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Journal of PetroleumScience and Technology
*Corresponding author
Saeid Ahmadjo
Email: [email protected]
Tel: +98 21 4866 2475
Fa:+98 21 4866 2475
Article history
!ecei"ed: #a$ 17% 2&1'
!ecei"ed i( re"ised )orm: *a(ar$ &8% 2&14
Accep,ed: *a(ar$ 18% 2&14
A"aila-le o(li(e: #arch 1&% 2&14
Journal of Petroleum Science and Technology 2014 , 41/% 2&028 h,,p:jps,.ripi.ir
2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/
20
IN SITU SILICA SUPPORTED METALLOCENE CATALYSTS FOR
ETHYLENE POLYMERIZATION
Saeid Ahmadjo1* !assan Ara"i1 #holam$!ossein %ohuri2 #holam$&e'a (eja"at1 )ojta"amid+ar
1 )ostafa Ahmadi
, and Seyed )ohammad )ahdi )orta'a+i
1
1 apar,me(, o) a,al$s,% 3ra( ol$mer a(d e,rochemical 3(s,i,,e 33/% Tehra(% 3ra(
2 epar,me(, o) hemis,r$% Facl,$ o) Scie(ce% Ferdosi (i"ersi,$ o) #ashhad% #ashhad% 3ra(
' epar,me(, o) ol$mer E(i(eeri( a(d olor Tech(olo$% Amira-ir (i"ersi,$ o) Tech(olo$% Tehra(% 3ra(
ABSTRACT
;is20!0i(d/<rl2 !: = or phe($l/ as sppor,ed o( di))ere(, ,$pes o) silica -$ i( si, impre(a,io(
me,hod a(d sed )or e,h$le(e pol$meri>a,io(. 3( ,his me,hod% ,he s,ep o) ca,al$s, loadi( o(
sppor, as elimi(a,ed a(d commo( al$l almi(m ,riiso-,$lalmi(m% Ti;A/ coca,al$s, assed i(s,ead o) epe(si"e me,h$l almi(imoa(e #A?/ coca,al$s, i( ,he pol$meri>a,io(. The
e))ec, o) sr)ace area o) silica o( ,he per)orma(ce o) ,he sppor,ed ca,al$s,s si( ,hree di))ere(,
,$pes o) silica i(cldi( E12 '9& m2r./% '&6& 57& m
2r./ a(d ##041 11&& m
2r./ as
i("es,ia,ed. The sr)ace area had a more cri,ical role rela,i"e ,o o,her charac,eris,ics o) ,he
sppor, i( ,he per)orma(ce o) ca,al$s,s. ;$ si( ##041 as sppor,% ,he i(e,ic s,a-ili,$ as
e(ha(ced. The ac,i"i,$ o) ,he sppor,ed ca,al$s,s as i(creased -$ i(creasi( ,he sr)ace area o)
silica i( ,he order o) ##041 '&6& E12. The morpholo$ o) pol$mer par,icles as impro"ed
a(d reac,or )oli( as elimi(a,ed -$ sppor,i( ,he ca,al$s,.
-ey.ords: 3( Si, 3mpre(a,io(% =e,eroe(eos a,al$sis% #e,alloce(e% ol$e,h$le(e% Silica
INTRODUCTION
ol$ole)i(s are ,he mos, idel$ sed pol$mers
a(d ,heir orld co(smp,io( eceeded 1&&
millio( ,o(s i( 2&1& B1C. Di,ho, a($ do-,% i,
ca( -e me(,io(ed ,ha, pol$meri>a,io( ca,al$s,s
pla$ ,he mos, "i,al role i( pol$ole)i( i(ds,r$ B20
4C. Amo( ,he (meros de"elopme(,s i(
pol$ole)i( ca,al$s,s% ,he disco"er$ o) me,al0
oce(e ca,al$s, is o(e o) ,he mos, crcial o(es
B5%6C. 3( ,he prese(ce o) #A? as coca,al$s,%
,hese ,$pes o) ca,al$s,s sho a co(sidera-l$
hih ac,i"i,$ )r,hermore% ,heir (ie co(,rol
o"er pol$mer micros,rc,re a(d prodci( (e
pol$mers mae ,hem as a promisi( ca,al$s, )or
"arios prposes B709C.
=oe"er% ,he homoe(eos me,alloce(e ca,a0
l$s,s ha"e some major dra-acs ,he lac o)
pol$mer morpholo$% reac,or )oli(% i(come0
pa,i-ili,$ i,h (e processes% a(d )i(all$ ,heir
e,reme co(smp,io( o) epe(si"e #A? as
coca,al$s, are o) mai( co(cer(s B1&016C. To
o"ercome ,hese pro-lems% di))ere(, approachesha"e -ee( sed% amo( hich ,he immo-ile0
>a,io( o) me,alloce(e ca,al$s, o( a sppor, has
-ee( o(e o) ,he -es, sol,io(s B17% 18C.
reser"i( ,he ad"a(,aes o) ,he homoe(eos
ca,al$s, hile ,he ca,al$s, is a(chored ,o a
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Journal of Petroleum3( Si, Silica Sppor,ed #e,alloce(e a,al$s,s G Science and Technology
Journal of Petroleum Science and Technology 2014% 41/% 2&028 h,,p:jps,.ripi.ir
2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/
/ 21
sppor, is ,he e$ poi(, hich has -ee( )ocsed
o( i( ,he las, decade.
As repor,ed i( ,he li,era,re B6%7%19C% ,he ro,e
o) a(chori( me,alloce(e ca,al$s,s a(d ,he
(a,re o) ,he sppor, pla$ ,he e$ roles i( ,heca,al$s, ac,i"i,$ a(d )i(al proper,ies o) ,he
pol$mer. There are a, leas, ,hree -asic me,hods
)or sppor,i( me,alloce(e ca,al$s,s hich
i(clde:
10
Sppor,i( ,he me,alloce(e a(d ,he(
reac,i( i,h almi(oa(e direc, me,hod/
20
Sppor,i( ,he almi(oa(e a(d ,he(
reac,i( i,h ,he me,al comple i(0
direc, me,hod/
'0
3mmo-ili>i( me,alloce(e compo(d o(
sppor, ,hroh co"ale(, ,e,hers B7%11%
2&C.
To ,he -es, o) or (olede% p ,o (o% mos,
o) a,,e(,io( has -ee( )ocsed o( )i(di( ,he
-es, sppor,i( me,hods a(d procedre
co(di,io(s B21C% hile ,he i("es,ia,io( o) ,he
e))ec,s o) ph$sical charac,eris,ics o) sppor,s
sch as sr)ace area% pore si>e% a(d pore "olme
o( ,he per)orma(ce o) sppor,ed ca,al$s,s
)orms a "er$ small por,io( o) ,hese ors B220
24C.
3( ,he prese(, s,d$% ,he i( si, impre(a,io(
me,hod as sed ,o immo-ili>e ;is20!0
i(d/<rl2!: = or he($l/ o( di))ere(, ,$pes o)
silica. ;$ si( ,his me,hod% ,he prepara,io(
complei,ies e(co(,ered i( ,he ,radi,io(al
me,hods o) sppor,i( me,alloce(e ca,al$s,s
sch as direc, me,hod% i(direc, me,hod% a(d
co"ale(, ,e,heri( me,hod ca( -e o"ercome B25%
26C. 3( ,his ,ech(ie% ,he s,ep o) ca,al$s, loadi(
o( sppor, as elimi(a,ed a(d a commo( al$l
almi(m Ti;A/ as sed i( ,he pol$meri>a,io(
B27%28C. !eardi( ,he (a,re o) ,his me,hod% ,he
e))ec, o) sppor, ,$pe o( ,he per)orma(ce o) ,he
immo-ili>ed ca,al$s, i( e,h$le(e pol$meri>a,io(
as )r,her i("es,ia,ed.
EXPERIMENTALS
Materials
Three ,$pes o) silica i(cldi( ##041% 0'&6&%
a(d E012 ere sed i( ,he crre(, or.
Spherical ##041 sppor, as s$(,hesi>ed
accordi( ,o Heooma(esh e, al. B29C 0'&6&as spplied -$ o. a(d E012 as pro"ided
-$ ross)ield o. #e,h$lalmi(oa(e #A?/ i(
,ole(e 1& ,.I/ a(d ,riiso-,$lalmi(m Ti;A/
ere spplied )rom Aldrich. ;is20!0i(d/<rl2!: =
or he($l/ as s$(,hesi>ed accordi( ,o ,he
procedre repor,ed elsehere B'&C. Tole(e a(d
hep,a(e ere dried o"er al2 -$ dis,illa,io(. All
,he ma(ipla,io( i("ol"i( air a(dor a,er
se(si,i"e compo(ds ere per0)ormed (der ,he
a,mosphere o) dried H2 i( a lo"e -o.
Support Treatment
Ta-le 1 shos ,he ph$sical proper,ies o) ,he
,hree ,$pes o) silica emplo$ed. As see( i( Fire
1 a(d Ta-le 1% ,he ##041 par,icles ere i( a
(a(o ra(e i,h a hih sr)ace area% hile ,he
si>e o) E12 a(d par,icles as i( ,he order o)
microme,er. 3( addi,io(% ,he imaes o) sppor,s
re"ealed ,ha, ,he 0'&6& a(d ##041
par,icles had a spherical shape% hile ,he
morpholo$ o) E012 as irrelar. For ,he
prepara,io( o) silica pre,rea,ed i,h #A?% )irs,
5 rams o) silica as calci(a,ed (der ,he
a,mosphere o) H2 a, 25& J )or 5 hors. The(% 1
ram o) ,he deh$dro$la,ed silica as ss0
pe(ded i( ,ole(e. A),erards% 4 ml o) #A? 1&
,.I i( ,ole(e/ as added ,o ,he sspe(sio(
a(d s,irred o"er (ih,. Fi(all$% ,he silica as
ashed i,h ,ole(e a(d hep,a(e )or ,imesa(d ,he )i(al sspe(sio( as sed as ,he
sppor, i( ,he pol$meri>a,io( s,ep.
Polymerization
E,h$le(e homopol$meri>a,io( as carried o, i(
a 10li,er ;chi reac,or ;chilas,er -md '&&/
eipped i,h )ll$ co(,rolled s$s,ems o) ,emp0
era,re% s,irri( speed% reac,io( pressre% a(d
mass )lo o) mo(omer. n0=ep,a(e as
i(,rodced i(,o ,he reac,or 4&& ml/ a(d as
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Journal of Petroleum
Science and Technology S. Ahmadjo% =. Ara-i% Kh. =. <ohri% Kh. !. Heja-a, e, al.
Journal of Petroleum Science and Technology 2014% 41/% 2&028 h,,p:jps,.ripi.ir
2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/
22 /
sa,ra,ed i,h e,h$le(e a, ,he reac,io( ,emp0
era,re. Ti;A as a sca"e(er/% #A?0modi)ied
silica% a(d ,he ca,al$s, sol,io(s ere added
respec,i"el$. A, ,he e(d o) ,he pol$meri>a,io(
mai(l$ a),er '& mi(/% ,he co(,e(, o) ,he reac,oras pored i(,o a( ecess amo(, o) me,ha(ol%
)olloed -$ )il,eri( a(d dr$i( o"er(ih,.
igure 1 S) images of the supports3 a5 P6$,070
magnification of 40853 "5 P$12magnification of
100853 c5 )C)$41 magnification of 2000859
Ta"le 1 Te:tural properties of the supports
Silica Surface aream
29gr9
$15
Pore +olumecm
,9gr9
$15
Pore diameternm5
E12 '9& 1.75 18
'&6& 57& '.&& 21
##041 11&& &.5& 2
Characterization
For measri( ,he sr)ace area o) ,he silica sam0
ples% ,he$ ere o,assed 1&02
m-ar/ a, 8& J
)or a, leas, 8 hrs. Adsorp,io(0desorp,io( (i,ro0e( iso,herms ere recorded a, L196 J i( a
Kemi(i 2'75 #icromeri,ics% Horcross% .S.A./.
Speci)ic sr)ace areas ere de,ermi(ed -$ ,he
;r(aer0Emme,,0Teller ea,io( PP&M&.&50&.'5/%
hile ,he pore "olmes a(d pore diame,ers
ere de,ermi(ed i,h ,he ;are,, *o$(er
=ale(da ;*=/ me,hod. The mel,i( poi(, o) ,he
pol$mer as measred si( S N model STA
78&/ a(d Al co(ce(,ra,io( as measred -$
i(dc,i"el$ copled plasma 3/ model 7'50ES
Oaria( o./. Fi(all$% ,he morphol0oies o) ,he
sppor,s a(d pol$e,h$le(e samples ere
mo(i,ored -$ a sca((i( elec,ro( microscope
OEKA E#3TE= P45&Q% >ech !ep-lic/ a),ercoa,i( ,he samples i,h a ,hi( la$er o) old.
RESULTS AND DISCUSSION
Effect of Polymerization Conditions on
the Performance of Bis(2-R-ind)ZrCl2 (R:
H or, Phenyl) /SiO2 (PQ 3060)
The resl,s prese(,ed i( Ta-le 2 sho ,he
depe(de(ce o) pol$meri>a,io( -eha"ior o(
reac,io( ,empera,re a(d mo(omer co(ce(,ra0,io(. The lo ac,i"i,ies a, ,empera,res a-o"e
6& J ca( -e a,,ri-,ed ,o ,he i(crease o)
deac,i"a,io( ra,e co(s,a(,s a(d% co(see(,l$%
,he deac,i"a,io( o) ac,i"e si,es pro-a-l$ -$
cha(i( ,heir s,rc,re B'1% '2C. A hiher
ca,al$s, ac,i"i,$ as o-,ai(ed a, hiher
mo(omer pressres i, ca( -e s,a,ed ,ha, -$
i(creasi( ,he pol$meri>a,io( pressre ,he
mo(omer co(ce(,ra,io( i(creased i( ,he reac0
,io( medim% hich led ,o a rise i( ,he prodc,0
i"i,$ o) ,he s$s,em B''0'5C. These resl,s also
i(dica,e ,ha, ,he ac,i"i,ies o) ,he sppor,ed
ca,al$s,s are loer compared ,o homoe(eos
co(,erpar,s i,h a redc,io( o) #A? co(smp0
,io(.
Fires 2 a(d ' sho ,he e))ec, o) pol$meri>e0
,io( ,empera,re a(d e,h$le(e pressre o(
pol$meri>a,io( ra,e respec,i"el$. As see(% ,he
i(e,ics o) ,he sppor,ed ca,al$s,s are s,ill o) ,he
deca$ ,$pe% hich is re)lec,ed i( ,he deca$ i(de
31/ resl,s Ta-le 2/.
=oe"er% ,he co("ere(ce o) 3 "ales ,oard
(i,$% i( compariso( ,o homoe(eos ca,al$s,s%
co()irms ,he i(creased ca,al$s, s,a-ili,$. This
impro"eme(, ca( -e a,,ri-,ed ,o ,he elimi(a0
,io( o) -imoleclar deac,i"a,io( -$ sppor,i(
,he ca,al$s, B'6%'7C.
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Journal of Petroleum3( Si, Silica Sppor,ed #e,alloce(e a,al$s,s G Science and Technology
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2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/
/ 2,
Ta"le 2 thylene polymeri'ations using P6$,070 silica supported catalyst
Type of catalysta Catalyst mol5 ;Al<)A;%r< Pressure "ar5 Tp =C5 Acti+ity >g P?mol %r9hr55 @
"
1 A 'R1&06
4&&:1 4 5& 5867 '.&
2 A 'R1&06
4&&:1 4 6& 7''' 2.'
' A 'R1&06 4&&:1 4 7& 65'' 2.7
4 A 'R1&06
4&&:1 4 8& 4''' 2.5
5 A 'R1&06
4&&:1 6 6& 1&667 2.7
6
Ao 1R1&06
5&&&:1 6 6& 4&&&& 8.6
7 ; 6R1&06
4&&:1 6 6& 27&& '.'
8 ; 6R1&06
4&&:1 6 7& '&'' 0
9 ; 6R1&06
4&&:1 6 8& 18'' 0
1& ;o 'R1&06
2''':1 6 6& 1&8&& 1&
ol$meri>a,io( co(di,io(s: ,imeM '& mi( (0hep,a(eM4&& ml BTi;ACM1.5 mmol as a sca"e(er/.a T$pe A: ;is3(d<rl2Si?2 /% Ao: ,he homoe(os )orm o) A% ,$pe ;: ;is2h3(d<rl2Si?2 /% ;o: ,he homoe(os
)orm o) ;.- 3: deca$ i(de: R p a, maimmR p a, ,he e(d o) reac,io( 3M R pmaimm/R p'& mi(//
igure 2 -inetic profiles of ethylene polymeri'ation
.ith Bisnd%rCl2?Silica P6$,0705 sho.ing the effect
of polymeri'ation temperature
The morpholo$ o) pol$mer par,icles depic,ed i(
Fire 4 shos ,ha, ,he sppor,ed ca,al$s,
prodces spherical pol$mer par,icles% replica,i(
,he i(i,ial shape o) sppor, par,icles ,his is i(
accorda(ce i,h ,he replica,io( phe(ome(o(
a(d (o e"ide(ce o) reac,or )oli( ca( -e )o(d
B21%'8%'9C. 3( co(,ras,% ,he shape o) ,he pol$mer
prodced -$ ,he homoe(eos ca,al$s, as
comple,el$ irrelar.
Effect of Polymerization Conditions on the
Performance of Bis(2-R-ind)ZrCl2 (R:H or
Phenyl)/SiO2 (MCM-41)
The pol$meri>a,io( resl,s ,a-la,ed i( Ta-le '
clearl$ i(dica,e ,he impro"eme(, achie"ed i(
,he per)orma(ce o) ,he immo-ili>ed ca,al$s, -$
si( ##041 as a sppor,.
igure , -inetic profiles of ethylene polymeri'ation
.ith Bisnd%rCl2?Silica P6$,0705 sho.ing the effect
of monomer pressure
3 "ales sho ,ha, ,he ca,al$s, sppor,ed o(
##041 is s,a-ler ,ha( ,he o(e sppor,ed o(
'&6&. 3( o,her ords% -$ cha(i( ,he ,$pe o)
,he sppor,% ,he i(e,ic cr"es ere shi),ed
)rom deca$ ,$pe ,o s,a-le ,$pe. =oe"er% ,he
morpholo$ o) pol$mer par,icle as irrelar%
hich as pro-a-l$ de ,o ,he (a(o si>e o) ,he
sppor, par,icles casi( pol$mer par,icles ,o
alomera,e B29C.
time s5
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Journal of Petroleum Science and Technology 2014% 41/% 2&028 h,,p:jps,.ripi.ir
2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/
/ 2
accessi-ili,$ o) ?= rops o) ,he sppor, rises
a(d% co(see(,l$% ,he pro-a-ili,$ o) loadi( Al
is e(ha(ced.
Ta"le 4 Al contents determined "y CP
Type ofSupport
nitial Aluminummmol9gr9 silica
$15
Doaded Al.t9E5
0'&6& ' 00
0'&6& 6 9.1
0'&6& 12 12.2
##041 ' 5.2
##041 6 9.5
##041 12 1'.6
Ta-le 5 shos ,ha, ,he sr)ace area ca( pla$ a
e$ role i( ,he per)orma(ce o) ,he ca,al$s,. 3,
as o-ser"ed ,ha, he( ,he sr)ace area o) ,he
ca,al$s, as i(creased% ,he ac,i"i,$ o) ca,al$s,
as raised ,oo% si(ce i, i(creased ,he pro-a-ili,$
o) co(,ac, -e,ee( ac,i"e ce(,ers a(d sp0
por,ed #A? B41C. (do-,edl$% ,he hiher
s,a-ili,$ o) ,he i(e,ic pro)ile o) ,he ca,al$s,
sppor,ed o( ##041 Fire 6/ ca( -e rela,ed
,o ,he -e,,er accessi-ili,$ o) ,he ac,i"e ce(,ers
dri( pol$meri>a,io(. 3, seems ,ha, i( ,he i(
si, sppor,ed ca,al$s,s (e ca,al$,ic si,es are
co(,i(osl$ )ormed o( ,he e,er(al sr)ace o)
,he silica par,icles -$ ,he a-sorp,io( o) ,he
ca,al$s, compo(ds hich are a"aila-le i( ,he
liid phase dri( pol$meri>a,io( B42C. The
s,dies o) Soa B4'C a(d Da(e B24% 44C ha"e
co()irmed ,he domi(a(, role o) ,he pore "olme
o) sppor, o( ca,al$s, ac,i"i,$% hereas ,he
e))ec, o) sr)ace area has (o, -ee( ,ae( i(,o
acco(,. The impor,a(ce o) ,he sr)ace area-ecomes more domi(a(, i( ,he i( si, im0
pre(a,io( me,hod i( compariso( ,o ,he
,radi,io(al ,ech(ies% si(ce ,he co(,ac, ,ime
-e,ee( ,he ca,al$s, species a(d ac,i"a,ed
sppor, dras,icall$ decreases.
Ta"le ffect of surface area on the performance of Bisnd%rCl2 catalyst in ethylene polymeri'ation
Type of support
Surface area
m29gr9
$15
Acti+ity
>g P9mol %r9hr5$1
5
T m =C5 Crystallinity E5
E012 '5& 17&& 1'6.5 0000'&6&
57& 57&& 1'8.1 51.2
##041 11&& 11'&& 14&.4 55
ol$meri>a,io( co(di,io(s: =ep,a(eM4&& ml BAlTi;ACM2 mmol as a sca"e(er/ M6 -ar BAl#A?CB<rCM12&:1 B<rCM1R1&05
mol
igure 7 ffect of the type of support on the >inetic
profiles in the polymeri'ation of ethylene
CONCLUSIONS
The e))ec,s o) pol$meri>a,io( co(di,io(s a(d
sppor, speci)ica,io(s o( 3(de($l0-ased sppor,ed
me,alloce(e ca,al$s,s ere i("es,ia,ed. The
;is3(d<rl2Si?2 / sp0por,ed ca,al$s, shoed
,he hihes, ac,i"i,$ 1&&&& Emol <r.hr// a,
6& J a(d 6 -ar. The ca,al$s, i,h s-s,i,,ed
i(de($l lia(d 20 phe($l i(de($l/ shoed a loer
ac,i"i,$ '&&& Emol <r.hr.// ,ha( i,s (o(0
s-s,i,,ed co(,erpar,. The morpholo$ o)pol$mer par,icles as impro"ed a(d reac,or
)oli( as elimi(a,ed -$ sppor,i( ,he ca,al$s,.
3, as o-ser"ed ,ha, ,he co(smp,io( o) #A? as
decreased -$ sppor,i( ,he ca,al$s, ,he ra,io o)
Al ,o <r BAlC:B<rC/ decreased )rom 5&&& ,o loer
,ha( 5&&. The ac,i"i,$ o) ;is3(d<rl2 ca,al$s,
sppor,ed -$ ,he i( si, impre(a,io( me,hod as
i("es,ia,ed si( ,hree ,$pes o) sppor,s. The
;is3(d<rl2##041 shoed ,he hihes, ac,i"i,$%
hich as ,ice as lare as ,he 0'&6& a(d E012
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Journal of Petroleum
Science and Technology S. Ahmadjo% =. Ara-i% Kh. =. <ohri% Kh. !. Heja-a, e, al.
Journal of Petroleum Science and Technology 2014% 41/% 2&028 h,,p:jps,.ripi.ir
2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/
27 /
sppor,ed ca,al$s,s. ##041 sppor, -$ ,he
sr)ace area o) 11&& m2.r.
01 shoed a ca,al$s,
ac,i"i,$ o) 11.' Emol <r.hr//% hile ,he micro0
si>ed sppor,s% (amel$ 0'&6& a(d E012% i,h
,he respec,i"e sr)ace area o) 59& a(d '9& m2
.r.01
shoed a ca,al$s, ac,i"i,$ o) 5.6 a(d 1.7
Emol <r.hr// respec,i"el$. 3, as co()irmed ,ha,
,he sr)ace area o) ,he sppor, had ,he mos,
crcial e))ec, o( ,he per)orma(ce o) ,he i( si,
sppor,ed ca,al$s,s. This -eha"ior ca( -e a,,ri-0
,ed ,o ,he decreased co(,ac, ,ime dri( ca,al$s,
impre(a,io( i( ,his me,hod% hich ampli)ies ,he
impor,a(ce o) ,he pro-a-ili,$ o) ,he co(,ac,
-e,ee( ca,al$s, compo(ds a(d ,he e,erior
po,e(,ial impre(a,io( si,es.
NOMENCLATURE
;*= ;are,, *o$(er =ale(da
;is3(d<rl2 ;isi(de($l/>irco(imdichloride
;is2h3(d<rl2 ;is20phe($l i(de($l/>irco(im
dichloride
3 eca$ i(de
3 3(dc,i"el$ copled plasma
#A? #e,h$l almi(imoa(eTi;A Triiso-,$lalmi(m
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Journal of Petroleum3( Si, Silica Sppor,ed #e,alloce(e a,al$s,s G Science and Technology
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B16C
#ares #. F. O. a(d o(,e A.% The
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Si?20 a(d <r?20sppor,ed <irco(oce(e
#A? a,al$s,s o( E,h$le(e10ole)i( o0
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Z0ole)i(s o( Kas0phase E,h$le(e ol$0
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ol$meri>a,io( o"er a Ha(o0si>ed Silica
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B2&C aredes ;.% Soares *. ;. .% Kriee( !. O.%
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E,h$le(e010hee(e opol$mers #ade
i,h Sppor,ed #e,alloce(e a,al$s,s:
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sppor,ed #e,alloce(e#A? a,al$s, i(
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Macromol .% 200% 3'% 467'04678.
B22C Do(aia,,a(al . a(d *o(somji, ;.%
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opol$meri>a,io( o) 10hee(e a(d
E,h$le(e i( ,he Kas hase i,h (0
;p/2<rl2 o( Sppor,s i,h i))ere(,
ore Si>es%X Polymer % 200,% ""% 47910
48&'.
B25C Sil"eira F.% Al"es #. . #.% S,edile F. .%
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B26C
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B27C
Fra(ceschi(i F. .% Ta"ares T. T. !.% Sa(,os
*. =. <.% Soares *. ;. .% e, al.% ompara,i"e
S,d$ o) rop$le(e ol$meri>a,io( si(
#e2Si!3(d/2<rl2Si?2eS#A?Al!' a(d
#e2Si !3(d/2<rl2#A? !M#e%=/%X Poly
mer % 200G% "'% 194&0195'.
B28C
Fra(ceschi(i F. .% Ta"ares T. T. !.% Kreco
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B29C
Heooma(esh #.% Ara-i =.% Heja-a, K. !.%
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#or,a>a"i #. #.% Ara-i =.% <ohri K. =.%
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Journal of Petroleum
Science and Technology S. Ahmadjo% =. Ara-i% Kh. =. <ohri% Kh. !. Heja-a, e, al.
Journal of Petroleum Science and Technology 2014% 41/% 2&028 h,,p:jps,.ripi.ir
2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/
2F /
opol$meri>a,io( si( a ;is03(d<rl2
#e,alloce(e a,al$s,: S,rc,ral omposi0
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Macromol. React. )ng.% 2011% 3% 26'027&.
B'1C os Sa(,os *. =. <.% Dilliams !. *. *.% Fasce
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E,h$le(e ol$meri>a,io( o(di,io(s o(
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B'2C Qiao Q.% S( *.% Ni Q.% Da( Y.% e, al.%
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;rided ,ri0 a(d Te,ra(clear Ti,a(o0
ce(e#A? S$s,ems%X )ur. Polym. J.% 200G%
"3% 1640171.B''C #a N.% She( Y.% =( .% <hao Y.% e, al.%
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a,al$s,s )or E,h$le(e ol$meri>a,io(%X J.
Polym. Sci. Part A: Polym. Chem.% 200F%
"6% ''0'7.
B'4C
;ers,ra #. F. a(d Deicer, K.% E,h$le(e
ol$meri>a,io( Pi(e,ics i,h a =e,ero0
e(eos #e,alloce(e a,al$s,0compari0
so( o) Kas a(d Slrr$ hases%X Macromol.
Mater. )ng.% 200% (*% 61&062&.
B'5C
Sha( . N. .% Soares *. ;. .% a(d e(lidis
A.% E,h$le(e10oc,e(e opol$meri>a,io(
S,dies i,h 3( si, Sppor,ed #e,allo0
ce(e a,al$s,s: E))ec, o) ol$meri>a,io(
arame,ers o( ,he a,al$s, Ac,i"i,$ a(d
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Part A: Polym. Chem.% 2002% "*% 44260
4454.
B'6C
Ad>a *. A. #. a(d Tai, . *. T.% The
Uomo(omer E))ec,V i( E,h$le(eZ0ole)i(
opol$meri>a,io( si( =omoe(eos
a(d Silica0sppor,ed p2<rl2#A?
a,al$s, S$s,ems: Some 3(sih,s )rom ,he
Pi(e,ics o) ol$meri>a,io(% Ac,i"e e(,er
S,dies% a(d ol$meri>a,io( Tempera0
,re%X J. Polym. Sci. Part A: Polym. Chem.%
200F% "6% 2670277.
B'7C Da( D.% Da( N.% Da( *.% #a <h.% e, al.%
S,d$ o( E,h$le(e co/ol$meri>a,io(
a(d i,s Pi(e,ics a,al$>ed -$ a !e"ersi-le
rossli(ed ol$s,$re(e0sppor,ed #e,al0
loce(e a,al$s,%X J. Appl. Polym. Sci .% 200%
($ % 16'2016'6.
B'8C ash,i A.% !ama>a(i A.% =iraoa Y.% Pim
SY.% e, al.% Pi(e,ic a(d #orpholoical
3("es,ia,io( o( ,he #a(esim E,hoide0
-ased <ieler Ha,,a a,al$s, )or rop$le(e
ol$meri>a,io( si( T$pical E,er(al
o(ors%X Macromol. Symp.% 200H% '!% 520
57.
B'9C Ahmadi #.% *amjah !.% Heooma(ehs #.%
<ohri K. =.% e, al.% <ieler0Ha,,a
#e,alloce(e =$-rid a,al$s, )or E,h$le(e
ol$meri>a,io(%X Macromol. React. )ng.%
200G% % 6&4061&.
B4&C oa,es K. D. a(d Da$mo,h !. #.%
?scilla,i( S,ereoco(,rol: a S,ra,e$ )or
,he S$(,hesis o) Thermoplas,ic Elas,o0
meric ol$prop$le(e%X Science.% 1HH% 6$ %2170219.
B41C ;ram-illa !.% !ad,e .% S,edile F. .% os
Sa(,os *. =. <.% e, al.% #e,alloce(e
a,al$s, Sppor,ed o( Silica[ma(esia
Qeroels )or E,h$le(e ol$meri>a,io(%X
Appl. Catal. A: -en.% 2010% 3'% 1&60114.
B42C
Nee =. D.% Ah( S. =.% a(d ar Y. =.%
opol$meri>a,io( harac,eris,ics o)
=omoe(eos a(d 3( Si, Sppor,ed
B=2/55=4/2CB9=7/<rl2C2 a,al$s,%X J.
Mol. Catal A: Chem.% 200,% ("%19028.
B4'C
Sa(o T.% =aimo,o =.% Smi$a S.% Hai,o Y.%
e, al.% Applica,io( o) oros 3(ora(ic
#a,erials ,o Adsorp,i"e Separa,io( o)
#e,h$lalmoa(e sed as o0ca,al$s, i(
?le)i( ol$meri>a,io(%X Micoropor.
Me&opor. Mat .% 2001% """!% 5570564.
B44C
Pmae .% Da(e S. E.% raser,hdam .%
a(mah .% e, al.% !a,es a(d rodc,
roper,ies o) ol$e,h$le(e rodced -$
opol$meri>a,io( o) 10hee(e a(d
E,h$le(e i( ,he Kas hase i,h (0
;p/2<rl2 o( Sppor,s i,h i))ere(,
ore Si>es%\ J. Appl. Polym. Sci .% 200,% '$ %
116101177.