of ortanometalli. vanadium catalyst for ethylene polymerization

lUM-7l oG' H '', łm.'ccz,Ą],Ą '\AT^lI^\U'KoVĄlF\A
Silica powder obtained bysol-8el metho.l as a support
of ortanometalli. vanadium catalyst for ethylene polymerization
RAPID COMMUNICATION
sumnary Sol gcltc.hniquc was enployed roobbin thc ili.i,iy p. pow
d.i vhich aftcl nrodjfi.iiion proredure was aPPlicd a suppoł 01Ór
ganondi]li. c ilyiic syśen for rdlylĆne polyń iz iol Tlt powds PrG
s
dud lvis synlhcsju.d usins hydblysis ańd condcnsation 01TEos, rhl],zcd
by mmoi.' obbin€d młłial and a Ęfer.Dc suPpolt (.omnelciil
Davisil) lvere d'aradd]zed lo deiemmc thef Palticl€ si? dishńutjons, 'lrc
BET
surla.e al.a, porc voluńc and diamcie. Gis.phase adsorption of Vanadju
cłblyśoń'nalyzcdsuPPo m eliłhaswPllasadsorPiionhonthesolution
atrił mabria ls wcrc ihem a lly pret.a lod
sy9ems
syntlrcas
and
thĆ innucn.c ol modjfi.atnrn ńethod
Pnor.ih]vti.
apPlild on rr llins ol8anońctallic c alyś.hiracfu wa5 $titahd in lowPr*slte slufy Polvńdizahon ot cihylcn.' obhimd l$ul6 Prov. dttsol.
gel ńabńal' duc to its advinbgeous moĘhologv Wth widc łnd shal]o\'
Pl[cs, allows b obhin cahlytic sydons o1lĘher adiYity in low_preŚue
ethy lcn. polymcńz.iion, in conPa dsol wi lh Ćońn {cń l sili.a Davis il '
(eywods: si]i.i suPPo ] sol*ol fuĆhni']ug' dhylcnc
Polymerizaiion' slp
po cd vinidn'm c ł1!d, sup pon porÓls stuĆfu lc
o€ahońctalli. calal],iic syshms fol ethylene polynltizahon rnd .opo\'nniz ion requir. bein8 hebro
lencous io. łpPli.łtion in nod.rn 8as Pha* ińdustial
PlJnb' Fu honore ld.rogenj5liÓn slvs ihc Posibi
lily lo reBuhh PÓlym.r produd ńorPho]ogyas i IGuh
oI "repli.atioi" Fhcnonrcm, wli.h o(ur dudng poly
nd Pa i.le gloNlh l1l $'ppoń mafuri^IŚ ńasn+
siuń dthlodde l2_5l and^soxide tyPe .ońFunds Gili
.ł or alunDa) a.c widcl], usc'l' ho
Rch.vior of suppo ed cablyti. !yś.ńdcPc|ds on
rie! Physical and .hemi.al proPeti.s a5 wcll For
cxamplc oxidełype makriól ńe.dś b b. todilieij io
Ć
pclrcial hydtoxyl gnuF, LvharĘ add jhonshould if'ect
thc a.hvity oI suPPołcd di'lyuc sy*cm and popełies
ply ptm.durc, dĆPlndins ol s'l
lo\fs lÓ obiiin ihe Pto]tkb th cJn
Iom lsl SiartitrE rrith. hosil(aic
cthylo hosili.at (TEos),lhc lib s, glłscs' ihin layere
and bulk powdcc Gn be produccd, where rhe powder
s!.ms tob.mo us€lul forn f.r olganoń&llic Ć alyst
Wc have łpPli.d ńenńoncd sn_gcl tc.hnĘuc to Pro.
duc. su@Śfun' 5ili.a tyP. Powdc. R..ovcd mric al
.nd conm.rcial sili(a (for cońPaljson) wcrc used in
slppo ed vanadlum ..tilvn plcp łtion by vocL
Prmursol 'l€posi&i Fgn'ncd ln gayphasc adsorption .nd sllEy inprcgn ion. suppo cd vanadium
catalyśs altel achvrhon wiih die
ride werc uscd m low.preŚUre polynerization ÓI ethy
LoÓkińg lor ncq .hloridc 1ree ofies we havc aP
plied a podld of i .ommon sol sr
Etl'ylĆńc for Polymcrization
try PKN orl.n'
slFpo{and caialyti. systum
glłdi delilelcd
_
tbżdhylorthosil jcżt oEos, >93 1', f luka)'
żńńonla (aqufuus 25 ?,,lloch cljwrc),
vamdium oxyticl o dc (Voclr,99 9l, Aldrió),
diet]rylalumi'n'n.hlorid€ (A]Et:cl, soIJtion jn
(c'adc6ł,, Aldnch)
was
!scd.
PleParalion lnd chandeńzltion of
c
Mclhng poinh and tne deErces oi -y*rlliriiy of
Polym$s włe meaŚlred by diffclcnti'lscrnnin8 dlo_
rimetry rcinE TA lnshmenb 2010 Dsc calorimehr ar
d'eheatinglatc10d%/nin Folyherpałi.l.siuedjsbi
bution was dd.rnined uŚing Fri
shakcr with setÓnprising lr sievs va.yins trcm 0'06]
alysb
An opetaiio'T, .i..pt fol sol8el ńaterial syńthesis,
lvele PłiÓmed lndd dty and o
mdlPh.rc' The PfuceduĘ of solE
was tak.n lrom th. htcIJfuro whcrc olloidłl siIio_gel
slspcnsion was obtiircd is i fir* śePin ligh taBpa
rcncy gla$ prcdudion l9l' W el, ]acE' edmnol GÓl
vcno ]d łmmonii kaiilyś) woe mixed iogethet in
molar mtios.15:]:ó:007 and *nte
powd.r prÓd!.t lvas obtaincd by
AFplicd cioic. maicriik wcrc nrodifi.d by anneal
ins rhcn at tcmpcnrurc 200 or 300
ahosphc,ca'lt rhcn foL r hour in argon.
Pa iclcsizcdisbibuiion was deter
sili.a pol'd$ obtłined by sol*cl svnlhesis showŚ
Pa i.le siŻe distibulion wjth don
sion about 5-20 !n (Fis. l). Taken as rcacrcn.c sample
.onńercial Davisil siliĆa exhibi6 "bulk}'" djstibution
włh thc hjghe*.Óntib!rjon of Patlclcs r.n]iing
]00_200 |'m Th!5 gńndmg of DaYńil nr ballnill Mś
app]ied io aPProich desned powder size .omF6jńon
(Era nulation) Hence fuo
PowdĆr natrials of grain dia'
meter aDund 10 !m wł. obianrcd, howcvs Davisil
wassli8htlyshifkd bla4e!dńmclcr (Fir ]).
bibuuoN ot $,P.
poł matrriarś Wdc d.bmincd usnrg nltogcn.dso+}
dolbyMiĆtomebińs A5A! 2000 j
Tr,unal anarysis of suppon simplcs rns pcrforned
chcm]sorPiionof voclr onsJPPÓrr5urfa.e Was rcal.
izcd by su.msivg inEddldif of.atalyś onpon.n6
(vocl]and then AlEĘcl) Iroń gżs Phasc łnd conbol of
ilre amounh ÓI .heńjcżlly adsorbcd .ompounds usińs
suPPo cd otilyśslor slury Po
prcParcd by reł.tion oI th.mally PĘbc cd suPPo
wilh voclr in hexanc ł bon lcńPcrafurc ltc.cLd
supporbd Plełalys Waswashcd with hexane (5! 20
mL), dri.d ald dEPcĘcd jn solvcni a8ah Amount of
adsorb.d voclr wis detemimd by abmi. absoęlion
sPrbo{oPy (^^s) using solłłA]\s sPedloneie.
j,r
t,
Fi! r'
Pl idl
sźl l1iłribuliar aJ srlta prŁdłlj ]
pnrdn|l)1;lrr*,1 ltb Dn&iI,3
illł1 Dlllil
Jł!'
Bolh obhined powds Batcn.L \!crc ch acbr'łl
usinE low i.nPcEforc nibogen a{isoĘiion' Re lis ol
rolymel Śynlhesis d tcstinB
su acc inv.sdsations show that raw poLvdlr synrhc
sjz€'l by sol gcl tehni']ue shows
Polymeriz ion pi&cs5 wds .a(,cd out ir Bii.hi
rd Śmallm Pore vÓlLn. and dńD.l.r m comP ison
rcactor,
ilr
h.xanc
5ltrry
45
t
and
under.on
l'itn
cońmcrbl Davilil (Tablc 1) cnnding opcntiol
8laŚ
śant.thyl.ncPrsslrc(0'5MPł)'Thcpre.łblyśsluEy rppkd lorDavGiland Iolowirg cal.inarion in200,'c
w a.tilatślby iddihon of orEa
kccps thes. propcriis alnci un.hangod, conbary ro
]yś(AlEi2cl)' Rcłction wm initialed by ińboducln8 sol.gcl powdeł thi.h dcmonśiłh
cihylcnc łnd qnenched afl.r 30 ńin by iddition of surfacc areł dtoP rd conlenpola
mcthanol .ontłnliry 5 lvt' ł' of Hcl
volume and diamctel in case ofĆal
lV' olĆĆt lar v.iE h r and n oIc li r w.i8hi distibJ tiÓn
enPłafu rc(200lt)' HowĆvgitshould bcstGscd thłt
ol inv*tigatcd sańPlcs vcrc dctnnrined bJ' 3€1 pernea
fu h.r ińgssc in am€alin8 ieńPelaforc uP lo 300 t
tbn ĆhrońatoEGphv (PLGPc220) at ]50!t in bichlo
dres noi .ause imporanr chans.s in sol-scl nahtul
'
nnoudr.'hńD's'cLń!Ińń
lil
ous
g.ninal rnd jsolat.d oH Bmups.Thus annolinsai
specific tcmPłature allolvs t. Óbla
tahon of superfi.ial hvdloxyk, whai śimpo n ij]
esc oloxidłtyPe naklials
Prepared slppofr mat liils wcrc uscd il.hcmisorption oft:6 hon mctJllomPonoł
a(oldiĘ
Fil 2 TC dn!Ś ł llżkirls rt\,]ixd rs snpp b'hulilNfib
10dt(lfrn1)1 łlźtl5i]nj,2 _ tklisł silia
obscned $rrace physi.al piope y variarion c probibly.żUsed by .hanBes i'\ 3.l s
changs thar dccu! dlrińg heating
n. anrlysis w.s pe orn.d (Fig. 2). A sho,Bcr d(cm!
nri iial weighi in .ase ot solgel silici, in .omp.rison
wiih Davisil sili.a, during the heati$ ai the bmperaiur.
!P 60 ]00 oc, ińdicat* hishel Nater (and probably dha
nol) ońtcnt ijr sol-!c] ńalcrial' as a synthśis lsiduc
Rcnoval of wato mol(ulcs is vcry impo antin cascoI
oĘ.nometalli. c ily s' which rcqunc sPe.iJI handlin€
h dr' oxĘen fr €atmosphele' Thus matedalann.alin€
al i.np.rafur. up lo 200 ijc should eliminat€ najority oI
\'ater moleol6, leaving cerhiń .Ón..ntation of sLP.l
Ii.il hvdroxyh, which alc podul'rcd to bc vicinrl,
Scmin i I or isolaied 13,111 At tempenture above 200
to.alĆination tńPerfot, Jre present.d nr
Tablc 1 ]d .ońPar.d w h oĘśpondin!Ya|adium
.onteni n\ .ablyns obtJincd by imPl.Elulion. R€eived
techniques Lsed lor
.atalyśPrcP ation Eive simi]al rsuxs: sol8el sili.^
calcjncd 200 t shÓws 0'3 nńolv/g..' (det.ńŃd by
gravimcbic le.hnique) and 03r ńńolv/g.il (dctcr
njned by AAs), Ę\P{ńVel),' Davisil siln t.it.d ir thc
ghcr vłnidlum on.
lent, !lł'at nay bc causcd by ih hi3hcr surfacc area' Boih
luPpÓ habnak innPaled 300 "c show almo*tipl.
.oncnhationolpkureol lall in.ÓmparisÓń Hith thĆse
th.i were.alĆined at 200 !c obscrvcd dcocdsc śob'
viously caus.d bt reducrion oi s
groups .onc.!batio.. Hoecvq it should bc shc$cd
that oveń thc suppo .al.inPd łł300'c, wlich s@ms to
b. sbongly d.hydrovlat€d'
is ill
j5
of vłnadn'n PrĆĆlsor'1}
5 !atidn nay bd ĆxPlaincd
by P ricipation or siroianc blid
Vocltr,brtirshould bcnoti.cd rhatoncbridsc,which rs
lorm€d Itom nvo hydroly] grcuPs
t
a Prcgrc$ivc rcmoval of hydroxyls ta*es plł.e, whłł
r6ulb in parhally dehydroxylared silic. as a resulr oI
? f .!q
-,.',,.
Finally' at hlshc! tńPerable, due io ńig.atjon of
individual hydroxyl group& funhcr dchydrłtahon is
pos,blc wh rcsulb in almGt tully dehydbxylated
su,Iacc wfth rcmainins siloxanc sroups d not num.F
lnvcshgJi€d .atalyli. sy*.ns were aPPlied in lÓw
presur. ethvlene Polyńe.iza hon Plocs ca h lyst suP'
pmktl on .ari.r lDavisil o! sol scl sili.a) caloncd a'
200'c shows $snińcan'ly highc! Plodudjvły (cx
pr€s.d in F PE/g.iJ jn onFrś
where $'PpÓń was am.ded
.l.al wh.n w. realize that
300.c k s*ńs
k] he
ar. Pocńtblly ']LaŃiry
fÓrngr {]ePeńds dnsdy on
thcquanhqof baŃilionlrchLconpound,}'hrhisPe
pni in caralyii. systcnr. Dilfcrcn.cs in polymo yipld obtajned wiih usc oI cłalysśsuPpo'
ntliuotr may be !x
&.
sańe
!vay'
Hi8het
prodUdivity
o1@lalysr
Plained
on
Davisil
is
ly
6upported
calsEd .!id.
by nc ly
'i!iĆa
biplc highervanad,un load,rE on slppo s surfi.e, in
.ompatuon wirh sol-gcl m c al.
HowevłÓmpa sonof adiviliesoli'Nenigabdsys
teńs (exPr€Śed in kg PE/mol9 Table 1) PR,ve that .aia
IytjĆ s}shns obtained with solg.
cient' Diffł.nĆs in adiviti.s błween Davn and solgelsJPpÓń.dcablysb,annealcda
fure, ńay be dPlańed by differenc$ jnvaladlum ]oad.
inF oń suppo suńa.c TakinE into .otrid.nlion ń€
amount of vanadn' m .ompound rixcd rd suppo ssur
Ia.e area 6 well we c see ihat DaviŚil suPPoted cab
lyśEAh blb clclnt muc dcNc d'.hbunon oI pn.ur
sor rpmolv/m') As ! rcsult rdN! sp! c, th Jre
Iomcd on Davńil supPon sulfJ.c m.y by les a..$sible
Ior .}!ibly* md nmmma hÓle
.",.'-r:"
gPeĆies rhat
Addińońally Daisi| dcmonst cs tlre surfa.e with
Mlowald dccP Pors cPrc$c
d żńchlto{o]unlc nno Ld] /l }l- wh Le fol!o źe 5
l'o $r pa'amd$ E hłic hjlhe
Pli€d..lcin ion knpd urc (Table 1)' As a r$!lrthe
najol pa{ of Dłvjsil surf..e area nay be lo.ated inside
lhe Porcs' vłnadium acŃt sib9lh aĘ łtrń.d ń the
"in lenal, Pał Óf th. ŚuPpÓł surfacc ńa y dil] bg a.es.
sible lor Ćo Ćataly* and nonomc. nolc.ulcs' but the
grÓwth o' ńasomolc.ulc clti| insidedeep por€s nay
obbjn(rl rcsłlts p.ovc rh.i solg!
ib rdvanhg.ous noryhology $ir
Lf
| ,..".
c^,,"
$e lool al p.]yms morpholoe] ltlhows
re
żh\cly
h'Ph bulLdens ĘLJ]'rG!2ooP/dmrlo. ]onN oolvne
ion time) what is benefici;l lor
ńlńeń_
zaiion proe$E. Addirionally it is known rhar polymei
z
fdstńl
pa id$ shouId exhibii Ónfulled sPhc cal morPh}
lo8y wi& dsired size and unifońiry' Hetercgen€ous
(esPeĆially suPpoń€d)
PÓIyhc! Par'ide
.atalysb sivc thc oPPoduniiy 01
as .t aly* paticle re
onEol *nown
ii''
ź
ź'
Ii! 3 Pł,nb Śźl disnib i. o|ulrl!]łŚ afri.ń rnd Ęs|hhlg Pruź rlb|. 1' 3 '
l gd Śi]ia dńd PE oblr d
fulhils Et,l*prlrlly)r,1 Da!śila|d PEdbrrińluilh
Porcs' allows ło obiain tI. .ałalyli. sy*eń5 Wiih highcl
adivity nr bn' pr*s!l. e$ylenc PÓ
Płrison with .ommctial Davi5il 5i|Ę
Mole.Ulal welght o1Polycthylcne obtained with uę
of sol3.l (.ahiŃd a' 200 !c) suPPolicd !żtalysb k
relatively hish (Mr;2 l0r) It is n.t slrprisinE, bc.
.a!se van'dium c aly s aE ki.wń k, FIodu.c thc
Polyńcls of exłemejy high ńÓIecllar voghś łnd
t)Iołd nole.ular k.isht Jin.butjons n3]. Howev.r
analyz€d samPl.Śh.w! qutc DJfow moleelar wethr
disbibuiiÓtr (MWD < 4) Whł poi|b io low hddÓB.
ne y o1 5ur1{c vaDrdium sP..iA
siÓre aĘ confilncd by Polyner proPdtiA li*ed in Tablc
2. Meltirg poini (139-1.10 t) and dysallBity (3940 "1) vr1u6 sem to b! jndŁPendcnt on ca[icr lyPe
ucd d way of iśhÓd i.ahoń n .y bc caus€d bv
th? łffinity oI aĆtile silĆŚ' hl.h a
Padion ol vocl1 ś'fthhydloxvl g'ouPs or siloxan€s
in any Ćase lanadiuń on is lixcd
oxygen leq (2)l.
'l'
ReŚUlts of caEier Pati.Ic di*obuhon rd relaled
polyneiśgranule dctibution (obłained !vi& Ćorc
sPońding .łlalyli. syst(' are P
can be mtied, ih bolh suppońed sysbms PÓducc the
Polymer of fDc Pa*i.les and uniforn disńbutions'
co'nparjsÓn of suPpon habńal Eianulalion wilh ade
quat. Poly€thyl.n. grrnulcs dtblbution shows that
Ths ulk bls |ńrncŻl bu Palish stck cod\lle
scilll!,kRa.żrch' pnrd 4T09B11a 23 Qaaz zaa4)
r
hl
cŹlli P, ce.din G', chadsnk J c,DclDumD',
vRnio
c.] jn "Mel.]oĘanic caialysb lÓr synthcsn
and
2'
3.
4.
5'
6'
7'
Polydelatud'
(Ed.
lGniBky w),
vdla& Bdlin 1999.
czj. K'' Biłlek M': MmMo|
springs.
Follesbd A, RyEer
8.,
Tob.t M., Y6bns M.), sprin
Bri <e! c schłe' 6 W] "sol{cl sic!..", Acl.
naP'?
dmic Prs'',lrc., san Di€8o r9o'
9' Tori M', Tal€udi T, Miyaś a s', (anb€ s.| /. Ml
Nowakomka M', Boś@gkźI(
s.L1sĄu,23v.
199zL93,339.
r0' czaja K', NovÓkshorcVa L' A'
Bo$wL. (, N@akowgrź M '| I. APpL' Pąn' s.i
r99& 69, 1005.
Mącnnol' char' Phls 1999,200, 9s3.
c'ajax',BiabrM:!ołr'f!20m.a7'6s5. ]]. llq R' K': 'The chemistry o' si
"Mehlotgań. cabrysś for syn$6ś ad Folynłi_
12' cżĄżK|PaWłaa0,41'3937
Ża'ion" (Ed. KamiNky w' sPiiry.Pvqla8, Balnl
13'clk.vaN,M,U3haLoEaM,
c', Meshkova l' N', Dya.hkovskii F. s.: lol']'.ry
"organÓbdaxic cŹhlysts and oleln PolFłizł
riÓn'
cahĘts
1or a
Ne Minmjffi"
(Eds. Blom R',