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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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/ 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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Science and Technology S. Ahmadjo% =. Ara-i% Kh. =. <ohri% Kh. !. Heja-a, e, al.



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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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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/ 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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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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a(d =ih0pressre E,h$le(e ol$meri>a0

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B4C hadic *. .% cha,ea !.% Freia <.%

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B5C

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#e(ehe,,i S. #. .% a(d #e(ehe,,i #.

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Aspec,s o) #e,alloce(e a,al$s, S,a-ili>a0

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B7C

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Ac,i"a,io( a(d eac,i"a,io( o) #e,allo0ce(es dri( ,he ol$meri>a,io( o)

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B1&C ;(cho(,raar( S.% *o(somji, ;.% a(d

raser,hdam .% 3mpac, o) ;imodal ore

##0410Sppor,ed

<irco(oce(e##A? a,al$s, o( opol$0

meri>a,io( o) E,h$le(e10oc,e(e%X Catal.

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B11C

Kriee( !. O.% arrero A.% Sare> 3.% a(daraedes ;.% E,h$le(e ol$meri>a,io(

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B12C Smi, #.% <he( Q.% Noos *.% hadic *. .%

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3mmo-ili>a,io( o( Silica o( ,he er)or0

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B1'C

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8/11/2019 02 1055 rev. 5 ver 2.0.0





/ 2G

E,h$le(e ol$meri>a,io( i,h Silica0

sppor,ed Hicel0diimi(e a,al$s,: E))ec,

o) Sppor, a(d ol$meri>a,io( o(di,io(s

o( a,al$s, Ac,i"i,$ a(d ol$mer roper0

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Pam)jord T. =.% Des,er T. =. S.% a(d !$,,er

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repared -$ 3mpre(a,io( o) #A?

#odi)ied Silica -$ a #e,alloce(e

#o(omer Sol,io(%X Macromol. Rapid.

Commun.% 1HHF% (% 5&505&9.

B15C

*o(somji, ;.% Hamposri S.% a(d

raser,hdam .% a,al$,ic Ac,i"i,$ ri(

opol$meri>a,io( o) E,h$le(e a(d 10

=ee(e Oia #ied Ti?2Si?20Sppor,ed

#A? i,h !ac0E,B3(dC2<rl2 #e,alloce(ea,al$s,%X Molecule&.% 200% *% 6720678.

B16C

#ares #. F. O. a(d o(,e A.% The

3()le(ce o) ,he repari( o(di,io(s o)

Si?2 Sppor,ed p2<rl2 a,al$s, o(

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B17C o,hira, T.% *o(somji, ;.% a(d

raser,hdam .% ompara,i"e S,d$ o)

Si?20 a(d <r?20sppor,ed <irco(oce(e

#A? a,al$s,s o( E,h$le(e10ole)i( o0

pol$meri>a,io(%X Catal. Comm.% 200F% (%

1426014'1.

B18C =ammaa =. a(d Da(e S. E.% 3()le(ce

o) Sppor, Fria-ili,$ a(d o(ce(,ra,io( o)

Z0ole)i(s o( Kas0phase E,h$le(e ol$0

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B19C Ni P. T.% ai . N.% a(d Po . D.% E,h$le(e

ol$meri>a,io( o"er a Ha(o0si>ed Silica

Sppor,ed p2<rl2#A? a,al$s,%X Catal.Comm.% 200G% '% 12&90121'.

B2&C aredes ;.% Soares *. ;. .% Kriee( !. O.%

arrero A.% e, al.% harac,eri>a,io( o)

E,h$le(e010hee(e opol$mers #ade

i,h Sppor,ed #e,alloce(e a,al$s,s:

3()le(ce o) Sppor, T$pe%X Macromol.

Symp.% 200G% !$ % 1&'0111.

B21C <he( Q.% Smi, #.% hadic *. .% a(d

Noos *.% Frame(,a,io( ;eha"ior o) Silica0

sppor,ed #e,alloce(e#A? a,al$s, i(

,he Earl$ S,aes o) ?le)i( ol$meri>a,io(%X

Macromol .% 200% 3'% 467'04678.

B22C Do(aia,,a(al . a(d *o(somji, ;.%

opol$meri>a,io( o) E,h$le(e10oc,e(e

"ia i))ere(, ore Si>ed Silica0-ased0

sppor,ed <irco(oce(ed##A? a,a0

l$s,s%X Catal Comm.% 200F% *% 1180122.B2'C Fra(ceschi(i F. .% Ta"ares T. T. !.%

;ia(chi(i .% Al"es #. . #.% e, al.%

harac,eri>a,io( a(d E"ala,io( o) Sp0

por,ed !ac0dime,h$lsil$le(e-is i(de($l/

>irco(im ichloride o( E,h$le(e ol$0

meri>a,io(%X J. Appl. Polym. Sci .% 200H%

% 56'0571.

B24C Pmae .% D N.% raser,hdam .% a(d

Da(e S. E.% !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%X Polymer % 200,% ""% 47910

48&'.

B25C Sil"eira F.% Al"es #. . #.% S,edile F. .%

erher S. ;.% e, al.% E))ec, o) ,he Silica

Te,re o( ,he S,rc,re o) Sppor,ed

#e,alloce(e a,al$s,s%X J. Mol. Catal. A:

Chem.% 200H% ('% 4&05&.

B26C

Sil"eira F.% e,r$ . F.% o>e-o( .% erherS. ;.% e, al.% Sppor,ed #e,alloce(e o(

#esoporos #a,erials%X Appl. Catal. A:

-en.% 200G% 333% 9601&6.

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

. .% ;ia(chi(i .% e, al.% ol$prop$le(e?-,ai(ed i,h 3( Si, Sppor,ed #e,allo0

ce(e a,al$s,s%X J. Mol. Catal. A: Chem.%

200,% *% 12701'4.

B29C

Heooma(esh #.% Ara-i =.% Heja-a, K. !.%

Emami #.% e, al.% repara,io( o)

ol$e,h$le(e Ha(o)i-ers si( !od0lie

##041Til4#l2T=F ;i0sppor,ed

<ieler0(a,,a a,al$,ic S$s,em%X #. J. Polym.

Sci. Tec.% 200F% 3% 24'025&.

B'&C

#or,a>a"i #. #.% Ara-i =.% <ohri K. =.%

Ahmadjo S.% e, al.% E,h$le(e =omo0 a(d

8/11/2019 02 1055 rev. 5 ver 2.0.0






2F /

opol$meri>a,io( si( a ;is03(d<rl2

#e,alloce(e a,al$s,: S,rc,ral omposi0

,io( is,ri-,io( o) ,he opol$mer%X

Macromol. React. )ng.% 2011% 3% 26'027&.

B'1C os Sa(,os *. =. <.% Dilliams !. *. *.% Fasce

. .% ellEr-a 3. E.% e, al.% E))ec,s o)

E,h$le(e ol$meri>a,io( o(di,io(s o(

,he Ac,i"i,$ o) Si?20sppor,ed <irco(o0

ce(e a(d o( ol$mer roper,ies%X J.

Polym. Sci. Part A: Polym. Chem.% 1HHH%

3$ % 198701996.

B'2C Qiao Q.% S( *.% Ni Q.% Da( Y.% e, al.%

E,h$le(e ol$meri>a,io( i,h Ho"el

;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.%

A Pi(d o) Ho"el Ho(me,alloce(e

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

ol$mer #icros,rc,re%X J. Polym. Sci.

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.

02 1055 rev. 5 ver 2.0.0

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