a por tion of cy clopen
tadieny l g r oup. Ex am ples of th e conj ug ated ? v e-m em ber ed
r ing include s ubs tituted or uns ubs tituted cy clopentadieny l
g r oup, indeny l g r oup and ? uor eny l g r oup. Ex am ples of th e
h alog en atom include ch lor ine atom , br om ine atom , iodine
atom and ? uor ine atom . As th e alkox y l g r oup, alkox y l
g r oups h av ing 1 to 12 car bon atom s ar e pr ef er able.
Ex am ples of th e h y dr ocar bon g r oup h av ing s ilicon include
g r oups r epr es ented by Si( R13) ( R14 ) ( R15) , Wh er ein R13,
R and R15 each r epr es ent a h y dr ocar bon g r oup h av ing 1 to
24 car bon atom s . Ex am ples of th e h y dr ocar bon g r oup h av
ing ph os ph or us atom , th e h y dr ocar bon g r oup h av ing nitr o
g en atom and th e h y dr ocar bon g r oup h av ing bor on atom
include g r oups r epr es ented by P( R16) ( R17) ,
16N ( R16) ( R17) and B( R16) ( R17) , r es pectiv ely , Wh er ein
R and R17 each r epr es ent a h y dr ocar bon g r oup h av ing 1 to
18 car bon atom s . Wh en a plur ality of g r oups r epr es ented by
any of R9 , R10 and R11 ar e pr es ent, th e plur ality of R9 , R10
or Rll m ay r epr es ent th e s am e g r oup or dif f er ent g r oups . In
US 2002/ 0173605 A1
g ener al f or m ula ( VI) , th e conj ug ated ? v e-m em ber ed lig ands
r epr es ented by ( C5H5_ a_ bR9 b) and ( C5H5_ a_ cR1Oc) m ay be th e
s am e With or dif f er ent f r om each oth er .
[ 004 3] M1 r epr es ents a tr ans ition m etal elem ent of any of
Gr oups 4 to 6 of th e Per iodic Table. Ex am ples of th e
tr ans ition m etal elem ent include titanium , Z ir conium ,
h af nium , niobium , m oly bdenum and tung s ten. Am ong th es e
elem ents , titanium , Z ir conium and h af nium ar e pr ef er able
and titanium is m or e pr ef er able. Z 1 r epr es ents a lig and
f or m ing a cov alent bond. Speci? cally , Z 1 r epr es ents ox y g en
( O) , s ulf ur ( S) , an alkox y l g r oup h av ing 1 to 20
car bon atom s and pr ef er ably 1 to 10 car bon atom s , a
th ioalkox y l g r oup h av ing 1 to 20 car bon atom s and pr ef er
ably 1 to 12 car bon atom s , a h y dr ocar bon g r oup h av ing
nitr og en atom and 1 to 4 0 car bon atom s and pr ef er ably 1 to
18 car bon atom s or a h y dr ocar bon g r oup h av ing ph os ph or us
atom and 1 to 4 0 car bon atom s and pr ef er ably 1 to 18 car bon
atom s . X 1 and Y1 each r epr es ent a lig and f or m ing a cov alent
bond Speci? cally , X 1 and Y1 each r epr es ent h y dr og en atom ,
a h alog en atom , a h y dr ocar bon atom h av ing 1 to 20 car bon
atom s and pr ef er ably 1 to 10 car bon atom s , an alkox y l g r oup
h av ing 1 to 20 car bon atom s and pr ef er ably 1 to 10 car bon
atom s , am ino g r oup, a h y dr ocar bon g r oup h av ing ph os ph o
r us atom and 1 to 20 car bon atom s and pr ef er ably 1 to 12
car bon atom s s uch as diph eny lph os ph ine g r oup, a h y dr o
car bon g r oup h av ing s ilicon and 1 to 20 car bon atom s and
pr ef er ably 1 to 12 car bon atom s s uch as tr im eth y ls ily l g r oup
or a bor on com pound h av ing h y dr ocar bon g r oups h av ing 1
to 20 car bon atom s and pr ef er ably 1 to 12 car bon atom s or
f abr ic, a container or an ar ticle pr epar ed in accor dance With
th e inj ection m olding or th e bloW m olding .
[ 004 4 ] As th e pr oces s f or pr oducing a m olded ar ticle f r om
th e s ty r enic copoly m er of th e pr es ent inv ention, v ar ious
pr oces s es can be us ed. Th e f olloWing pr oces s es can be
adv antag eous ly us ed. Th e abov e s ty r enic copoly m er or a
com pos ition pr epar ed by adding v ar ious com ponents
des cr ibed abov e to th e s ty r enic copoly m er is pr elim inar ily
f or m ed into a pr elim inar ily m olded ar ticle f or th e h eat
tr eatm ent ( a ? lm , a s h eet or a container ) . In th is pr oces s , th e
m ater ial f or th e m olding pr epar ed abov e is m elted by
h eating and ex tr uded into a s uitable s h ape. A? lm or a s h eet
can be pr epar ed in accor dance With th e T-die m olding
pr oces s and oth er s tr uctur al ar ticles s uch as a container can
be pr epar ed in accor dance With th e inj ection m olding pr o
ces s . As th e ex tr us ion m ach ine us ed in th e abov e m olding
pr oces s es , any of a s ing le s cr eW ex tr uder and a tWin-s cr eW
ex tr uder With or With out v ents can be us ed. Th e condition of
th e ex tr us ion is not par ticular ly lim ited and can be s uitably
s elected in accor dance With th e s ituation. It is pr ef er able th at
th e tem per atur e dur ing th e m elting is s elected in th e r ang e of
th e m elting point of th e m ater ial us ed f or th e m olding to th e
tem per atur e h ig h er th an th e decom pos ition point by 50 C.
and th e s h ear ing s tr es s is s elected at 5> < 107 ptcm 2 or loWer
s ince th e pr elim inar ily m olded ar ticle f or th e h eat tr eatm ent
can be obtained With little f or m ation of r oug h s ur f aces .
[ 004 5] Af ter th e abov e ex tr us ion and m olding , it is pr ef
er able th at th e obtained pr elim inar ily m olded ar ticle f or th e
h eat tr eatm ent is s olidi? ed by cooling . As th e m edium f or
cooling , v ar ious m edia s uch as a g as , a liq uid and a m etal can
be us ed. Wh en th e pr elim inar ily m olded ar ticle f or lig and as
th at r epr es ented by X 1 Y1 or W1. In oth er Wor ds , U1
r epr es ents a lig and f or m ing a cov alent bond. Speci? cally , U1
r epr es ents h y dr og en atom , a h alog en atom , a h y dr ocar bon
N ov . 21, 2002
atom h av ing 1 to 20 car bon atom s and pr ef er ably 1 to 10
car bon atom s , an alkox y l g r oup h av ing 1 to 20 car bon atom s
and pr ef er ably 1 to 10 car bon atom s , am ino g r oup, a
h y dr ocar bon g r oup h av ing ph os ph or us atom and 1 to 20
car bon atom s and pr ef er ably 1 to 12 car bon atom s s uch as
diph eny lph os ph ine g r oup, a h y dr ocar bon g r oup h av ing s ili
con and 1 to 20 car bon atom s and pr ef er ably 1 to 12 car bon
atom s s uch as tr im eth y ls ily l g r oup or a bor on com pound
h av ing h y dr ocar bon g r oups h av ing 1 to 20 car bon atom s and
pr ef er ably 1 to 12 car bon atom s or h alog en atom s s uch as
B( C6H5) 4 and BF 4 . Am ong th e abov e lig ands , h alog en atom s
and h y dr ocar bon g r oups ar e pr ef er able. Th e lig ands r epr e
s ented X 1, Y1, W1 and U1 m ay be th e s am e With or dif f er ent
f r om each oth er . Th e lig ands r epr es ented by X 1, Y1, W1 and
U1 m ay be bonded to each oth er to f or m a cy clic s tr uctur e.
[ 004 6] ( a) Ex am ples of th e tr ans ition m etal com pounds
r epr es ented by g ener al f or m ulae ( VI) and ( VII) include th e
f olloWing com pounds .
[ 004 7] ( D Tr ans ition m etal com pounds h av ing tWo con
j ug ated ? v e-m em ber ed cy clic lig ands and no g r oups con
necting th e tWo lig ands s uch as bis ( cy clopentadieny l) tita
nium dich lor ide, bis ( m eth y lcy clopentadieny l) -titanium
dich lor ide, bis ( dim eth y lcy clopentadieny l) titanium dich lo
r ide, bis ( tr im eth y lcy clopentadieny l) titanium dich lor ide,
bis ( tetr am eth y l-cy clopentadieny l) titanium dich lor ide,
bis ( pentam eth y lcy clopentadieny l) -titanium dich lor ide,
bis ( n-buty lcy clopentadieny l) titanium dich lor ide, bis ( inde
ny l) titanium dich lor ide, bis ( ? uor eny l) titanium dich lor ide,
bis ( cy clopentadieny l) titanium ch lor oh y dr ide, bis ( cy clopen
tadieny l) -m eth y ltitanium ch lor ide, bis ( cy clopentadieny l
) eth y ltitanium ch lor ide, bis ( cy clopentadieny l) ph eny lti
tanium ch lor ide, bis ( cy clopentadieny l) -dim eth y ltitanium ,
bis ( cy clopentadieny l) diph eny ltitanium , bis -( cy clopentadi
eny l) dineopenty ltitanium , bis ( cy clopentadieny l) dih y dr o-ti
tanium , ( cy clopentadieny l) ( indeny l) titanium dich lor ide and
( cy clopentadieny l) ( ? luor eny l) titanium dich lor ide.
[ 004 8 ] @ Tr ans ition m etal com pounds h av ing tWo con
j ug ated ? v e-m em ber ed cy clic lig ands connected With an
alky lene g r oup s uch as m eth y lenebis ( indeny l) titanium
dich lor ide, eth y lenebis ( indeny l) titanium dich lor ide, m eth y l
enebis ( indeny l) titanium ch lor oh y dr ide, eth y lenebis -( inde
ny l) m eth y ltitanium ch lor ide, eth y lenebis ( indeny l) m eth ox y
ch lor o-titanium , eth y lenebis ( indeny l) titanium dieth ox ide,
eth y lenebis ( indeny l) -dim eth y ltitanium , eth y lenebis ( 4 , 5, 6, 7
tetr ah y dr oindeny l) titanium dich lor ide, eth y lenebis ( 2-m eth
y lindeny l) titanium dich lor ide, eth y lenebis -( 2, 4 -dim eth y lin
deny l) titanium dich lor ide, eth y lenebis ( 2-m eth y l-4
tr im eth y ls ily lindeny l) titanium dich lor ide, eth y lenebis ( 2, 4
dim eth y l-S, 6, 7-tr ih y dr oindeny l) titanium dich lor ide,
eth y lene( 2, 4 -dim eth y l-cy clopentadieny l) ( 3 , 5 -dim eth y lcy
clopentadieny l) titanium dich lor ide, eth y lene ( 2-m eth y l-4 -t
buty lcy clopentadieny l) ( 3 -t-buty l-5 -m eth y l-cy clopentadi
eny l) titanium dich lor ide, eth y lene( 2, 3, S-tr im eth y l
cy clopentadieny l) ( 2 , 4 , 5
tr im eth y lcy clopentadieny l) titanium dich lor ide,
is opr opy lidenebis ( 2-m eth y lindeny l) titanium dich lor ide, is o
pr opy lidenebis -( indeny l) titanium dich lor ide, is opr opy
lidenebis ( 2, 4 -dim eth y lindeny l) -titanium dich lor ide, is opr o
py lidene( 2, 4 -dim eth y lcy clopentadieny l) ( 3 , 5
dim eth y lcy clopentadieny l) titanium dich lor ide,
is opr opy lidene( 2-m eth y l-4 -t-buty lcy clopentadieny l) ( 3 -t
buty l-S -m eth y lcy clopentadieny l) titanium dich lor ide, m eth
y lene( cy clopentadieny l) ( 3, 4 -dim eth y lcy clopentadieny l) -ti
US 2002/ 0173605 A1
tanium dich lor ide, m eth y lene( cy clopentadieny l) ( 3, 4
dim eth y l-cy clopentadieny l) titanium ch lor oh y dr ide,
m eth y lene( cy clopentadieny l) -( 3, 4 -dim eth y lcy clopentadi
eny l) dim eth y ltitanium , m eth y lene-( cy clopentadieny l) ( 3, 4
dim eth y lcy clopentadieny l) diph eny ltitanium , m eth y lene( cy
clopentadieny l) ( tr im eth y lcy clopentadieny l) titanium
dich lor ide, m eth y lene( cy clopentadieny l) ( tet
r am eth y lcy clopentadieny l) -titanium dich lor ide, is opr opy
lidene( cy clopentadieny l) ( 3, 4 -dim eth y l-cy clopentadieny l) ti
tanium dich lor ide, is opr opy lidene( cy clopentadieny l) -( 2, 3, 4 ,
5-tetr am eth y lcy clopentadieny l) titanium dich lor ide,
is opr opy lidene-( cy clopentadieny l) ( 3-m eth y lindeny l) tita
nium dich lor ide, is opr opy lidene-( cy clopentadieny l) ( ? uor e
ny l) titanium dich lor ide, is opr opy lidene( 2-m eth y lcy clopen
tadieny l) ( ? uor eny l) titanium dich lor ide, is opr opy lidene( 2, 5
dim eth y lcy clopentadieny l) ( 3, 4
dim eth y lcy clopentadieny l) titanium dich lor ide,
is opr opy lidene( 2, 5-dim eth y lcy clopentadieny l) ( ? uor eny l)
titanium dich lor ide, eth y lene( cy clopentadieny l) ( 3, S-dim
eth y l-cy clopentadieny l) titanium dich lor ide, eth y lene( cy clo
pentadieny l) -( ? uor eny l) titanium dich lor ide, eth y lene( 2, 5
dim eth y lcy clopentadieny l) -( ? uor eny l) titanium dich lor ide,
eth y lene( 2, 5-dieth y lcy clopentadieny l) -( ? uor eny l) titanium
dich lor ide, diph eny lm eth y lene( cy clopentadieny l) ( 3, 4 -dieth
y lcy clopentadieny l) titanium dich lor ide, diph eny lm eth y lene
( cy clopentadieny l) ( 3, 4 -dieth y lcy clopentadieny l) titanium
dich lor ide, cy cloh eX y lidene( cy clopentadi
eny l) ( ? uor eny l) titanium dich lor ide and cy cloh eX y lidene( 2,
5-dim eth y lcy clopentadieny l) ( 3 , 4 -dim eth y l-cy clopentadi
eny l) titanium dich lor ide.
[ 004 9 ] @ Tr ans ition m etal com pounds h av ing tWo con
j ug ated ? v e-m em ber ed cy clic lig ands connected With a
s ily lene g r oup s uch as dim eth y ls ily lenebis ( indeny l) titanium
dich lor ide, dim eth y ls ily lenebis -( 4 , 5, 6, 7-tetr ah y dr oinde
ny l) titanium dich lor ide, dim eth y ls ily lenebis ( 2-m eth y linde
ny l) titanium dich lor ide, dim eth y ls ily lenebis ( 2, 4 -dim eth y l
indeny l) titanium dich lor ide, dim eth y ls ily lenebis ( 2, 4
dim eth y l-cy clopentadieny l) ( 3 , 5
dim eth y lcy clopentadieny l) titanium dich lor ide,
ph eny lm eth y ls ily lenebis ( indeny l) titanium dich lor ide, ph e
ny lm eth y l-s ily lenebis ( 4 , 5, 6, 7-tetr ah y dr oindeny l) titanium
dich lor ide, ph eny lm eth y l-s ily lenebis ( 2, 4 -dim eth y linde
ny l) titanium dich lor ide, ph eny lm eth y l-s ily lene( 2, 4 -dim eth
y lcy clopentadieny l) ( 3 , 5 -dim eth y lcy clopentadieny l) -tita
nium dich lor ide, ph eny lm eth y ls ily lene( 2, 3, S-tr im eth y l
cy clopentadieny l) ( 2 , 4 , 5
tr im eth y lcy clopentadieny l) titanium
ph eny lm eth y ls ily lenebis ( tet
r am eth y lcy clopentadieny l) titanium dich lor ide, diph eny ls i
ly lenebis ( 2, 4 -dim eth y lindeny l) titanium dich lor ide, diph e
ny l-s ily lenebis ( indeny l) titanium dich lor ide,
diph eny ls ily lenebis ( 2-m eth y lindeny l) titanium dich lor ide,
tetr am eth y ldis ily lenebis ( indeny l) titanium dich lor ide, tet
r am eth y ldis ily lenebis ( cy clopentadieny l) titanium dich lor ide,
tetr am eth y ldis ily lene( 3-m eth y lcy clopentadieny l) ( indeny l)
titanium dich lor ide, dim eth y ls ily lene( cy clopentadieny l) ( 3,
4 -dim eth y lcy clopentadieny l) titanium dich lor ide, dim eth y l
s ily lene
( cy clopentadieny l) ( tr im eth y lcy clopentadieny l) titanium
dich lor ide, dim eth y ls ily lene( cy clopentadi
eny l) ( tetr am eth y lcy clopentadieny l) titanium dich lor ide,
dim eth y ls ily lene( cy clopentadieny l) ( 3, 4 -dieth y l-cy clopenta
dieny l) titanium dich lor ide, dim eth y ls ily lene( cy clopentadi
eny l) -( tr ieth y lcy clopentadieny l) titanium dich lor ide, dim eth
dich lor ide,
N ov . 21, 2002
y ls ily lene
( cy clopentadieny l) ( tetr aeth y lcy clopentadieny l) titanium
dich lor ide, dim eth y ls ily lene( cy clopentadi
eny l) ( ? uor eny l) titanium dich lor ide, dim eth y ls ily lene( cy clo
pentadieny l) ( 2, 7-di-t-buty l? uor eny l) titanium dich lor ide,
dim eth y ls ily lene( cy clopentadieny l) ( octah y dr o? uor eny l) -ti
tanium dich lor ide, dim eth y ls ily lene( 2-m eth y lcy clopentadi
eny l) -( ? uor eny l) titanium dich lor ide, dim eth y ls ily lene( 2, 5
dim eth y l-cy clopentadieny l) ( ? uor eny l) titanium dich lor ide,
dim eth y ls ily lene( 2-eth y lcy clopentadieny l) ( ? uor e
ny l) titanium dich lor ide, dim eth y ls ily lene( 2, 5-dieth y lcy clo
pentadieny l) ( ? uor eny l) titanium dich lor ide, dieth y ls i
ly lene( 2-m eth y lcy clopentadieny l) ( 2 , 7 -di-t
buty l? uor eny l) titanium dich lor ide, dim eth y ls ily lene( 2, 5
dim eth y lcy clopentadieny l) ( 2 , 7 -di-t-buty l? uor eny l)
titanium dich lor ide, dim eth y ls ily lene( 2
eth y lcy clopentadieny l) ( 2 , 7 -di-t-buty l? uor eny l) titanium
dich lor ide, dim eth y ls ily lene( dieth y l-cy clopentadieny l) ( 2, 7
di-t-buty l? uor eny l) titanium dich lor ide, dim eth y l-s ily len
e( m eth y lcy clopentadieny l) ( octah y dr o? uor eny l) titanium
dich lor ide, dim eth y ls ily lene( dim eth y lcy c
lopentadieny l) ( octah y dr o? uor eny l) titanium dich lor ide, dim
eth y ls ily lene( eth y lcy clopentadieny l) ( octah y dr o? uor eny l)
titanium dich lor ide and
dim eth y ls ily lene( dieth y lcy clopentadieny l) -( octah y dr o? uo
r eny l) titanium dich lor ide.
[ 0050] @ Tr ans ition m etal com pounds h av ing tWo con
j ug ated ? v e-m em ber ed cy clic lig ands connected With a
h y dr ocar bon g r oup h av ing g er m anium atom , alum inum
atom , bor on atom , ph os ph or us atom or nitr og en atom s uch
as dim eth y lg er m y lenebis ( indeny l) titanium dich lor ide, dim
eth y lg er m y lene( cy clopentadieny l) ( ? uor eny l) titanium
dich lor ide, m eth y lalum y lenebis ( indeny l) titanium dich lo
r ide, ph eny lalum y lenebis -( indeny l) titanium dich lor ide, ph e
ny lph os ph y lenebis ( indeny l) titanium dich lor ide, eth y l
bor enebis ( indeny l) titanium dich lor ide, ph eny lalum y lene
bis ( indeny l) titanium dich lor ide and
ph eny lalum y lene( cy clopentadieny l) -( ? uor eny l) titanium
dich lor ide.
[ 0051] @ Tr ans ition m etal com pounds h av ing one con
j ug ated ? v e-m em ber ed cy clic lig and s uch as pentam eth y l
cy clopentadieny lbis ( ph eny l) -am inotitanium dich lor ide,
indeny lbis ( ph eny l) am inotitanium dich lor ide, pentam eth y l
cy clopentadieny lbis ( tr im eth y ls ily l) am inotitanium dich lo
r ide, pentam eth y lcy clopentadieny lph enoX y titanium dich lo
r ide, dim eth y l
s ily lene( tetr am eth y lcy clopentadieny l) ph eny lam inotitanium
dich lor ide, dim eth y ls ily lene( tetr am eth y lcy clopenetadieny l)
t-buty lam inotitanium dich lor ide, dim eth y ls ily lene( tetr ah y
dr oindeny l) decy lam inotitanium dich lor ide, dim eth y ls i
ly lene ( tetr ah y dr oindeny l) [ bis ( tr im eth y ls ily l) am ino]
titanium dich lor ide,
dim eth y lg er m y lene( tetr am eth y lcy clopentadieny l) -ph eny
lam inotitanium dich lor ide, pentam eth y lcy clopentadi
eny ltitanium tr im eth oX ide, pentam eth y lcy clopentadi
eny ltitanium tr ich lor ide, ( ter tiar y -buty lam ido) ( tetr am eth y l
115-cy clopentadieny l) -1, 2-eth andiy ltitanium dich lor ide,
( m eth y lam ido) ( tetr am eth y l-n5-cy clopentadieny l) -1, 2
eth andiy l-titanium dich lor ide, ( eth y lam ido) ( tetr am eth y l-115
cy clopentadieny l) -m eth y lenetitanium dich lor ide, ( ter tiar y
buty lam ido) dim eth y l( tetr am eth y l-n5
cy clopentadieny l) s ilanetitanium dich lor ide,
( benZ y lam ido) dim eth y l-( tetr am eth y l-nS-cy clopentadieny l
US 2002/ 0173605 A1
) s ilanetitanium dich lor ide and ( ph eny lph os ph ido) dim eth
y l( tetr am eth y l-n5-cy clopentadieny l) s ilane-titanium diben
Z y l.
[ 0052] @ Tr ans ition m etal com pounds h av ing tWo doubly
connected conj ug ated ? v e-m em ber ed cy clic lig ands s uch as
( 1, 1 -dim eth y ls ily lene) ( 2, 2 -is opr opy lidene) bis ( cy clopenta
dieny l) titanium dich lor ide, ( 1, 1 -dim eth y ls ily lene) ( 2, 2
dim eth y ls ily lene) bis -( cy clopentadieny l) titanium dich lor ide,
( 1, 1 -dim eth y ls ily lene) ( 2, 2 -is opr opy lidene) bis ( cy clopenta
dieny l) dim eth y ltitanium , ( 1, 1 -dim eth y l-s ily lene) ( 2, 2 -is o
pr opy lidene) bis ( cy clopentadieny l) dibenZ y ltitanium , ( 1, 1
dim eth y ls ily lene) ( 2, 2
is opr opy lidene) bis ( cy clopentadieny l) bis ( tr im eth y l
s ily l) titanium , ( 1, 1 -dim eth y ls ily lene) ( 2, 2
is opr opy lidene) bis
( cy clopentadieny l) bis ( tr im eth y ls ily lm eth y l) titanium , ( 1, 2
dim eth y l-s ily lene) ( 2, 1 -eth y lene) bis ( indeny l) titanium
dich lor ide, ( 1, 1 -dim eth y l-s ily lene) ( 2, 2 -eth y lene) bis ( inde
ny l) titanium dich lor ide, ( 1, 1 -eth y lene) ( 2, 2 -dim eth y ls ily le
ne) bis ( indeny l) titanium dich lor ide and ( 1, 1 -dim eth y l-s i
ly lene) ( 2, 2 -cy cloh eX y lidene) bis ( indeny l) titanium
dich lor ide.
[ 0053] @ Com pounds obtained by r eplacing ch lor ine
atom in th e abov e com pounds ( D to @ With br om ine atom ,
iodine atom , h y dr og en atom , m eth y l g r oup or ph eny l g r oup;
and com pounds obtained by r eplacing titanium as th e centr al
m etal of th e abov e tr ans ition m etal com pounds With Z ir co
nium , h af nium , niobium , m oly bdenum or tung s ten.
[ 0054 ] @ Am ong com pounds ( D to @ des cr ibed abov e,
com pounds Wh ich ar e th e tr ans ition m etal com pounds
h av ing one conj ug ated ? v e-m em ber ed cy clic lig and ar e
pr ef er ably us ed f or pr oducing th e s ty r enic copoly m er s h av
ing th e s y ndiotactic con? g ur ation.
[ 0055] ( b) Ex am ples of th e tr ans ition m etal com pounds
r epr es ented by th e abov e g ener al f or m ula ( VIII) Will be
des cr ibed in th e f olloWing .
[ 0056] Am ong th e tr ans ition m etal com pounds r epr e
s ented by g ener al f or m ula ( VIII) , com pounds r epr es ented by
g ener al f or m ula ( VIII) in Wh ich ( C5H5_ eR12e) r epr es ents a
g r oup s elected f r om th e g r oups r epr es ented by th e f olloWing
g ener al f or m ulae ( X I) to ( X VII) ar e pr ef er able.
( X I)
IIKS
R A R
R R
( X II)
R R
R
R
R
R
R
N ov . 21, 2002
-continued
( X III)
R, R
\
A
R? A) n R
\
A
/
R, R
( X Iv )
R R
R R
R R
R
R R
( X V)
R, R
\
A R
/
RTf AX .
\
A: : 9 g R /
Ra
R R
( X v I)
R
R, Ra
/
A A
/ \
Ra_ f A) n ( A? FRa
\ A A/
| |
R, R,
( X v II)
[ 0057] In th e abov e f or m ulae, A r epr es ents an elem ent of
any of Gr oups 13, 14 , 15 and 16 and, Wh en a plur ality of A
ar e pr es ent, th e plur ality of A m ay r epr es ent th e s am e g r oup
or dif f er ent g r oups . R r epr es ents h y dr og en atom , a h alog en
atom s , an aliph atic h y dr ocar bon g r oup h av ing 1 to 30 car bon
atom s , an ar om atic h y dr ocar bon g r oups h av ing 6 to 30
car bon atom s , an alkoX y l g r oup h av ing 1 to 30 car bon atom s ,
an ar y loX y l g r oup h av ing 6 to 30 car bon atom s , a th ioalkoX y l
g r oup h av ing 1 to 30 car bon atom s , a th ioar y loX y l g r oup
h av ing 6 to 30 car bon atom s , am ino g r oup, am ido g r oup,
car boX y l g r oup, an alky ls ily l g r oup h av ing 3 to 30 car bon
atom s or an alky ls ily lalky l g r oup. Th e plur ality of R m ay
r epr es ent th e s am e atom or g r oup or dif f er ent atom s and
g r oups and m ay be bonded to each oth er to f or m a cy clic
s tr uctur e. a r epr es ents 0, 1 or 2 and n and In each r epr es ent
an integ er of 1 or g r eater .
US 2002/ 0173605 A1
[ 0058 ] Speci? c ex am ples of th e g r oup r epr es ented by
( C5H5_ eR12e) include th e f ollow ing g r oups .
[ 0059 ] For indeny l der iv ativ es and ? uor eny l der iv ativ es ,
th e pos itions of s ubs tituents ar e s h oWn by th e num ber s
s h oWn in th e f ollow ing :
[ 0060] Cy clopentadieny l g r oup, m eth y lcy clopentadieny l
g r oup, 1, 2-dim eth y lcy clopentadieny l g r oup, 1, 3-dim eth y l
cy clopentadieny l g r oup, 1, 2, 3-tr im eth y lcy clopentadieny l
g r oup, 1, 3, 4 -tr im eth y lcy clopentadieny l g r oup, tetr am eth y l
cy clopentadieny l g r oup, pentam eth y lcy clopentadieny l
g r oup, eth y lcy clopentadieny l g r oup, 1, 2-dieth y lcy clopenta
dieny l g r oup, 1, 3-dieth y lcy clopentadieny l g r oup, 1, 2, 3-tr i
eth y lcy clopentadieny l g r oup, 1, 3, 4 -tr ieth y lcy clopentadieny l
g r oup, tetr aeth y lcy clopentadieny l g r oup, pentaeth y lcy clo
pentadieny l g r oup, indeny l g r oup, 1-m eth y lindeny l g r oup,
1, 2-dim eth y lindeny l g r oup, 1, 3-dim eth y lindeny l g r oup, 1, 2,
3-tr im eth y l-indeny l g r oup, 2-m eth y lindeny l g r oup, 1-eth y l
indeny g r oup, 1-eth y l-2-m eth y lindeny l g r oup, 1-eth y l-3
m eth y lindeny l g r oup, 1-eth y l-2, 3-dim eth y lindeny l g r oup,
1, 2-dieth y lindeny l g r oup, 1, 3-dieth y lindeny l g r oup, 1, 2, 3
tr ieth y lindeny l g r oup, 2-eth y lindeny l g r oup, 1-m eth y l-2
eth y lindeny l g r oup, 1, 3-dim eth y l-2-eth y lindeny l g r oup, 4 , 5,
6-7-tetr ah y dr oindeny l g r oup, 1 -m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 1 , 2-dim eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 1 , 3 -dim eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 1 , 2, 3 -tr im eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 2-m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 1-eth y l-4 , 5, 6, 7-tetr ah y dr oindeny l
g r oup, 1-eth y l-2-m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny l g r oup,
1-eth y l-3-m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny l g r oup, 1-eth y l
2, 3-dim eth y l-4 , 5, 6, 7-tetr ah y dr oindeny l g r oup, 1, 2-dieth y l
4 , 5, 6, 7-tetr ah y dr oindeny l g r oup, 1, 2-dieth y l-3-m eth y l-4 , 5,
6, 7-tetr ah y dr oindeny l g r oup, 1 , 3-dieth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 1, 3-dieth y l-2-m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 1 , 2, 3 -tr ieth y l-4 , 5 , 6, 7
tetr ah y dr oindeny l g r oup, 2-eth y l-4 , 5, 6, 7-tetr ah y dr oindeny l
g r oup, 1-m eth y l-2-eth y l-4 , 5, 6, 7-tetr ah y dr oindeny l g r oup,
1, 3-dim eth y l-2-eth y l-4 , 5, 6, 7-tetr ah y dr oindeny l g r oup, ? uo
r eny l g r oup, 9 -m eth y l? uor eny l g r oup, 9 -eth y l? uor eny l
g r oup, 1, 2, 3, 4 -tetr ah y dr o? uor eny l g r oup, 9 -m eth y l-1, 2, 3, 4
tetr ah y dr o? uor eny l g r oup, 9 -eth y l-1, 2, 3, 4 -tetr ah y dr o-? uo
r eny l g r oup, 1, 2, 3, 4 , 5, 6, 7, 8 -octah y dr o? uor eny l g r oup,
9 -m eth y l-1, 2, 3, 4 , 5, 6, 7, 8 -octah y dr o? uor eny l g r oup and
9 -eth y l-1, 2, 3, 4 , 5, 6, 7, 8 -octah y dr o? uor eny l g r oup.
[ 0061] Ex am ples of th e com pound r epr es ented by g ener al
f or m ula ( VIII) include th e f olloWing com pounds : cy clopen
tadieny l titanium tr ich lor ide, cy clopentadieny ltitanium tr i
m eth y l, cy clopentadieny ltitanium tr im eth oX ide, cy clopenta
dieny ltitanium tr ibenZ y l, m eth y l-cy clopentadieny ltitanium
tr ich lor ide, m eth y lcy clopentadieny ltitanium tr im eth y l,
m eth y lcy clopentadieny ltitanium tr im eth oX ide, m eth y lcy clo
pentadieny ltitanium tr ibenZ y l, dim eth y lcy clopentadieny lti
tanium tr ich lor ide, dim eth y lcy clopentadieny ltitanium tr im
N ov . 21, 2002
eth y l, dim eth y lcy clopentadieny ltitanium tr im eth oX ide,
dim eth y lcy clopentadieny ltitanium tr ibenZ y l, tr im eth y lcy
clopentadieny ltitanium tr ich lor ide, tr im eth y lcy clopentadi
eny ltitanium tr im eth y l, tr im eth y lcy clopentadieny ltitanium
tr im eth oX ide, tr im eth y lcy clopentadieny ltitanium tr ibenZ y l,
tetr am eth y lcy clopentadieny ltitanium tr ich lor ide, tetr am eth
y lcy clopentadieny ltitanium tr im eth y l, tetr am eth y lcy clopen
tadieny ltitanium tr im eth oX ide, tetr am eth y lcy clopentadi
eny ltitanium tr ibenZ y l,
pentam eth y lcy clopentadieny ltitanium tr ich lor ide, pentam
eth y lcy clopentadieny ltitanium tr im eth y l, pentam eth y lcy clo
pentadieny ltitanium tr im eth oX ide, pentam eth y lcy clopenta
dieny ltitanium tr ibenZ y l, indeny ltitanium tr ich lor ide,
indeny ltitanium tr im eth y l, indeny ltitanium tr im eth oX ide,
indeny ltitanium tr ibenZ y l, 1-m eth y lindeny ltitanium tr ich lo
r ide, 1-m eth y lindeny ltitanium tr im eth y l, 1-m eth y lindeny lti
tanium tr im eth oX ide, 1-m eth y lindeny ltitanium tr ibenZ y l,
2-m eth y lindeny ltitanium tr ich lor ide, 2-m eth y lindeny ltita
nium tr im eth y l, 2-m eth y lindeny ltitanium tr im eth oX ide,
2-m eth y lindeny ltitanium tr ibenZ y l, 1, 2-dim eth y l-indeny lti
tanium tr ich lor ide, 1, 2-dim eth y lindeny ltitanium tr im eth y l,
1, 2-dim eth y lindeny ltitanium tr im eth oX ide, 1, 2-dim eth y lin
deny ltitanium tr ibenZ y l, 1, 3-dim eth y lindeny ltitanium
tr ich lor ide, 1, 3-dim eth y l-indeny ltitanium tr im eth y l, 1, 3
dim eth y lindeny ltitanium tr im eth oX ide, 1, 3-dim eth y linde
ny ltitanium tr ibenZ y l, 1, 2, 3-tr im eth y lindeny ltitanium
tr ich lor ide, 1, 2, 3-tr im eth y lindeny ltitanium tr im eth y l, 1, 2, 3
tr im eth y lindeny ltitanium tr im eth oX ide, 1, 2, 3-tr im eth y linde
ny ltitanium tr ibenZ y l, 1, 2, 3, 4 , 5, 6, 7-h eptam eth y lindeny ltita
nium tr ich lor ide, 1, 2, 3, 4 , 5, 6, 7-h eptam eth y lindeny ltitanium
tr im eth y l, 1, 2, 3, 4 , 5, 6, 7-h eptam eth y lindeny ltitanium tr i
m eth oX ide, 1, 2, 3, 4 , 5, 6, 7-h eptam eth y lindeny ltitanium
tr ibenZ y l, 4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr ich lor ide, 4 , 5,
6, 7-tetr ah y dr oindeny ltitanium tr im eth y l, 4 , 5, 6, 7-tetr ah y
dr oindeny ltitanium tr im eth oX ide, 4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr ibenZ y l, 1 -m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny ltitanium tr ich lor ide, 1 -m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny ltitanium tr im eth y l, 1 -m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny ltitanium tr im eth oX ide, 1-m eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr ibenZ y l, 2-m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny ltitanium tr ich lor ide, 2-m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny ltitanium tr im eth y l, 2-m eth y l-4 , 5 , 6, 7
tetr ah y dr oindeny ltitanium tr im eth oX ide, 2-m eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr ibenZ y l, 1, 2-dim eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr ich lor ide, 1, 2-dim eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth y l, 1, 2-dim eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth oX ide, 1, 2-dim eth y l-4 , 5, 6,
7-tetr ah y dr oindeny ltitanium tr ibenZ y l, 1, 3-dim eth y l-4 , 5, 6,
7-tetr ah y dr oindeny ltitanium tr ich lor ide, 1, 3-dim eth y l-4 , 5, 6,
7-tetr ah y dr oindeny ltitanium tr im eth y l, 1, 3-dim eth y l-4 , 5, 6,
7-tetr ah y dr oindeny ltitanium tr im eth oX ide, 1, 3-dim eth y l-4 ,
5, 6, 7-tetr ah y dr oindeny ltitanium tr ibenZ y l, 1, 2, 3-tr im eth y l
4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr ich lor ide, 1, 2, 3
tr im eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr im eth y l, 1, 2,
3-tr im eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr im eth oX ide,
1, 2, 3-tr im eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr ibenZ y l,
1 -eth y l-4 , 5 , 6, 7-tetr ah y dr oindeny ltitanium tr ich lor ide,
1 -eth y l-4 , 5 , 6, 7-tetr ah y dr oindeny ltitanium tr im eth y l,
1 -eth y l-4 , 5 , 6, 7-tetr ah y dr oindeny ltitanium tr im eth oX ide,
1 -eth y l-4 , 5 , 6, 7-tetr ah y dr oindeny ltitanium tr ibenZ y l,
1-eth y l-2-m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr ich lo
r ide, 1-eth y l-2-m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium
tr im eth y l, 1-eth y l-2-m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltita
nium tr im eth oX ide, 1-eth y l-2-m eth y l-4 , 5, 6, 7-tetr ah y dr oin
US 2002/ 0173605 A1
deny ltitanium tr ibenZ y l, 1-eth y l-3-m eth y l-4 , 5, 6, 7-tetr ah y
dr oindeny ltitanium tr ich lor ide, 1-eth y l-3-m eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth y l, 1-eth y l-3-m eth y l-4 , 5,
6, 7-tetr ah y dr oindeny ltitanium tr im eth ox ide, 1-eth y l-3
m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr ibenZ y l,
1-eth y l-2, 3-dieth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium
tr ich lor ide, 1-eth y l-2, 3-dim eth y l-4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr im eth y l, 1-eth y l-2, 3-dim eth y l-4 , 5, 6, 7-tetr ah y
dr oindeny ltitanium tr im eth ox ide, 1-eth y l-2, 3-dim eth y l-4 , 5,
6, 7-tetr ah y dr oindeny ltitanium tr ibenZ y l, 1, 2-dieth y l-4 , 5, 6,
7-tetr ah y dr oindeny ltitanium tr ich lor ide, 1, 2-dieth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth y l, 1, 2-dieth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth ox ide, 1, 2-dieth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr ibenZ y l, 1, 2-dieth y l-3-m eth y l
4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr ich lor ide, 1, 2-dieth y l-3
m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr im eth y l, 1, 2
dieth y l-3-m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium
tr im eth ox ide, 1, 2-dieth y l-3-m eth y l-4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr ibenZ y l, 1, 3-dieth y l-4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr ich lor ide, 1, 3-dieth y l-4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr im eth y l, 1, 3-dieth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth ox ide, 1, 3-dieth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr ibenZ y l, 1, 3-dieth y l-2-m eth y l
4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr ich lor ide, 1, 3-dieth y l-2
m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr im eth y l, 1, 3
dieth y l-2-m eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium
tr im eth ox ide, 1, 3-dieth y l-2-m eth y l-4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr ibenZ y l, 1, 2, 3-tr ieth y l-4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr ich lor ide, 1, 2, 3-tr ieth y l-4 , 5, 6, 7-tetr ah y dr oin
deny ltitanium tr im eth y l, 1, 2, 3-tr ieth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth ox ide, 1, 2, 3-tr ieth y l-4 , 5,
6, 7-tetr ah y dr oindeny ltitanium tr ibenZ y l, 2-eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr ich lor ide, 2-eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth y l, 2-eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr im eth ox ide, 2-eth y l-4 , 5, 6, 7
tetr ah y dr oindeny ltitanium tr ibenZ y l, 1-m eth y l-2-eth y l-4 , 5,
6, 7-tetr ah y dr oindeny ltitanium tr ich lor ide, 1-m eth y l-2-eth y l
4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr im eth y l, 1-m eth y l-2
eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr im eth ox ide,
1-m eth y l-2-eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium tr iben
Z y l, 1, 3-dim eth y l-2-eth y l-4 , 5, 6, 7-tetr ah y dr oindeny ltitanium
tr ich lor ide, 1, 3-dim eth y l-2-eth y l-4 , 5, 6, 7-tetr ah y dr oinde
ny ltitanium tr im eth y l, 1, 3-dim eth y l-2-eth y l-4 , 5, 6, 7-tetr ah y
dr oindeny ltitanium tr im eth ox ide, 1, 3-dim eth y l-2-eth y l-4 , 5,
6, 7-tetr ah y dr oindeny ltitanium tr ibenZ y l, 1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr ich lor ide, 1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr im eth y l, 1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr im eth ox ide, 1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr ibenZ y l, 9 -m eth y l-1, 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr ich lor ide, 9 -m eth y l-1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr im eth y l, 9 -m eth y l-1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr im eth ox ide, 9 -m eth y l-1, 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr ibenZ y l, 9 -eth y l-1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr ich lor ide, 9 -eth y l-1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr im eth y l, 9 -eth y l-1 , 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr im eth ox ide, 9 -eth y l-1, 2, 3, 4
tetr ah y dr o? uor eny ltitanium tr ibenZ y l, 1, 2, 3, 4 , 5 , 6, 7, 8
octah y dr o? uor eny ltitanium tr ich lor ide, 1, 2, 3, 4 , 5 , 6, 7, 8
octah y dr o? uor eny ltitanium tr im eth y l, 1, 2, 3, 4 , 5 , 6, 7, 8
octah y dr o? uor eny ltitanium tr im eth ox ide, 1, 2, 3, 4 , 5, 6, 7, 8
octah y dr o? uor eny ltitanium tr ibenZ y l, 9 -m eth y l-1, 2, 3, 4 , 5, 6,
7, 8 -octah y dr o? uor eny ltitanium tr ich lor ide, 9 -m eth y l-1, 2, 3,
4 , 5, 6, 7, 8 -octah y dr o? uor eny ltitanium tr im eth y l, 9 -m eth y l-1,
2, 3, 4 , 5, 6, 7, 8 -octah y dr o? uor eny ltitanium tr im eth ox ide,
N ov . 21, 2002
9 -m eth y l-1, 2, 3, 4 , 5, 6, 7, 8 -octah y dr o? uor eny ltitanium tr iben
Z y l, 9 -eth y l-1, 2, 3, 4 , 5, 6, 7, 8 -octah y dr of uor eny ltitanium
tr ich lor ide, 9 -eth y l-1, 2, 3, 4 , 5, 6, 7, 8 -octah y dr o? uor eny ltita
nium tr im eth y l, 9 -eth y l-1, 2, 3, 4 , 5, 6, 7, 8 -octah y dr o? uor e
ny ltitanium tr im eth ox ide, 9 -eth y l-1, 2, 3, 4 , 5, 6, 7, 8 -octah y
dr o? uor eny ltitanium tr ibenZ y l, com pounds obtained by
r eplacing titanium in th e abov e com pounds With Z ir conium
or h af nium and s im ilar com pounds of tr ans ition m etal
elem ents of oth er Gr oups and Lanth anoid s er ies . HoWev er ,
th e com pound r epr es ented by g ener al f or m ula ( VIII) is not
lim ited to th e com pounds s h oWn abov e as th e ex am ples .
Am ong th e abov e com pounds , titanium com pounds ar e
pr ef er able.
[ 0062] ( c) Ex am ples of th e com pound r epr es ented by
g ener al f or m ula ( IX ) include th e f olloWing com pounds :
tetr am eth y ltitanium , tetr abenZ y ltitanium , tetr aeth y ltitanium ,
tetr aph eny ltitanium , tetr am eth ox y titanium , tetr aeth ox y tita
nium , tetr aph enox y titanium , tetr a( dim eth y lam ino) -titanium ,
tetr a( dieth y lam ino) titanium , tetr a( diph eny lam ino) titanium ,
bis ( ph enox o) titanium com pounds des cr ibed in Macr om ol
ecules 19 9 7, 30, 1562-1569 and J our nal of Or g anom etallic
Ch em is tr y 514 ( 19 9 6) , 213-217, diam idotitanium com
pounds des cr ibed in Macr om olecules 19 9 6, 29 , 524 1-524 3
and Or g anom etallics 19 9 7, 16, 14 9 1-14 9 6, com pounds
obtained by r eplacing titanium in th e abov e com pounds With
Z ir conium or h af nium and s im ilar com pounds of tr ans ition
m etals of oth er Gr oups and Lanth anoid s er ies .
[ 0063] ( d) In th e tr ans ition m etal com pounds r epr es ented
by g ener al f or m ula ( X ) , M2 r epr es ents a tr ans ition m etal of
Gr oup 8 to 10 of th e Per iodic Table. Ex am ples of s uch
tr ans ition m etal include ir on, cobalt, nickel, palladium and
platinum . Am ong th es e tr ans ition m etals , nickel a n d
palladium ar e pr ef er able. L1 and L2 each r epr es ent a lig and
f or m ing a coor dinating bond and X 1 and Y1 each r epr es ent
a lig and f or m ing a cov alent bond or a lig and f or m ing an
ionic bond. As des cr ibed abov e, s peci? cally , X 1 and Y1 each
r epr es ent h y dr og en atom , a h alog en atom ; a h y dr ocar bon
g r oup h av ing 1 to 20 car bon atom s and pr ef er ably 1 to 10
car bon atom s , an alkox y l g r oup h av ing 1 to 20 car bon atom s
and pr ef er ably 1 to 10 car bon atom s , am ino g r oup, a
h y dr ocar bon g r oup h av ing ph os ph or us atom and 1 to 20
car bon atom s and pr ef er ably 1 to 12 car bon atom s s uch as
diph eny lph os ph ine g r oup, a h y dr ocar bon g r oup h av ing s ili
con atom and 1 to 20 car bon atom s and pr ef er ably 1 to 12
car bon atom s s uch as tr im eth y ls ily l g r oup or a bor on com
pound h av ing a h y dr ocar bon g r oup h av ing 1 to 20 car bon
atom s and pr ef er ably 1 to 12 car bon atom s or h alog en atom s
s uch as B( C6H5) 4 and BF4 . Am ong th es e lig ands , h alog en
atom s and h y dr ocar bon g r oups ar e pr ef er able. X 1 and Y1
m ay r epr es ent th e s am e lig and or dif f er ent lig ands .
Ex am ples of th e lig ands r epr es ented by L1 and L2 include
tr iph eny lph os ph ine, acetonitr ile, benZ onitr ile, 1, 2-bis diph e
ny lph os ph inoeth ane, 1, 3-bis diph eny lph os ph inopr opane,
1, 1 -bis diph eny lph os ph inof er r ocene, cy clooctadiene, py r i
dine and bis tr im eth y ls ily lam inobis tr i
m eth y lim inoph os ph or ane.
[ 0064 ] Th e g r oups r epr es ented by L1, L2, X 1 and Y1 m ay
be bonded to each to oth er to f or m a cy clic s tr uctur e.
[ 0065] As th e tr ans ition m etal com pounds of Gr oups 8 to
10 of th e Per iodic Table Wh ich ar e r epr es ented by g ener al
f or m ula ( X ) , com pounds h av ing a diim ine com pound as th e
lig and ar e pr ef er able. Ex am ples of s uch com pounds include
US 2002/ 0173605 A1
com plex com pounds r epr es ented by th e f ollow ing g ener al
f or m ula ( X VIII) :
( X VIII)
R18
19 I
R N
/ \ \ / X
M2
\ , \ Y
R20 N
R21
[ 0066] Wh er ein R18 and R21 each independently r epr es ent
an aliph atic h y dr ocar bon g r oup h av ing 1 to 20 car bon atom s
or an ar om atic g r oup h av ing 7 to 20 total car bon atom s and
a h y dr ocar bon g r oup on th e r ing , R19 and R20 each inde
pendently r epr es ent h y dr og en atom or a h y dr ocar bon g r oup
h av ing 1 to 20 car bon atom s , th e g r oups r epr es ented by R19
and R20 m ay be bonded to each oth er to f or m a r ing , X and
Y each independently r epr es ent h y dr og en atom or a h y dr o
car bon g r oup h av ing 1 to 20 car bon atom s and M2 r epr es ents
a tr ans ition m etal s elected f r om m etals of Gr oups 8 to 10 of
th e Per iodic Table.
[ 0067] In th e abov e g ener al f or m ula ( X VIII) , ex am ples of
th e aliph atic h y dr ocar bon g r oup h av ing 1 to 20 car bon atom s
Wh ich is r epr es ented by R18 or R21 include linear and
br anch ed alky l g r oups h av ing 1 to 20 car bon atom s and
cy cloalky l g r oups h av ing 3 to 20 car bon atom s . Speci? c
ex am ples of s uch g r oups include m eth y l g r oup, eth y l g r oup,
n-pr opy l g r oup, is opr opy l g r oup, n-buty l g r oup, is obuty l
g r oup, s ec-buty l g r oup, ter t-buty l g r oup, penty l g r oup, h ex y l
g r oup, octy l g r oup, decy l g r oup, tetr adecy l g r oup, h ex adecy l
g r oup, octadecy l g r oup, cy clopenty l g r oup, cy cloh ex y l
g r oup and cy cloocty l g r oup. Th e cy cloalky l g r oup m ay h av e
s uitable s ubs tituents s uch as loWer alky l g r oups on th e r ing .
Ex am ples of th e ar om atic g r oup h av ing 7 to 20 total car bon
atom s and a h y dr ocar bon g r oup on th e r ing include g r oups
h av ing ar om atic r ing s s uch as ph eny l g r oup and naph th y l
g r oup and one or m or e linear , br anch ed or cy clic alky l
g r oups h av ing 1 to 10 car bon atom s intr oduced into th e
ar om atic r ing s . As th e g r oup r epr es ented by R18 or R21,
ar om atic g r oups h av ing h y dr ocar bon g r oups on th e r ing ar e
pr ef er able and 2, 6-diis opr opy lph eny l g r oup is m or e pr ef er
able. R18 and R21 m ay r epr es ent th e s am e g r oup or dif f er ent
g r oups .
[ 0068 ] Ex am ples of th e h y dr ocar bon g r oup h av ing 1 to 20
car bon atom s Wh ich is r epr es ented by R19 or R20 include
linear and br anch ed alky l g r oups h av ing 1 to 20 car bon
atom s , cy cloalky l g r oups h av ing 3 to 20 car bon atom s , ar y l
g r oups h av ing 6 to 20 car bon atom s and ar alky l g r oups
h av ing 7 to 20 car bon atom s . Ex am ples of th e linear and
br anch ed alky l g r oups h av ing 1 to 20 car bon atom s and th e
cy cloalky l g r oups h av ing 3 to 20 car bon atom s include th e
g r oups des cr ibed abov e as th e ex am ples of th e aliph atic
h y dr ocar bon g r oup h av ing 1 to 20 car bon atom s Wh ich is
r epr es ented by R18 or R21. Ex am ples of th e ar y l g r oup
h av ing 6 to 20 car bon atom s include ph eny l g r oup, toly l
g r oup, x y ly l g r oup, naph th y l g r oup and m eth y lnaph th y l
g r oup. Ex am ples of th e ar alky l g r oup h av ing 7 to 20 car bon
atom s include benZ y l g r oup and ph enety l g r oup. Th e g r oups
r epr es ented by R19 and R20 m ay be th e s am e With or dif f er ent
f r om each oth er and m ay be bonded to each oth er to f or m a
r ing .
N ov . 21, 2002
[ 0069 ] Ex am ples of th e h y dr ocar bon g r oup h av ing 1 to 20
car bon atom s Wh ich is r epr es ented by X or Y include th e
g r oups des cr ibed abov e as th e ex am ples of th e h y dr ocar bon
g r oup h av ing 1 to 20 car bon atom s Wh ich is r epr es ented by
R19 or R20. It is pr ef er able th at X and Y r epr es ent m eth y l
g r oup. X and Y m ay r epr es ent th e s am e g r oup or dif f er ent
g r oups .
[ 0070] Ex am ples of th e tr ans ition m etal s elected f r om
m etals of Gr oups 8 to 10 of th e Per iodic Table Wh ich is
r epr es ented by M2 include nickel, palladium , platinum , ir on,
cobalt, r h odium and r uth enium . Am ong th es e m etals , nickel
and palladium ar e pr ef er able.
[ 0071] Ex am ples of th e com plex com pound r epr es ented
by g ener al f or m ula ( X VIII) include com pounds ex pr es s ed
by th e f olloWing f or m ulae:
US 2002/ 0173605 A1
-continued
( CH3) 2CH CH( CH3) 2
CH3 / N \ / Br
N i
\ \ Br
CH3 N
( CH3) 2CH CH( CH3) 2
[ 0072] Speci? c ex am ples of th e tr ans ition m etal com
pound r epr es ented by g ener al f or m ula ( X VIII) include
dibr om obis tr iph eny lph os ph ine nickel, dich lor obis tr iph
eny lph os ph ine nickel, dibr om odiacetonitr ile nickel, dibr o
m odibenZ onitr ile nickel, dibr om o( 1, 2-bis diph eny lph os ph i
noeth ane) nickel, dibr om o( 1 , 3
bis diph eny lph os ph inopr opane) nickel, dibr om o( 1 , 1
diph eny lbis ph os ph inof er r ocene) nickel, dim eth y lbis
diph eny lph os ph ine nickel, dim eth y l( 1 , 2
bis diph eny lph os ph inoeth ane) nickel, m eth y l( 1 , 2
bis diph eny lph os ph inoeth ane) nickel tetr a? uor obor ate,
( 2-diph eny lph os ph ino-1-ph eny leth y leneox y ) ph eny lpy r idine
nickel, dich lor obis tr iph eny lph os ph ine palladium , dich lor od
ibenZ onitr ile palladium , dich lor odiacetonitr ile palladium ,
dich lor o( 1, 2-bis diph eny lph os ph inoeth ane) palladium , bis
tr iph eny lph os ph inepalladium bis tetr a? uor obor ate and bis ( 2,
2 -bipy r idine) m eth y lir on tetr a? uor obor ate eth er ate.
[ 0073] Am ong th es e com pounds , cationic com plex com
pounds s uch as m eth y l( 1, 2-bis diph eny lph os ph inoeth ane) n
ickel tetr a? uor obor ate, bis tr iph eny lph os ph inepalladium
bis tetr a? uor obor ate and bis ( 2, 2 -bipy r idine) m eth y lir on tet
r a? uor obor ate eth er ate ar e pr ef er able.
[ 0074 ] In th e pr es ent inv ention, th e abov e com plex com
pounds m ay be us ed s ing ly or in com bination of tWo or
m or e.
[ 0075] Com ponent ( B)
[ 0076] Com ponent ( B) com pr is es at leas t one com pound
s elected f r om [ a] com pounds h av ing ox y g en and [ b] com
pounds Wh ich can f or m ionic com plex com pounds by r eac
tion With th e tr ans ition m etal com pound. Am ong th es e
com pounds , th e com pounds h av ing ox y g en of com ponent
[ a] ar e pr ef er able.
[ 0077] Th e com pound h av ing ox y g en of com ponent [ a] is
a com pound h av ing ox y g en Wh ich is at leas t one of com
pounds r epr es ented by th e f olloWing g ener al f or m ula ( X IX ) :
( X IX )
R23 R24 R25
[ 0078 ] and com pounds r epr es ented by th e f olloWing g en
er al f or m ula
12
N ov . 21, 2002
( X X )
R27 R28
Y5_ O) c ( Y6_ O) d
[ 0079 ] In th e abov e g ener al f or m ulae ( X IX ) and ( X X ) , R22
to R28 each r epr es ent an alky l g r oup h av ing 1 to 8 car bon
atom s . Ex am ples of th e alky l g r oup include m eth y l g r oup,
eth y l g r oup, n-pr opy l g r oup, is opr opy l g r oup, v ar ious ty pes
of buty l g r oup, v ar ious ty pes of penty l g r oup, v ar ious ty pes
of h ex y l g r oup, v ar ious ty pes of h epty l g r oup and v ar ious
ty pes of octy l g r oup. R22 to R26 m ay r epr es ent th e s am e
g r oup or dif f er ent g r oups . R27 and R28 m ay r epr es ent th e
s am e g r oup or dif f er ent g r oups . Y2 to Y6 each r epr es ent an
elem ent of Gr oup 13. Ex am ple of s uch an elem ent include
B, Al, Ga, In and Tl. Am ong th es e elem ents , B and A1 ar e
pr ef er able. Y2 to Y4 m ay r epr es ent th e s am e elem ent or
dif f er ent elem ents . Y5 and Y6 m ay r epr es ent th e s am e ele
m ent or dif f er ent elem ents . a to d each r epr es ent a num ber
of 0 to 50 and ( a+b) and ( c+d) r epr es ent each a num ber of
1 or g r eater . It is pr ef er able th at a to d each r epr es ent a
num ber in th e r ang e of 1 to 20 and m or e pr ef er ably in th e
r ang e of 1 to 5.
[ 008 0] As th e com pound h av ing ox y g en us ed as th e com
ponent of th e cataly s t, alky lalum inox anes ar e pr ef er able.
Ex am ples of th e alky lalum inox ane include m eth y lalum inox
ane and is obuty lalum inox ane.
[ 008 1] Com ponent ( B) m ay als o com pr is e [ b] a com pound
Wh ich can f or m an ionic com plex com pound by r eaction
With th e tr ans ition m etal com pound.
[ 008 2] Ex am ples of th e com pound Wh ich can f or m an
ionic com plex com pound by r eaction With th e tr ans ition
m etal com pound include LeWis acids and coor dinated com
plex com pounds com pr is ing an anion in Wh ich a plur ality of
g r oups ar e bonded to a m etal and a cation. As th e coor di
nated com plex com pound com pr is ing an anion in Wh ich a
plur ality of g r oups ar e bonded to a m etal and a cation,
v ar ious com pounds can be us ed. Ex am ples of s uch a com
pound include com pounds r epr es ented by th e f olloWing
g ener al f or m ulae ( X X I) and ( X X II) :
[ 008 3] In g ener al f or m ulae ( X X I) and ( X X II) , L4 r epr e
s ents a m etal r epr es ented by M5 or a g r oup r epr es ented by
R29 R3OM6 or R313C Wh ich Will be des cr ibed later ; L3 r ep
r es ents a LeWis bas e; M3 and M4 each r epr es ent a m etal
s elected f r om m etals of Gr oups 5 to 15 of th e Per iodic Table;
M5 r epr es ents a m etal s elected f r om m etals of Gr oup 1 and
Gr oups 8 to 12 of th e Per iodic Table; M6 r epr es ents a m etal
s elected f r om m etals of Gr oups 8 to 10 of th e Per iodic Table;
X 2 to X n each r epr es ent h y dr og en atom , a dialky lam ino
g r oup, an alkox y l g r oup, an ar y lox y l g r oup, an alky l g r oup
h av ing 1 to 20 car bon atom s , an ar y l g r oup h av ing 6 to 20
car bon atom s , an alky lar y l g r oup, an ar y lalky l g r oup, a
s ubs tituted alky l g r oup, an or g anom etalloid g r oup or a
h alog en atom ; R29 and R30 each r epr es ent cy clopentadieny l
g r oup, a s ubs tituted cy clopentadieny l g r oup, indeny l g r oup
or ? uor eny l g r oup; R31 r epr es ents an alky l g r oup; m r epr e
( X X I)
( x x n)
US 2002/ 0173605 A1
s ents th e v alence of th e atom r epr es ented by M3 or M4 Wh ich
is an integ er of 1 to 7; n r epr es ents an integ er of 2 to 8 , g
r epr es ents th e ionic v alence of an ion r epr es ented by L3-H
or L4 Wh ich is an integ er of 1 to 7; h r epr es ents an integ er
of 1 or g r eater ; and i=h > < g / ( n-m ) .
[ 008 4 ] Ex am ples of th e m etal r epr es ented by M3 and M4
include B, Al, Si, P, As and Sb. Ex am ples of th e m etal
r epr es ented by M5 include Ag , Cu, N a and Li. Ex am ples of
th e m etal r epr es ented by M6 include Fe, Co and N i.
Ex am ples of th e g r oup r epr es ented by X 2 to X n include
dialky lam ino g r oups s uch as dim eth y lam ino g r oup and
dieth y lam ino g r oup; alkox y l g r oups s uch as m eth ox y g r oup,
eth ox y g r oup and n-butox y g r oup; ar y lox y l g r oups s uch as
ph enox y g r oup, 2, 6-dim eth y lph enox y g r oup and naph th y
lox y g r oup; alky l g r oups h av ing 1 to 20 car bon atom s s uch
as m eth y l g r oup, eth y l g r oup, n-pr opy l g r oup, is opr opy l
g r oup, n-buty l g r oup, n-octy l g r oup and 2-eth y lh ex y l g r oup;
ar y l g r oups h av ing 6 to 20 car bon atom s , alky lar y l g r oups
and ar y lalky l g r oups s uch as ph eny l g r oup, p-toly l g r oup,
benZ y l g r oup, penta? uor oph eny l g r oup, 3, 5-di( tr i? uor om
eth y l) ph eny l g r oup, 4 -ter tiar y -buty lph eny l g r oup, 2, 6-dim
eth y lph eny l g r oup, 3, 5-dim eth y lph eny l g r oup, 2, 4 -dim eth
y lph eny l g r oup and 1, 2-dim eth y lph eny l g r oup; h alog en
atom s s uch as F, Cl, Br and I; and or g anom etalloid g r oups
s uch as pentam eth y lantim ony g r oup, tr im eth y ls ily l g r oup,
tr im eth y lg er m y l g r oup, diph eny lar s ine g r oup, dicy cloh ex y
lar s ine g r oup and diph eny lbor on g r oup. Ex am ples of th e
s ubs tituted cy clopentadieny l g r oup r epr es ented by R29 and
R include m eth y lcy clopentadieny l g r oup, buty lcy clopenta
dieny l g r oup and pentam eth y lcy clopentadieny l g r oup.
[ 008 5] In th e pr es ent inv ention, ex am ples of th e anion in
Wh ich a plur ality of g r oups ar e bonded to a m etal include
B( C6F5) 4 > B( C6HF4 ) 4 > B( C6H2F3) 4 > B( C6H3F2) 4 >
B( C6H4 F) 4 > B( C6CF3F4 ) 4 > B( C6H5) 4 > PF6>
P( C6F5) 6 and Al( C6HF4 ) 4 . Ex am ples of m etal cations
as th e abov e cation include Cp2Fe+, ( MeCp) 2Fe+,
( tBuCp) 2Fe+, ( Me2Cp) 2Fe+, ( Me3Cp) 2Fe+, ( Me4 Cp) 2Fe+,
( Me5Cp) 2Fe+, Ag " , N a+ and Li" . Ex am ples of oth er cations
as th e abov e cation include cations of com pounds h av ing
nitr og en atom s uch as py r idinium cation, 2, 4 -dinitr o-N , N
dieth y lanilinium cation, diph eny lam m onium cation, p-ni
tr oanilinium cation, 2, 5-dich lor oanilinium cation, p-nitr o-N ,
N -dim eth y lanilinium cation, q uinolinium cation, N , N
dim eth y lanilinium cation and N , N -dieth y lanilinium cation;
car benium cations s uch as tr iph eny l car benium cation, tr i( 4
m eth y lph eny l) car benium cation and tr i( 4 -m eth ox y ph eny l
[ 008 6] Am ong th e com pounds r epr es ented by g ener al
f or m ulae ( X X I) and ( X X II) , th e f olloWing com pounds can
be pr ef er ably us ed. Ex am ples of th e pr ef er able com pound
r epr es ented by g ener al f or m ula ( X X I) include tr ieth y lam
m onium tetr aph eny lbor ate, tr i( n-buty l) am m onium tetr aph e
ny lbor ate, tr im eth y lam m onium tetr aph eny lbor ate, tr ieth y
lam m onium tetr akis ( penta? uor oph eny l) bor ate, tr i( n
buty l) am m onium tetr akis ( penta? uor oph eny l) bor ate,
tr ieth y lam m onium h ex a? uor oar s enate, py r idinium tetr ak
N ov . 21, 2002
is ( penta? luor oph eny l) bor ate, py r r olinium tetr akis ( pen
ta? uor oph eny l) bor ate, N , N -dim eth y lanilinium tetr akis ( pen
ta? uor oph eny l) bor ate and m eth y ldiph eny lam m onium
tetr akis ( penta? uor oph eny l) bor ate. Ex am ples of th e pr ef er
able com pound r epr es ented by g ener al f or m ula ( X X II)
include f er r ocenium tetr aph eny lbor ate, dim eth y f er r ocenium
tetr akis ( penta? uor oph eny l) bor ate, f er r ocenium tetr akis ( pen
ta? uor oph eny l) bor ate, decam eth y lf er r ocenium tetr akis ( pen
ta? uor oph eny l) bor ate, acety lf er r ocenium tetr akis penta? uo
r oph eny l) bor ate, f or m y lf er r ocenium
tetr akis ( penta? uor oph eny l) bor ate, cy anof er r ocenium tetr ak
is ( penta? uor oph eny l) bor ate, s ilv er tetr aph eny lbor ate, s ilv er
tetr akis ( penta? uor oph eny l) bor ate, tr ity l tetr aph eny lbor ate,
tr ity l tetr akis ( penta? uor oph eny l) bor ate, s ilv er h ex a? uor o
ar s enate, s ilv er h ex a? uor oantim onate and s ilv er tetr a? uo
r obor ate.
[ 008 8 ] Com ponent ( C)
[ 008 9 ] In th e cataly s t us ed in th e pr oces s of th e pr es ent
inv ention, Wh er e neces s ar y , ( C) an or g anom etallic com
pound m ay als o be us ed in com bination With com ponent ( A)
and com ponent ( B) des cr ibed abov e.
[ 009 0] Th e or g anom etallic com pound of com ponent ( C)
com pr is es a com pound r epr es ented by th e f olloWing g ener al
[ 009 1]
es s ar y .
( X X III)
and an alky lating ag ent Wh ich is us ed Wh er e nec
[ 009 2] In g ener al f or m ula ( X X III) , R32 r epr es ents h y dr o
g en atom , a h alog en atom , an aliph atic h y dr ocar bon g r oup
h av ing 1 to 30 car bon atom s , an ar om atic h y dr ocar bon g r oup
h av ing 6 to 30 car bon atom s , an alkox y l g r oup h av ing 1 to
30 car bon atom s , an ar y lox y l g r oup h av ing 6 to 30 car bon
atom s , a th ioalkox y l g r oup h av ing 1 to 30 car bon atom s , a
th ioar y lox y l g r oup h av ing 6 to 30 car bon atom s , am ino
g r oup, am ido g r oup or car box y l g r oup; th e plur ality of
g r oups r epr es ented by R32 m ay be th e s am e With or dif f er ent
f r om each oth er and m ay be bonded to each oth er to f or m a
cy clic s tr uctur e; X r epr es ents an elem ent of Gr oup 14 ; Y
r epr es ents an elem ent of Gr oup 16, Z r epr es ents a m etal
elem ent s elected f r om elem ents of Gr oups 2 to 13; R33
r epr es ents a h y dr ocar bon g r oup; In r epr es ents an integ er
Wh ich is th e v alence of th e m etal elem ent r epr es ented by Z ;
and n r epr es ents an integ er of 1 to ( m 1) .
[ 009 3] Am ong th e com pounds r epr es ented by g ener al
f or m ula ( X X III) , th e f olloWing com pounds ar e pr ef er ably
us ed: ( 1) com pounds r epr es ented by g ener al f or m ula
( X X III) in Wh ich X r epr es ents car bon atom , Y r epr es ents
ox y g en atom and Z r epr es ents alum inum atom ; ( 2) com
pounds r epr es ented by g ener al f or m ula ( X X III) in Wh ich at
leas t one of th r ee R32 r epr es ents an ar om atic h y dr ocar bon
g r oup h av ing 6 to 30 car bon atom s ; ( 3) com pounds r epr e
s ented by g ener al f or m ula ( X X III) in Wh ich th r ee R32 each
r epr es ent a h y dr ocar bon g r oup h av ing 1 or m or e car bon
atom s ; ( 4 ) com pounds r epr es ented by g ener al f or m ula
( X X III) in Wh ich th r ee R32 each r epr es ent an ar om atic
h y dr ocar bon g r oup h av ing 6 to 30 car bon atom s and pr ef
US 2002/ 0173605 A1
er ably ph eny l g r oup; and ( 5) com pounds r epr es ented by
g ener al f or m ula ( X X III) in Wh ich R33 r epr es ents an alky l
g r oup h av ing 2 or m or e car bon atom s .
[ 009 4 ] Speci? cally , th e com pound r epr es ented by g ener al
f or m ula ( X X III) in Wh ich th r ee R32 each r epr es ent ph eny l
g r oup, X r epr es ents car bon atom , Y r epr es ents ox y g en atom ,
Z r epr es ents alum inum atom , n r epr es ents 1 and R33 r epr e
s ents is obuty l g r oup is m or e pr ef er able.
[ 009 5] Th e pr oces s f or pr epar ing th e com pound of com
ponent ( C) is not par ticular ly lim ited as long as th e com
pound h as th e s tr uctur e r epr es ented by th e abov e g ener al
f or m ula. Com pounds obtained by r eaction of ( D at leas t one
com pound s elected f r om com pounds r epr es ented by g ener al
f or m ulae ( R32) 3COR32, R32COR32 and R32
COOR32 With @ a com pound r epr es ented by a g ener al
f or m ula Z ( R33) r n ar e pr ef er ably us ed. In th e abov e f or m ulae,
R32, Z and R33 ar e as de? ned abov e.
[ 009 6] Speci? cally , th e abov e com pound is a r eaction
pr oduct of at leas t one com pound s elected f r om alcoh ols ,
eth er s , aldeh y des , ketones , car box y lic acids and es ter s of
car box y lic acids With an alum inum com pound and pr ef er
ably a r eaction pr oduct of an alcoh ol and an alum inum
com pound. Am ong th es e r eaction pr oducts , com pounds s at
is f y ing any of th e f olloWing conditions ar e pr ef er ably us ed:
( 1) at leas t one of th r ee R32 in ( R32) 3 r epr es ents an ar om atic
h y z dr ocar bon g r oup h av ing 6 to 30 car bon atom s ; ( 2) th r ee
R in ( R32) 3 each r epr es ent a h y dr ocar bon g r oup h av ing 1 or
m or e car bon atom s ; ( 3) th r ee R32 in ( R32) 3 each r epr es ent an
ar om atic h y dr ocar bon g r oup h av ing 6 to 30 car bon atom s
and pr ef er ably ph eny l g r oup; and ( 4 ) R33 r epr es ents a alky l
g r oup h av ing 2 or m or e car bon atom s . Speci? cally , th e
com pound s atis f y ing th e condition s uch th at th r ee R32 each
r epr es ent ph eny l g r oup and R33 r epr es ents is obuty l g r oup is
m or e pr ef er able. In oth er Wor ds , th e r eaction pr oduct of
tr iph eny lm eth y l alcoh ol With tr iis obuty lalum inum is m or e
pr ef er able.
[ 009 7] Th e condition of th e r eaction of com pound ( D With
com pound @ is not par ticular ly lim ited. Th e pr ef er able
condition is as f olloWs : th e r atio of th e am ounts by m ole of
com pound ( D to com pound @ is in th e r ang e of 1: 0. 1 to 10,
pr ef er ably in th e r ang e of 1: 0. 5 to 2 and m or e pr ef er ably in
th e r ang e of 1: 0. 8 to 1. 2; th e r eaction tem per atur e is in th e
r ang e of 8 0 to 300 C. and pr ef er ably in th e r ang e of 10
to 50 C. ; and th e r eaction tim e is in th e r ang e of 0. 1 m inute
to 50 h our s and pr ef er ably in th e r ang e of 0. 1 m inute to 3
h our s . Th e s olv ent us ed in th e r eaction is not par ticular ly
lim ited. Th e s olv ent us ed f or th e poly m er iZ ation is pr ef er
able.
[ 009 8 ] As com ponent ( C) , com pound ( C1) and com pound
( C2) Wh ich ar e s h oWn beloW m ay be dir ectly added into th e
? eld of th e s y nth es is of th e cataly s t or th e ? eld of th e
poly m er iZ ation in place of th e com pound des cr ibed abov e.
In th is cas e, th e com ponents of th e cataly s t ar e ( A) th e
tr ans ition m etal com pound, ( B) at leas t one com pound
s elected f r om com pounds h av ing ox y g en and com pounds
Wh ich can f or m ionic com plex com pounds by r eaction With
th e tr ans ition m etal com pound, com pounds ( C-1) and ( C-2)
and an alky lating ag ent Wh ich is us ed Wh er e neces s ar y .
[ 009 9 ] Com pound ( C-1) is at leas t one com pound s elected
f r om com pounds r epr es ented by g ener al f or m ulae ( R32) 3
COR32, R32COR32 and R32COOR32 and com
pound ( C-2) is a com pound r epr es ented by a g ener al f or m ula
Z ( R33) m .
N ov . 21, 2002
[ 0100] In th e abov e g ener al f or m ulae, R32 r epr es ents
h y dr og en atom , a h alog en atom , an aliph atic h y dr ocar bon
g r oup h av ing 1 to 30 car bon atom s , an ar om atic h y dr ocar bon
g r oup h av ing 6 to 30 car bon atom s , an alkox y l g r oup h av ing
1 to 30 car bon atom s , an ar y lox y l g r oup h av ing 6 to 30
car bon atom s , a th ioalkox y l g r oup h av ing 1 to 30 car bon
atom s , a th ioar y lox y l g r oup h av ing 6 to 30 car bon atom s ,
am ino g r oup, am ido g r oup or car box y l g r oup; th e plur ality
of g r oups r epr es ented by R32 m ay be th e s am e With or
dif f er ent f r om each oth er and m ay be bonded to each oth er
to f or m a cy clic s tr uctur e; Z r epr es ents a m etal elem ent of
any of Gr oups 2 to 13; m r epr es ents an integ er Wh ich is th e
v alence of th e m etal elem ent r epr es ented by Z ; and R33
r epr es ents a h y dr ocar bon g r oup.
[ 0101] Speci? cally , com pound ( C-1) is at leas t one com
pound s elected f r om alcoh ols , eth er s , aldeh y des , ketones ,
car box y lic acids and es ter s of car box y lic acids and pr ef er
ably an alcoh ol and com pound ( C-2) is an alum inum com
pound. Com pounds s atis f y ing any of th e f olloWing condi
tions ar e pr ef er ably us ed: ( 1) at leas t one of th r ee R32 in
( R32) 3 r epr es ents an ar om atic h y dr ocar bon g r oup h av ing 6
to 30 car bon atom s ; ( 2) th r ee R32 in ( R32) 3 each r epr es ent a
h y dr ocar bon g r oup h av ing 1 or m or e car bon atom s ; ( 3) th r ee
R32 in ( R32) 3 each r epr es ent an ar om atic h y dr ocar bon g r oup
h av ing 6 to 30 car bon atom s and pr ef er ably ph eny l g r oup;
and ( 4 ) R33 r epr es ents a alky l g r oup h av ing 2 or m or e car bon
atom s . Mor e s peci? cally , tr iph eny lm eth y l alcoh ol is m or e
pr ef er able as com pound ( C-1) and tr iis obuty lalum inum is
m or e pr ef er able as com pound ( C-2) .
[ 0102] Alky lating Ag ent
[ 0103] Com ponent ( C) of th e cataly s t us ed in th e pr es ent
inv ention m ay com pr is e an alky lating ag ent, Wh er e neces
s ar y . Var ious com pounds can be us ed as th e alky lating ag ent.
Ex am ples of th e alky lating ag ent include:
[ 0104 ] alum inum com pounds h av ing alky l g r oups
Wh ich ar e r epr es ented by g ener al f or m ula ( X X IV) :
[ 0105] Wh er ein R34 and R35 each r epr es ent an alky l g r oup
h av ing 1 to 8 car bon atom s and pr ef er ably 1 to 4 car bon
atom s , X r epr es ents h y dr og en atom or a h alog en atom , m
r epr es ents a num ber s atis f y ing 0< m 3, pr ef er ably 2 or 3
and m or e pr ef er ably 3 and n r epr es ents a num ber s atis f y ing
0n< 3 and pr ef er ably 0 or 1;
[ 0106] m ag nes ium com pounds h av ing alky l g r oups
Wh ich ar e r epr es ented by g ener al f or m ula ( X X V) :
R34 2 Mg ( X X V)
[ 0107]
[ 0108 ] Z inc com pounds h av ing alky l g r oups Wh ich
ar e r epr es ented by g ener al f or m ula ( X X VI) :
Wh er ein R34 is as de? ned abov e; and
R34 2Z n
[ 0109 ] Wh er ein R34 is as de? ned abov e.
[ 0110] Am ong th es e com pounds h av ing alky l g r oups , alu
m inum com pound h av ing alky l g r oups ar e pr ef er able and
tr ialky lalum inum com pounds and dialky lalum inum com
pounds ar e m or e pr ef er able. Ex am ples of th e com pound
h av ing alky l g r oups include tr ialky lalum inum s s uch as tr i
m eth y lalum inum , tr ieth y lalum inum , tr i-n-pr opy lalum inum ,
tr iis opr opy lalum inum , tr i-n-buty lalum inum , tr iis obuty lalu
m inum and tr it-buty lalum inum ; dialky lalum inum h alides
US 2002/ 0173605 A1
s uch as dim eth y lalum inum ch lor ide, dieth y lalum inum ch lo
r ide, di-n-pr opy lalum inum ch lor ide, diis opr opy lalum inum
ch lor ide, di-n-buty lalum inum ch lor ide, diis obuty lalum inum
ch lor ide and di-t-buty lalum inum ch lor ide; dialky lalum inum
alkox ides s uch as dim eth y lalum inum m eth ox ide and dim
eth y lalum inum eth ox ide; dialky lalum inum h y dr ides s uch as
dim eth y lalum inum h y dr ide, dieth y lalum inum h y dr ide and
diis obuty lalum inum h y dr ide; dialky lm ag nes ium s s uch as
dim eth y lm ag nes ium , dieth y lm ag nes ium , di-n-pr opy lm ag
nes ium and diis opr opy lm ag nes ium ; and dialky lZ incs s uch as
dim eth y lZ inc, dieth y lZ inc, di-n-pr opy lZ inc and diis opr opy
lZ inc.
[ 0111] Th e cataly s t can be pr epar ed in accor dance With th e
f ollow ing pr oces s .
[ 0112] ( 1) Or der of Contact of th e Com ponents
[ 0113] In th e pr es ent inv ention, th e or der of br ing ing th e
com ponents into contact With each oth er is not par ticular ly
lim ited. Th e com ponents can be br oug h t into contact With
each oth er in or der s s h oWn in th e f olloWing .
[ 0114 ] Wh en com ponent ( A) , com ponent ( B) and com
ponent ( C) ar e us ed, f or ex am ple, com ponent ( A) is
br oug h t into contact With com ponent ( B) and th en com po
nent ( C) is br oug h t into contact With th e r es ultant m ix tur e;
@ com ponent ( A) is br oug h t into contact With com ponent
( C) and th en com ponent ( B) is br oug h t into contact With th e
r es ultant m ix tur e; com ponent ( B) is br oug h t into contact
With com ponent ( C) and th en com ponent ( A) is br oug h t into
contact With th e r es ultant m ix tur e; or th r ee com ponents
ar e s im ultaneous ly br oug h t into contact With each oth er .
[ 0115] Wh en an alky lating ag ent is us ed as one of com
ponent ( C) in accor dance With neces s ity , th e or der of br ing
ing com ponent ( C) into contact With oth er com ponents is not
par ticular ly lim ited. Th e alky lating ag ent m ay be us ed af ter
being br oug h t into contact With com ponent ( A) ; th e alky
lating ag ent m ay be us ed af ter being br oug h t into contact
With com ponent ( B) ; th e alky lating ag ent m ay be us ed af ter
being br oug h t into contact With th e or g anom etallic com
pound r epr es ented by g ener al f or m ula ( X X III) of com ponent
( C) ; or com ponent ( A) , com ponent ( B) and th e alky lating
ag ent as one of com ponent ( C) ar e br oug h t into contact With
each oth er in adv ance and th en th e or g anom etallic com
pound r epr es ented by g ener al f or m ula ( X X III) of com ponent
( C) m ay be br oug h t into contact With th e r es ultant m ix tur e.
[ 0116] ( ii) Wh en com ponent ( A) , com ponent ( B) , com po
nent ( C1) and com ponent ( C2) ar e us ed, s im ilar ly to des cr ibed abov e, th e or der of br ing ing th e com ponents into
contact With each oth er is not par ticular ly lim ited. It is
pr ef er able th at com ponent ( C1) and com ponent ( C2) ar e
br oug h t into each oth er bef or e th es e com ponents ar e br oug h t
into contact With oth er com ponents . Wh en an alky lating
ag ent is us ed in accor dance With neces s ity , th e com ponents
m ay be br oug h t into contact With each oth er in a s im ilar
m anner to th at in des cr ibed abov e.
[ 0117] ( 2) Relativ e Am ounts of th e Com ponents
[ 0118 ] Wh en th e com pound h av ing ox y g en is us ed as
com ponent ( B) and an or g anoalum inum com pound is us ed
as th e com pound h av ing ox y g en, th e or g anoalum inum com
pound is us ed in an am ount s uch th at th e am ount of
alum inum atom is , in g ener al, in th e r ang e of 1 to 10, 000
m oles and pr ef er ably in th e r ang e of 10 to 1, 000 m oles per
N ov . 21, 2002
1 m ole of com ponent Wh en th e com pound Wh ich can
f or m an ionic com plex com pound by r eaction With th e
tr ans ition m etal com pound is us ed as com ponent ( B) and a
bor on com pound is us ed as th e com pound Wh ich can f or m
an ionic com plex com pound by r eaction With th e tr ans ition
m etal com pound, th e bor on com pound is us ed in an am ount
s uch th at th e am ount of bor on atom is , in g ener al, in th e
r ang e of 0. 5 to 10 m oles and pr ef er ably in th e r ang e of 0. 8
to 5 m oles per 1 m ole of com ponent
[ 0119 ] Wh en com ponent ( C) , is us ed, th e am ount of
com ponent ( C) is as f olloWs . Wh en an alum inum com pound
is us ed as th e or g anom etallic com pound r epr es ented by
g ener al f or m ula ( X X III) , th e alum inum com pound is us ed in
an am ount s uch th at th e am ount of alum inum atom is in th e
r ang e of 0. 5 to 1, 000 m oles and pr ef er ably in th e r ang e of 1
to 100 m oles per 1 m ole of com ponent Wh en an
alky lating ag ent is us ed and an alum inum com pound is us ed
as th e alky lating ag ent, th e alum inum com pound is us ed in
an am ount s uch th at th e am ount of alum inum atom is in th e
r ang e of g r eater th an 0 ( ex cluding 0) to 1, 000 m oles ,
pr ef er ably in th e r ang e of 1 to 500 m oles and m or e pr ef er
ably in th e r ang e of 10 to 300 m oles per 1 m ole of
com ponent
[ 0120] Wh en com ponent ( C) is not us ed but com ponent
( C1) and com ponent ( C2) ar e us ed, th e am ounts of th e
com ponents ar e as f olloWs . Th e r atio of th e am ounts by m ole
of com ponent ( Cl) to com ponent ( C2) is s elected in th e
r ang e of 110. 1 to 10, pr ef er ably in th e r ang e of 1: 05 to 2 and
m or e pr ef er ably in th e r ang e of 110. 8 to 1. 2. Com ponent
( C2) is us ed in an am ount s uch th at th e am ount of alum inum
atom is in th e r ang e of 0. 5 to 1, 000 m oles and pr ef er ably in
th e r ang e of 1 to 100 m oles of per 1 m ole of com ponent
Th e am ount of th e alky lating ag ent is th e s am e as th at
des cr ibed abov e.
[ 0121] ( 3) Condition of Contact of th e Com ponents
[ 0122] Th e com ponents of th e cataly s t can be br oug h t into
contact With each oth er in an iner t g as s uch as nitr og en g as
at th e tem per atur e of th e poly m er iZ ation or loWer . Th e
tem per atur e m ay be in th e r ang e of 30 to 200 C.
[ 0123] In th e pr oces s of th e pr es ent inv ention, th e m etal
com pound des cr ibed abov e is br oug h t into inter action With
th e v iny l com pound h av ing a f unctional g r oup and th e
f unctional g r oup is m as ked. For th is pur pos e, it is s uf f icient
th at th e v iny l com pound h av ing a f unctional g r oup is
br oug h t into contact With th e m etal com pound and th e
conditions of th e contact s uch as th e or der of addition, th e
pr es ence or th e abs ence of a s olv ent, th e tem per atur e and th e
tim e dur ing th e contact ar e not par ticular ly lim ited. As f or
th e am ount of th e m etal com pound r elativ e to th e am ount of
th e v iny l com pound h av ing a f unctional g r oup, th e am ount
of th e m etal com pound is 1 m ole or m or e and pr ef er ably in
th e r ang e of 1 to 109 m oles per 1 m ole of th e v iny l com pound
h av ing a f unctional g r oup. Wh en th e v iny l com pound h av ing
a f unctional g r oup tr eated as des cr ibed abov e is us ed f or th e
copoly m er iZ ation With th e s ty r enic com pound, th e liq uid
obtained af ter th e m as king Wh ich contains th e r es idual m etal
com pound m ay be us ed f or th e poly m er iZ ation With out any
tr eatm ents or th e m as ked v iny l com pound h av ing a f unc
tional g r oup m ay be is olated f r om th e liq uid obtained af ter
th e m as king and us ed f or th e copoly m er iZ ation.
[ 0124 ] It is cons ider ed th at, by m as king th e v iny l com
pound h av ing a f unctional g r oup With th e m etal com pound,
US 2002/ 0173605 A1
inter action betw een th e m etal com pound and th e f unctional
g r oup takes place and a v iny l com pound containing th e
m etal com pound is f or m ed. As th e inter action, th e f ollow ing
th r ee r eactions m ay be cons ider ed: ( 1) th e r eaction of th e
activ e h y dr og en in f or m y l g r oup, car bony l g r oup or im ino
g r oup With a s ubs tituent g r oup of th e m etal com pound, ( 2)
th e r eaction of f or m y l g r oup, car bony l g r oup or im ino g r oup
With a s ubs tituent g r oup of th e m etal com pound and ( 3)
coor dination of th e m etal com pound to eth er g r oup or
ter tiar y am ino g r oup. HoWev er , th e inter action is not lim ited
to th e abov e r eactions .
[ 0125] Ex am ples of th e abov e r eactions ( 1) , ( 2) and ( 3) ar e
s h oWn in th e f olloWing :
Reaction ( 1)
Reaction ( 2)
[ 0126] ( R: a h y dr ocar bon g r oup; iBu: is obuty l g r oup)
[ 0127] Reactions ( 1) , ( 2) and ( 3) can be con? r m ed by th e
m eas ur em ent of th e pr oton nuclear m ag netic r es onance
s pectr um ( lH-N MR) . For ex am ple, r eaction ( 1) can be
con? r m ed by dis appear ance of th e peak of th e activ e h y dr o
g en der iv ed f r om th e v iny l com pound due to th e inter action
With th e m etal com pound. Reactions ( 2) and ( 3) can be
con? r m ed by th e ch ang e in th e ch em ical s h if t of th e peak
der iv ed f r om th e v iny l com pound to a dif f er ent v alue due to
th e inter action With th e m etal com pound.
[ 0128 ] In th e pr oces s of th e pr es ent inv ention, th e v iny l
com pound h av ing a f unctional g r oup Wh ich h as been
m as ked With th e m etal com pound is copoly m er iZ ed With th e
s ty r enic com pound in th e pr es ence of th e poly m er iZ ation
cataly s t des cr ibed abov e.
[ 0129 ] In th e copoly m er iZ ation, a pr elim inar y poly m er iZ a
tion m ay be conducted. Th e pr elim inar y poly m er iZ ation can
be conducted, f or ex am ple, by br ing ing th e abov e cataly s t
With a s m all am ount of a s ty r enic com pound. Th e pr oces s of
th e pr elim inar y poly m er iZ ation is not par ticular ly lim ited
and can be conducted in accor dance With a conv entional
pr oces s . Th e s ty r enic com pound us ed f or th e pr elim inar y
poly m er iZ ation is not par ticular ly lim ited and th e s ty r enic
com pound des cr ibed abov e can be us ed. Th e tem per atur e of
th e pr elim inar y poly m er iZ ation is , in g ener al, in th e r ang e of
20 to 200 C. and pr ef er ably in th e r ang e of 10 to 130 C.
As th e s olv ent, an iner t h y dr ocar bon, an aliph atic h y dr ocar
bon, an ar om atic h y dr ocar bon or a m onom er can be us ed.
N ov . 21, 2002
[ 0130] Th e pr oces s f or copoly m er iZ ing th e s ty r enic m ono
m er and th e v iny l com pound h av ing a f unctional g r oup is not
par ticular ly lim ited. Any poly m er iZ ation pr oces s s uch as th e
s lur r y poly m er iZ ation pr oces s , th e s olution poly m er iZ ation
pr oces s , th e g as ph as e poly m er iZ ation pr oces s , th e bulk
poly m er iZ ation pr oces s and th e s us pens ion poly m er iZ ation
pr oces s can be us ed. Th e or der of br ing ing th e com ponents
of th e cataly s t and th e m onom er s into contact With each
oth er is not par ticular ly lim ited. Speci? cally , th e cataly s t
m ay be pr epar ed by m ix ing th e com ponents in adv ance as
des cr ibed abov e and th e m onom er s m ay be added to th e
pr epar ed cataly s t. Alter nativ ely , th e com ponents of th e cata
ly s t and th e m onom er s m ay be placed into th e ? eld of th e
copoly m er iZ ation in a des ir ed or der With out pr epar ing th e
cataly s t in adv ance by m ix ing th e com ponents . Th e pr ef er
able pr oces s is as f olloWs : com ponent ( A) , com ponent ( B)
and th e alky lating ag ent in com ponent ( C) ar e m ix ed
tog eth er in adv ance, Wh er ein th e com pound r epr es ented by
g ener al f or m ula ( X X III) , com ponent ( C1) and com ponent
( C2) in com ponent ( C) ar e ex cluded; s epar ately , th e m ono
m er s ar e m ix ed With th e com pound r epr es ented by g ener al
f or m ula ( X X III) or a com bination of com ponent ( C1) and
com ponent ( C2) ; and th e copoly m er iZ ation is conducted by
m ix ing th e tWo m ix tur es pr epar ed abov e im m ediately bef or e
th e copoly m er iZ ation.
[ 0131] Wh en a s olv ent is us ed, ex am ples of th e s olv ent
include h y dr ocar bons and h alog enated h y dr ocar bons s uch as
benZ ene, toluene, x y lene, n-h ex ane, n-h eptane, cy cloh ex ane,
m eth y lene ch lor ide, ch lor of or m , 1, 2-dich lor oeth ane and
ch lor obenZ ene. Th e s olv ent m ay be us ed s ing ly or in com
bination of tWo or m or e. Th e m onom er us ed f or th e copo
ly m er iZ ation m ay be us ed as th e s olv ent Wh en th e ty pe of th e
m onom er is s uitable.
[ 0132] As f or th e conditions of th e copoly m er iZ ation, in
g ener al, th e pr es s ur e is s elected in th e r ang e of th e or dinar y
pr es s ur e to 2, 000 kg / cm 2. G and th e tem per atur e is s elected
in th e r ang e of 50 to 250 C. Th e m olecular Weig h t of th e
copoly m er can be adj us ted, f or ex am ple, by s uitably s elect
ing th e ty pes and th e am ounts of th e com ponents of th e
cataly s t and th e tem per atur e of th e copoly m er iZ ation or by
intr oducing h y dr og en.
[ 0133] In th e pr oces s of th e pr es ent inv ention, af ter th e
copoly m er iZ ation is conducted as des cr ibed abov e, th e m etal
com pound m as king th e f unctional g r oup can be r em ov ed by
br ing ing th e m as ked f unctional g r oup into contact With an
aq ueous s olution or an alcoh ol and th e f unctional g r oup can
be r eg ener ated. Th e des ir ed r andom copoly m er can be
obtained af ter r em ov ing th e m etal com pound m as king th e
f unctional g r oup as des cr ibed abov e. Th e r eaction of
r em ov al of th e m etal com pound can be s h oWn by th e
f olloWing eq uations ( 4 ) and ( 5) :
Reaction ( 4 )
US 2002/ 0173605 A1
-continued
A1 ' B
I ( 1 Us
N ' < R _ > N R2
R
[ 0134 ] Ex am ples of th e aq ueous s olution include Water
and aq ueous s olutions containing an acid or a bas e.
Ex am ples of th e acid include HCl, HBr , HN O3, HZ SO4 and
H3PO4 and ex am ples of th e bas e include am m onia, s odium
h y dr ox ide and s odium m eth ox ide. Ex am ples of th e alcoh ol
include alcoh ols h av ing 1 to 10 car bon atom s s uch as
m eth anol, eth anol, is opr opanol and t-butanol.
[ 0135] Th e condition f or br ing ing th e aq ueous s olution or
th e alcoh ol into contact With th e pr oduct of th e copoly m er
iZ ation is not par ticular ly lim ited. Th e tem per atur e is , in
g ener al, in th e r ang e of 100 to 300 C. and pr ef er ably in th e
r ang e of 0 to 300 C. Th e pr es s ur e is , in g ener al, in th e r ang e
of th e or dinar y pr es s ur e to 200 MPa. G.
[ 0136] In accor dance With th e pr oces s of th e pr es ent
inv ention des cr ibed abov e, th e s ty r enic copoly m er h av ing a
f unctional g r oup Wh ich is a copoly m er of th e v iny l com
pound h av ing a f unctional g r oup and th e s ty r enic m onom er
and in Wh ich th e r epeating unit der iv ed f r om th e s ty r enic
m onom er h as th e s y ndiotactic con? g ur ation can be ef ?
ciently pr oduced.
[ 0137] Th e r andom s ty r enic copoly m er of th e pr es ent
inv ention h av ing a f unctional g r oup and th e s y ndiotactic
con? g ur ation com pr is es :
[ 0138 ] ( a) s ty r enic r epeating units r epr es ented by
g ener al f or m ula ( II) :
( H)
CH2 CH
/ |
\ \
( R01
[ 0139 ] Wh er ein R8 and t ar e as de? ned abov e, and
[ 014 0] ( b) r epeating units Wh ich ar e der iv ed f r om a
v iny l com pound h av ing a f unctional g r oup and r ep
r es ented by g ener al f or m ula ( III) :
[ 014 1] Wh er ein D r epr es ents a s ubs tituent h av ing OR1,
COR1, CO2R1, CN , N R1R2, _ s R1 or PR1R2,
( III)
N ov . 21, 2002
R1 and R2 each r epr es enting h y dr og en atom , an alky l g r oup
h av ing 1 to 20 car bon atom s , an ar y l g r oup h av ing 6 to 20
car bon atom s or an alky ls ily l g r oup h av ing 3 to 20 car bon
atom s ; R r epr es ents a linear or br anch ed h y dr ocar bon g r oup
h av ing 1 to 20 car bon atom s ; Wh en a plur ality of D ar e
pr es ent, th e plur ality of D m ay r epr es ent a s am e g r oup or
dif f er ent g r oups ; n r epr es ents an integ er of 1 to 5; m
r epr es ents an integ er of 0 to 4 ; and n+m 5,
[ 014 2] Wh er ein th e copoly m er com pr is es r epeating
unit ( b) and a s ter ic r eg ular ity of th e copoly m er
com pr is ing r epeating unit ( a) and r epeating unit ( b)
is s y ndiotactic.
[ 014 3] Th e s y ndiotactic con? g ur ation m eans th at th e s te
r eoch em ical s tr uctur e h as a h ig h ly s y ndiotactic con? g ur a
tion. In oth er Wor ds , ph eny l g r oups of th e s ide g r oups ar e
alter nately placed at th e oppos ite pos itions With r es pect to
th e m ain ch ain f or m ed With th e car bon-car bon bonds . Th e
tacticity in th e s ter eoch em ical s tr uctur e is q uantitated by th e
m eas ur em ent of th e nuclear m ag netic r es onance us ing an
is otope of car bon ( 13CN MR) . Th e tacticity m eas ur ed in
accor dance With th e 13CN MR m eth od can s h oW th e
content of a s eq uence in Wh ich a s peci? c num ber of th e
cons tituting units ar e bonded in s eq uence, s uch as a diad in
Wh ich tWo cons tituting units ar e bonded in s eq uence, a tr iad
in Wh ich th r ee cons tituting units ar e bonded in s eq uence, and
a pentad in Wh ich ? v e cons tituting units ar e bonded in
s eq uence. In th e pr es ent inv ention, th e s ty r enic copoly m er
h av ing th e s y ndiotactic con? g ur ation m eans a copoly m er
h av ing th e s eq uence of th e r epeating units of th e s ty r enic
m onom er Wh ich g ener ally h as a s y ndiotacticity of 75% or
m or e and pr ef er ably 8 5% or m or e as ex pr es s ed in ter m s of
th e content of th e diad, or 30% or m or e and pr ef er ably 50%
or m or e as ex pr es s ed in ter m s of th e content of th e pentad.
[ 014 4 ] In th e copoly m er of th e pr es ent inv ention, th e
content of th e abov e r epeating unit ( b) is s elected in th e
r ang e of 0. 01 to 50% by m ole. Wh en th e content is s m aller
th an 0. 01% by m ole, th e ef f ect of im pr ov ing th e ph y s ical
pr oper ties of th e copoly m er s uch as adh es ion is not s uf ?
ciently ex h ibited. Wh en th e content ex ceeds 50% by m ole,
h eat r es is tance of th e copoly m er deter ior ates . Fr om th e
s tandpoint of th e ef f ect of im pr ov ing th e ph y s ical pr oper ties
and h eat r es is tance, it is pr ef er able th at th e content of
r epeating unit ( b) is in th e r ang e of 0. 5 to 30% by m ole and
m or e pr ef er ably in th e r ang e of 1 to 20% by m ole.
[ 014 5] Th e s ty r enic copoly m er of th e pr es ent inv ention
h av ing a f unctional g r oup and th e s y ndiotactic con? g ur ation
h as ex cellent ph y s ical pr oper ties s uch as adh es ion With
v ar ious ty pes of adh es iv e and com patibility With v ar ious
ty pes of r ubber and can be adv antag eous ly us ed as m olded
ar ticles in v ar ious applications as des cr ibed later .
[ 014 6] Th e s ty r enic copoly m er of th e pr es ent inv ention
h av ing a f unctional g r oup and th e s y ndiotactic con? g ur ation
can be ef f iciently pr oduced in accor dance With th e pr oces s of
th e pr es ent inv ention des cr ibed abov e.
[ 014 7] Th e s ty r enic copoly m er of th e pr es ent inv ention
can be f or m ed into v ar ious m olded ar ticles . Th e s ty r enic
copoly m er m ay als o be us ed as com pos itions com pr is ing
conv entional th er m oplas tic r es ins , r ubber y elas tom er s , anti
ox idants , inor g anic ? ller s , cr os s linking ag ents , aux iliar y
cr os s linking ag ents , nucleating ag ents , plas ticiZ er s , com pati
biliZ er s , color ing ag ents and antis tatic ag ents as long as th e
obj ect of th e pr es ent inv ention is not adv er s ely af f ected.
US 2002/ 0173605 A1
[ 014 8 ] Ex am ples of th e th er m oplas tic r es in include s ty
r enic poly m er s s uch as poly s ty r ene h av ing th e atactic con
? g ur ation, poly s ty r ene h av ing th e is otactic con? g ur ation,
AS r es ins and ABS r es ins ; poly es ter s s uch as poly eth y lene
ter eph th alate; poly car bonates ; poly eth er s s uch as poly ph e
ny lene eth er s , poly s ulf ones and poly eth er s ulf ones ; conden
s ation poly m er s s uch as poly am ides , poly ph eny lene s ul? des
( PPS) and poly ox y m eth y lene; acr y lic poly m er s s uch as
poly acr y lic acid, poly acr y lic es ter s and poly m eth y l m eth
acr y late; poly ole? ns s uch as poly eth y lene, poly pr opy lene,
poly butene, poly -4 -m eth y lpentene-1 and eth y lene-pr opy
lene copoly m er s ; poly m er s of v iny l com pounds h av ing
h alog en atom s s uch as poly v iny l ch lor ide, poly v iny lidene
ch lor ide and poly v iny lidene ? uor ide; and m ix tur es of th es e
poly m er s .
[ 014 9 ] Ex am ples of th e r ubber y elas tom er include natur al
r ubber ; poly butadiene; poly is opr ene; poly is obuty lene; neo
pr ene; poly s ul? de r ubber s ; th iokol r ubber s ; acr y lic r ubber s ;
ur eth ane r ubber s ; s ilicone r ubber s ; epich lor oh y dr ine r ub
ber s ; s ty r ene-butadiene block copoly m er s ( SBR) ; h y dr og e
nated s ty r ene-butadiene block copoly m er s ( SEB) ; s ty r ene
butadiene-s ty r ene block copoly m er s ( SBS) ; h y dr og enated
s ty r ene-butadiene-s ty r ene block copoly m er s ( SEBS) ; s ty
r ene-is opr ene block copoly m er s ( SIR) ; h y dr og enated s ty
r ene-is opr ene block copoly m er s ( SEP) ; s ty r ene-is opr ene
s ty r ene block copoly m er s ( SIS) ; h y dr og enated s ty r ene
is opr ene-s ty r ene block copoly m er s ( SEPS) ; s ty r ene
butadiene r andom copoly m er s ; h y dr og enated s ty r ene
butadiene r andom copoly m er s ; s ty r ene-eth y lene-pr opy lene
r andom copoly m er s ; s ty r ene-eth y lene-buty lene r andom
copoly m er s ; eth y lene-pr opy lene r ubber s ( EPR) ; eth y lene
pr opy lene-diene r ubber s ( EPD M) ; par ticulate elas tom er s of
th e cor e-s h ell ty pe s uch as butadiene-acr y lonitr ile-s ty r ene
cor e-s h ell r ubber s ( ABS) , m eth y l m eth acr y late-butadiene
s ty r ene cor e-s h ell r ubber s ( MBS) , m eth y l m eth acr y late
buty l acr y late-s ty r ene cor e-s h ell r ubber s ( MAS) , octy l acr y
late-butadiene-s ty r ene cor e-s h ell r ubber s ( MABS) , alky l
acr y late-butadiene-acr y lonitr ile-s ty r ene cor e-s h ell r ubber s
( AABS) , butadiene-s ty r ene cor e-s h ell r ubber s ( SBR) , cor e
s h ell r ubber s containing s ilox anes s uch as m eth y l m eth acr y
late-buty l acr y late-s ilox ane cor e-s h ell r ubber s ; and r ubber s
obtained by m odif y ing th es e r ubber s .
[ 0150] Am ong th es e r ubber y elas tom er s , SBR, SBS, SEB,
SEBS, SER, SEP, SIS, SEPS, cor e-s h ell r ubber s and r ubber s
obtained by m odif y ing th es e r ubber s ar e pr ef er ably us ed.
[ 0151] Ex am ples of th e m odi? ed r ubber y elas tom er
include r ubber s obtained by m odif y ing s ty r ene-buty l acr y
late copoly m er r ubber s , s ty r ene-butadiene block copoly m er s
( SBR) , h y dr og enated s ty r ene-butadiene block copoly m er s
( SEB) , s ty r ene-butadiene-s ty r ene block copoly m er s ( SBS) ,
h y dr og enated s ty r ene-butadiene-s ty r ene block copoly m er s
( SEBS) , s ty r ene-is opr ene block copoly m er s ( SIR) , h y dr o
g enated s ty r ene-is opr ene block copoly m er s ( SEP) , s ty r ene
is opr ene-s ty r ene block copoly m er s ( SIS) , h y dr og enated s ty
r ene-is opr ene-s ty r ene block copoly m er s ( SEPS) , s ty r ene
butadiene r andom copoly m er s , h y dr og enated s ty r ene
butadiene r andom copoly m er s , s ty r ene-eth y lene-pr opy lene
r andom copoly m er s , s ty r ene-eth y lene-buty lene r andom
copoly m er s , eth y lene-pr opy lene r ubber s ( EPR) and eth y l
ene-pr opy lene-diene r ubber s ( EPD M) With a m odi? er h av
ing a polar f unctional g r oup. Am ong th es e r ubber s , r ubber s
obtained by m odif y ing SEB, SEBS, SEP, SEPS, EPR and
EPD M ar e pr ef er ably us ed. Speci? c ex am ples of th e abov e
N ov . 21, 2002
r ubber s include SEBS m odi? ed With m aleic anh y dr ide,
SEPS m odi? ed With m aleic anh y dr ide, EPR m odi? ed With
m aleic anh y dr ide, EPD M m odi? ed With m aleic anh y dr ide,
SEBS m odi? ed With epox y g r oup and SEPS m odi? ed With
epox y g r oup.
[ 0152] Th e r ubber y elas tom er m ay be us ed s ing ly or in
com bination of tWo or m or e.
[ 0153] As th e antiox idant, v ar ious com pounds can be
us ed. Pr ef er able ex am ples of th e antiox idant include anti
ox idants h av ing ph os ph or us and ph enolic antiox idants .
Ex am ples of th e antiox idant h av ing ph os ph or us include
m onoph os ph ites and diph os ph ites s uch as tr is ( 2, 4 -di-t-bu
ty lph eny l) ph os ph ite and tr is ( m ono- and di-nony lph eny l)
ph os ph ites . As th e diph os ph ite, it is pr ef er able th at ph os
ph or us com pounds r epr es ented by th e f olloWing g ener al
f or m ula ar e us ed:
[ 0154 ] Wh er ein R36 and R37 each independently r epr es ent
an alky l g r oup h av ing 1 to 20 car bon atom s , a cy cloalky l
g r oup h av ing 3 to 20 car bon atom s or an ar y l g r oup h av ing
6 to 20 car bon atom s .
[ 0155] Speci? c ex am ples of th e ph os ph or us com pound
r epr es ented by th e abov e g ener al f or m ula include dis tear y l
pentaer y th r itol diph os ph ite, diocty lpentaer y th r itol diph os
ph ite, diph eny lpentaer y th r itol diph os ph ite, bis ( 2, 4 -di-t-bu
ty lph eny l) pentaer y th r itol diph os ph ite, bis ( 2, 6-di-t-buty l-4
m eth y lph eny l) pentaer y th r itol diph os ph ite and
dicy cloh ex y lpentaer y th r itol diph os ph ite.
[ 0156] As th e ph enolic antiox idant, conv entional ph enolic
antiox idants can be us ed. Ex am ples of th e ph enolic antiox i
dant include 2, 6-di-t-buty l-4 -m eth y lph enol, 2, 6-diph eny l-4
m eth ox y ph enol, 2, 2 -m eth y lenebis ( 6-t-buty l-4 -m eth y lph e
nol) , 2, 2 -m eth y lenebis ( 6-t-buty l-4 -m eth y lph enol) , 2, 2
m eth y lenebis [ 4 -m eth y l-6-( a-m eth y lcy cloh ex y l) ph enol] ,
1, 1-bis ( 5-t-buty l-4 -h y dr ox y -2-m eth y lph eny l) butane, 2, 2
m eth y lenebis ( 4 -m eth y l-6-cy cloh ex y lph enol) , 2, 2 -m eth y l
enebis ( 4 -m eth y l-6-nony lph enol) , 1, 1, 3-tr is ( 5-t-buty l-4 -h y
dr ox y -2-m eth y lph eny l) butane, 2, 2-bis ( 5-t-buty l-4 -h y dr ox y
2-m eth y lph eny l) -4 -n-dodecy lm er captobutane, eth y lene
g ly col-bis [ 3, 3-bis ( 3-t-buty l-4 -h y dr ox y ph eny l) buty r ate] ,
1, 1-bis ( 3, 5-dim eth y l-2-h y dr ox y ph eny l) -3-( n-dodecy lth
io) butane, 4 , 4 -th iobis ( 6-t-buty l-3-m eth y lph enol) , dioctade
cy l 1, 3, 5-tr is ( 3, 5-di-t-buty l-4 -h y dr ox y benZ y l) -2, 4 , 6-tr im
eth y lbenZ ene, dioctadecy l 2, 2-bis ( 3, 5-di-t-buty l-4
h y dr ox y benZ y l) m alonate, n-octadecy l 3-( 4 -h y dr ox y -3, 5-di
t-buty lph eny l) pr opionate and tetr akis [ m eth y lene ( 3, 5-di-t
buty l-4 -h y dr ox y h y dr ocinnam ate) ] m eth ane.
[ 0157] As antiox idants oth er th an th e antiox idants h av ing
ph os ph or us and th e ph enolic antiox idants des cr ibed abov e,
am ine antiox idants and antiox idants containing s ulf ur m ay
be us ed s ing ly or as a m ix tur e.
[ 0158 ] Th e abov e antiox idant is us ed, in g ener al, in an
am ount of 0. 0001 to 1 par t by Weig h t per 100 par ts by Weig h t
of th e s ty r enic copoly m er of th e pr es ent inv ention. Wh en th e
US 2002/ 0173605 A1
am ount is les s th an 0. 0001 par t by Weig h t, a m ar ked
decr eas e in th e m olecular Weig h t takes place. Wh en th e
am ount ex ceeds 1 par t by Weig h t, m ech anical s tr eng th is
adv er s ely af f ected. Th er ef or e, am ounts outs ide th e abov e
r ang e ar e not pr ef er able.
[ 0159 ] As th e inor g anic ? ller , any of ? ller s h av ing a ? ber
s h ape, g r anular ? ller s and poWder ? ller s m ay be us ed.
Ex am ples of th e inor g anic ? ller h av ing a ? ber s h ape include
g las s ? ber s , car bon ? ber s and alum ina ? ber s . Ex am ples of
th e g r anular ? ller s and th e poWder ? ller s include talc, car bon
black, g r aph ite, titanium diox ide, s ilica, m ica, calcium car
bonate, calcium s ulf ate, bar ium car bonate, m ag nes ium car
bonate, m ag nes ium s ulf ate, bar ium s ulf ate, ox y s ulf ates , tin
ox ides , alum ina, kaolin, s ilicon car bide and m etal poWder s .
[ 0160] Th e s h ape of th e m olded ar ticle pr epar ed f r om th e
s ty r enic copoly m er of th e pr es ent inv ention is not par ticu
lar ly lim ited. For ex am ple, th e m olded ar ticle m ay be a
s h eet, a ? lm , a ? ber , a non-Wov en f abr ic, a container or an
ar ticle pr epar ed in accor dance With th e inj ection m olding or
th e bloW m olding .
[ 0161] As th e pr oces s f or pr oducing a m olded ar ticle f r om
th e s ty r enic copoly m er of th e pr es ent inv ention, v ar ious
pr oces s es can be us ed. Th e f olloWing pr oces s es can be
adv antag eous ly us ed. Th e abov e s ty r enic copoly m er or a
com pos ition pr epar ed by adding v ar ious com ponents
des cr ibed abov e to th e s ty r enic copoly m er is pr elim inar ily
f or m ed into a pr elim inar ily m olded ar ticle f or th e h eat
tr eatm ent ( a ? lm , a s h eet or a container ) . In th is pr oces s , th e
m ater ial f or th e m olding pr epar ed abov e is m elted by
h eating and ex tr uded into a s uitable s h ape. A? lm or a s h eet
can be pr epar ed in accor dance With th e T-die m olding
pr oces s and oth er s tr uctur al ar ticles s uch as a container can
be pr epar ed in accor dance With th e inj ection m olding pr o
ces s . As th e ex tr us ion m ach ine us ed in th e abov e m olding
pr oces s es , any of a s ing le s cr eW ex tr uder and a tWin-s cr eW
ex tr uder With or With out v ents can be us ed. Th e condition of
th e ex tr us ion is not par ticular ly lim ited and can be s uitably
s elected in accor dance With th e s ituation. It is pr ef er able th at
th e tem per atur e dur ing th e m elting is s elected in th e r ang e of
th e m elting point of th e m ater ial us ed f or th e m olding to th e
tem per atur e h ig h er th an th e decom pos ition point by 50 C.
and th e s h ear ing s tr es s is s elected at 5> < 107 ptN / cm 2 or loWer
s ince th e pr elim inar ily m olded ar ticle f or th e h eat tr eatm ent
can be obtained With little f or m ation of r oug h s ur f aces .
[ 0162] Af ter th e abov e ex tr us ion and m olding , it is pr ef
er able th at th e obtained pr elim inar ily m olded ar ticle f or th e
h eat tr eatm ent is s olidi? ed by cooling . As th e m edium f or
cooling , v ar ious m edia s uch as a g as , a liq uid and a m etal can
be us ed. Wh en th e pr elim inar ily m olded ar ticle f or th e h eat
tr eatm ent is pr epar ed in accor dance With a s h eet m olding
pr oces s us ing a m etal r oll, us ing an air knif e, an air ch am ber
or a touch r oll or apply ing s tatic electr icity is ef f ectiv e f or
pr ev enting f or m ation of unev en th icknes s or a Wav ed s h ape.
Th e tem per atur e of s olidi? cation by cooling is , in g ener al, in
th e r ang e of 0 C. to a tem per atur e h ig h er th an th e g las s
tr ans ition tem per atur e of th e pr elim inar ily m olded ar ticle f or
th e h eat tr eatm ent by 30 C. and pr ef er ably in th e r ang e of
a tem per atur e loWer th an th e tr ans ition tem per atur e by 70
C. to th e g las s tr ans ition tem per atur e. Th e r ate of cooling is
not par ticular ly lim ited. Th e r ate of cooling is s elected, in
g ener al, in th e r ang e of 200 to 3 C. / s econd and pr ef er ably
in th e r ang e of 200 to 10 C. / s econd.
N ov . 21, 2002
[ 0163] Th e pr elim inar ily m olded ar ticle f or th e h eat tr eat
m ent m ay h av e v ar ious s h apes . In g ener al, th e pr elim inar ily
m olded ar ticle f or th e h eat tr eatm ent is a s h eet, a ? lm or a
container s uch as a tube and a tr ay h av ing a th icknes s of 5
m m or s m aller and pr ef er ably 3 m m or s m aller . Wh en th e
pr elim inar ily m olded ar ticle f or th e h eat tr eatm ent h as a
th icknes s ex ceeding 5 m m bef or e th e h eat tr eatm ent, cr y s
talliZ ation occas ionally takes place dur ing pr epar ation of th e
pr elim inar ily m olded ar ticle f or th e h eat tr eatm ent and a
tur bid pr oduct is obtained. Th e deg r ee of cr y s talliZ ation of
th e pr elim inar ily m olded ar ticle f or th e h eat tr eatm ent is
20% or s m aller and pr ef er ably 15% or s m aller . Wh en th e
deg r ee of cr y s talliZ ation of th e pr elim inar ily m olded ar ticle
f or th e h eat tr eatm ent ex ceeds 20%, tr ans par ency of th e
m olded ar ticle of th e s ty r enic copoly m er obtained af ter th e
h eat tr eatm ent is not s uf f icient.
[ 0164 ] Th e m olded ar ticle can be obtained by th e h eat
tr eatm ent of th e pr elim inar ily m olded ar ticle f or th e h eat
tr eatm ent pr epar ed abov e at a tem per atur e in th e r ang e of
14 0 to 18 0 C. and pr ef er ably in th e r ang e of 150 to 170 C.
Wh en th e tem per atur e of th e h eat tr eatm ent is loWer th an
14 0 C. , h eat r es is tance is ins uf ? cient and a tur bid pr oduct
is occas ionally obtained. Wh en th e tem per atur e of th e h eat
tr eatm ent ex ceeds 18 0 C. , tr ans par ency is ins uf ? cient. Th e
tim e of th e h eat tr eatm ent is , in g ener al, in th e r ang e of 1
s econd to 30 m inutes and pr ef er ably in th e r ang e of 1 s econd
to 10 m inutes . Wh en th e tem per atur e is r ais ed, it is pr ef er
able th at th e pr elim inar ily m olded ar ticle f or th e h eat tr eat
m ent is h eated in a m anner s uch th at th e tem per atur e of th e
ar ticle r apidly r each es th e pr es cr ibed tem per atur e of th e h eat
tr eatm ent. Fr om th is s tandpoint, th e r ate of r ais ing th e
tem per atur e is , in g ener al, 30 C. / m inute or g r eater and
pr ef er ably 50 C. / m inute or g r eater . Wh en th e r ate of r ais ing
th e tem per atur e is s m aller th an 30 C. / m inute, th e h eat
tr eatm ent takes place at tem per atur es loWer th an th e pr e
s cr ibed tem per atur e and tr ans par ency of th e m olded ar ticle
of th e s ty r enic copoly m er is occas ionally adv er s ely af f ected.
Th e m eth od of h eating in th e h eat tr eatm ent is not par ticu
lar ly lim ited. For ex am ple, th e pr elim inar ily m olded ar ticle
f or th e h eat tr eatm ent is br oug h t into contact With a m edium
f or h eating s uch as a g as , a liq uid and a m etal at a
tem per atur e in th e r ang e of 120 to 200 C. Th e m olded
ar ticle of th e s ty r enic copoly m er Wh ich h as been s ubj ected
to th e h eat tr eatm ent under th e abov e condition m ay be
s ubj ected to a f ur th er h eat tr eatm ent, Wh er e neces s ar y . In th e
f ur th er h eat tr eatm ent, it is pr ef er able th at th e tem per atur e is
in th e r ang e of th e g las s tr ans ition tem per atur e to th e m elting
point and th e tim e is 1 s econd or long er . Th e h eat def or m a
tion tem per atur e of th e m olded ar ticle of th e s ty r enic copoly
m er can be im pr ov ed With out adv er s e ef f ects on tr ans par
ency by th e f ur th er h eat tr eatm ent alth oug h im pr ov em ent in
th e deg r ee of cr y s talliZ ation cannot be ex pected.
EX AMPLES
[ 0165] Th e pr es ent inv ention Will be des cr ibed m or e s pe
ci? cally With r ef er ence to ex am ples in th e f olloWing . HoW
ev er , th e pr es ent inv ention is not lim ited to th e ex am ples .
[ 0166] Th e m elting point and th e adh es iv e pr oper ty of th e
copoly m er s obtained in th e ex am ples Wer e obtained in
accor dance With th e f olloWing m eth ods .
[ 0167] ( 1) Melting Point
[ 0168 ] Us ing an ins tr um ent D SC7 m anuf actur ed by
Per kin Elm er Com pany , a s am ple Was kept at 50 C. f or 1