Note: Descriptions are shown in the official language in which they were submitted.
PROCI~SS FOR P~PARING POLYOLEF'INS
~CKG~OUND OF '~ INV~NTION
The present invention relates to a process
fo= preparing polyole:~ins using a nove.1 po]ymeri.zation
5 catalyst.
Ileretofore, in tl1e technical field of lhis
sort ~ re llas been Icl1owll :EroM Japanese ~atent
licatiol1 No.121()5/1964 a catalyst comprisin~ a
Iml~Jlles;illln lla:lide ~nd a tral1sitiol1 metal coln~)ound such
1() as a tita~ m conl~oul1c1 supported thereon. Further,
a catcll.yst obta.il1ed by the co-pulverization o:E a
ma~llesillm l1alide and titanium tetrachloride is known
~rom RelcJian Patent No,742,112.
~lowever, when viewed from the standpoin-t
that the catalyst activity is clesired to be as high
as possible in the manufacture of polyolefins, the
process disclosed in the Japanese Patent Publication
No.12105/1964 is stil~ unsatisEactory beca~lse of a
low polymerization activity, while the polymerization
activity attail1ed in the process oE Belgian Patent
742,112 is fairly hial1, but a further improvement
is c1esired.
ln the process disclosed in German Patent
No.2137872, the anloul1t o~ a magnesium halide used
2r~ is su~stal1ti.al~y decreased by the co-pulverizat:ion
_
thereof with titanium tetraehloride and alumina, but
a remarkable i.nerease in aeti.vity per solid, whieh
can b~ reeoynized as a (3uideline or produetivity,
is not reeoynized, ancl it is desired to develop a
catalyst of a h.igl1er acti.vity~
In the manuEacture of polyo1efins, moreover,
it .is a1so des:i.rable from -the aspeets o~ productivity
ant1 sl~lrry hclndlillc3 that tt-~e bulk dens:ity of the
r.es~llt:i.l1cl po].ylTIer be as hi~h as possible. F'rom this
I() sLalldL)o.i.nt, the l~rocess d.iselosed in the Japanese
t~ltel1t P~lblieat:i.on No.12105/1964 is no-t satisfaetory
:in loth the bul)c dens.ity of the resulting polymer
al1d polymerization activi-ty, while in the proeess
diselosed in the Belgian Patent 742,112, -the polymeri-
~5 zation activi-ty is hic3h, but the bulk density of the
resulting polymer is low. Thus, in both -the proeesses,
a further improvement is desired.
SUMMI~RY OF TIIE: INVl~:NTION
It .is tl~e object oE the present invention
to ~)rovide a nove.1 polymeriza-tion eata]yst and a
proeess for the holllopot.ymerization or copolymerizatio
o~ olefiT1s usin~3 the catalyst, eapable of remedying
the above~ el1tiolled drawbaeks, attainin~ a high
po.lylllerizati.on activity, affordinc3 polymers wi-th a
hiclh bul)c density in higt1 yield and prac-ticing a
eontinuous polymeriza-tion extremely easily.
The present inven-tion resides in a process
Eor preparing ~olyoleEins by the ho3l10polymerization
or copolymerization oE oleEins using a eatalyst whieh
comprises the combi31atio1l of:
[I~ a solid substance obtained by the reaction
oE at least the Eollowing two co1npo1lents:
(i) a ma(11lesium halide and
(ii) a tita~ n compound and/or a vanadil1m
1() con1poln~d;
~II] a compoulld represented by the general formula
R~ 5i(0l~2)4 1~ wl1erein R1 and 1~2 are hydrocarbon
radicals havinc~ 1 to 24 carton atoms and
O ~- m ~ 3;
[III~ a eompound represented by the general formula
R3n~l(0R4)3_n wherein R3 and R4 are hydrocarbon
radicals havinc~ 1 to 24 carbon atoms and
1 C- n < 2; and
[IV3 an organo1netall3c compound,
and which catalyst satisfies the cond:it:ions that the
mola3- ratio o~ s:i1:icon in tl-1e compo1le11t [II] to titanium
ancl/or va11ad:ium in tl-1e component LI~ s1~ould be in
the range of 0.1 to 100, the molar ra-tio of aluminum
in the compo1le1lt lI:1I~ to silicon in the con1por1ent
LII~ sllo-1ld be in the range of 0.01 to 10 and the
molar ratio oE t11e n1elal in the componen-t [IV~ to
tltanium and/or vanadium in the componen-t ~I~ should
be :in the rancle of 0.1 to 1000.
Sir1ce the polymerization catalyst used in
the present invention exhibits a very hlgh polymeriza-
tion activity, the partial pressure of monomer duringpolymerizatio11 is ~.ow, and because of a hic3h bulk
density o.~ the result:i11c3 polymer, the productivity
cal-l be :iln~rovecl. Moreover, -the amount of -the catalyst
~ lla~ .ill(J i.n tl1e l^es~ltinc3 polymer a~ter polyme:rization
1() is so sll1al.l thclt the polyole.Ein manu:Eacturing process
can d:ispense w:ith the catalyst removing s-tep, which
leac1s to silnp].lfication of the polymer trea-ting s-tep,
and consequently polyolefins can be prepared very
economically.
~ccording to the process of the present
invention, the amount of polymer procluced per unit
polymerization reactor is large because of a high
bulk density of -the resulting polymer.
The present invention is Eurther advantage-
_() ol1s in t.hat wl1en viewed from the stancdpoi.nt of particlesi~e of the resLl1tinq polymer, the propor-tion Or
coarse par-t:ic1.es ancl that of fine particles below
50 ~Im are small desp:ite oF a high bullc density of
the polymer, a~ hat the1~efore not on].y it becomes
easy to perfol-ln a Co~ti.lluo~s polymer:i.zation re~ction
but also the centriEuclal separati.on i.n the polymer
treating step as well as the handling of polymer
pa.r-ticles in powder transport become easy.
~ ccorcling -to the present i.nven-ti.on, in
addit:ion to the high bulk densi-ty of polyolefins
obtained by usin~ the catalyst of the lnvention as
previously noted, polyolefins havina a desired melt
illdeX can be prepal-ed at a lower hydroqen concentra-
tion thall in convelltiollal me-thods, thus permitt,ing
E-o.l.ylne.L-.ization to be carried out a-t a relatively
ln slllall total pressure, and th.is ~reatly cont:ributes
to the .imp.roveme1lt oE ecollomy and productivity.
~ dditi.onally, in -the oleEin pol.ymerlza-tion
using -the catalys-t oE -the present invention, the
olefin absorbincJ rate does not decrease so much even
with lapse of tirne, and therefore the polymerization
can be conducted for a long time in a small amount
of the catalyst.
Furthermore, polymers prepared by using
the catalyst of the present inven-tion i-lave a very
2Q narrow molecular wei~ht d:istributi.on and their he~ane
e~traction :is very small, reflectln~ nllnimlzed by-
production of low c~rade polymers. There:Eore, for
example, in the film grade, -those polymers can afford
products of good (luali.ty such as a superior anti-
l~locking property.
DESCRIPTION OF PREFERRE:D EMBODIMENTS
~ xamples of the magnesium halide used intlle p:resellt :inventioll include substantially anllydrous
maclrles:ium .Eluorlde, magnesium chloride, magnesium
brolnide, macJIlesium iodide, and mi.x-tures -thereof,
with magnesium chloride being mos-t preEerable.
Exalllyles of the titanium compound and/or
vallaclium compoulld used in -the present inven-tion include
Il~I.icl~s, all;oxyllal:i.clcs, a]kox,ides and haloc7enated
1() ox.i.(lcs, o.E t.itall iUIll alld/Or ValladiUm . ~S pre:Eerred
e,Yllnp.les o.E the -titanium compound there may be men-
tione~ tetravalent and trivalent -titallium compounds.
~s tetravalent titanium compounds, those represented
by the general Eormula Ti(OR) X3_r are preEerred
wherein R i.s an allcyl, aryl or aralkyl group having
1 to 24 carbon atoms, X is a halogen atom and r is
0 < r C 4, such as titanium -te-trachloride, titanium
tetrabromide, -titar3ium tetraiodide, monomethoxy-tri-
chlorotitaniuln, dimethoxydichlorotitanium, trimethoxy-
monochlorotitanium, d:ietlloxydi.cllloro-t.itani.um, tetra-
metho~y-titalli.uln, mcllloethoxytrj.clllorotita~ m, tri-
etlloxymonoch~oroti tal~ m, te-traethoxy~i.talli.um~ mono-
i.soyropoxytrich:l.oroti-tanium, diisopropoxydichloro-
titanium, triisopror)oxymollochlorotitanium, tetraiso-
~ropoxytitanium, monobutoxytrichloroti-tanium, di~utoxy-
'clichlorotital~ m, monopelltoxytriclllorotitanium,
monophenoxytriehlorotitanium, diphenoxydiehlorotitanium,triphenoxymonoehlorotitanium and -tetraphenoxytitanium.
~s trivalent titanium eompounds there may be used, :Eor
exanlple, titanium trihalides ob-tained by redueing
titanium tetrahalides such as titanium tetraehloride
and titanium tetrabromide with hydrogen, aluminum,
ti~an:ium or an orcJal1ollletclllie eompound o~ ~ nletal
.selected ~rrom Groups l tl1rougl1 III in tl1e Periodie
Table r as we:Ll as trivalent tital1ium eompounds
cbta~ ed by rec1ucin~ tet:ravalent alkoxytitanium
l1alicles o.E the general :~ormula Ti(OR)SX4_s with an
orcJallometallie compound of a metal selected ~rom
Groups I througl1 III in the Periodie Table in whieh
formula R is an alkyl, aryl or aralkyl group having
1 to 24 earbon atoms, X is a halogen atom and s is
0 ~ s < 4~ Examples oE the vanadium eompound include
tetravalent vanadium compounds such as vanadium
tetraehloride, vanadiulll tetrabromide, vanaclium tetra-
iodide and tetraetl1oxyvanadium; pentavalent vanadium
compounds sueh as vanadium oxytriehlori.~le, ethoxy-
dichlorovanaclyl, triethoxyvanadyl and trihutoxyvanadyl;
and trivalent vanadium eompounds sueh as vanadi.um
tricl1loride and vanadium triethoxide. Tetravalent
titanium eompounds are most preferable in the present
invention.
9~
To make the present invention more effective
the titanium compound and the vanadium compound are
orten used tccJether. In this case it is preferable
Lllat the V/Ti mole ratio be in the ranc~e 2/1 -to
0.01/1.
The metl~od o:E obtaining the catalys-t compo-
nel1t ¦I~ by reactinq -tlle magnesium halide ~i) with
tl~e titanium cornpouncl and/or vanadium compound (ii)
in the pl^esel1t ~ vel1tiol1 is not specially limlted.
otl1 (i) al1d (:iL) Incly be reacte~ by contacting toge-
lllel- llsual:ly Eor 5 minutes to 20 hours under heating
at: a tell1perature o:E 20 to 400 C pre:Eerably 50
to 300C in the presence or absence of an iner-t
solvent. ~lterna-tively the reac-tion may be carried
out by a co-pulverization treatment. The lat-ter
is preferable in the present inventiol1.
q~he inert solvent which may be used in
prep3ring tl1e cal-alyst compol1en-t ~I~ is not specially
limited. I~drocarbons al1d/or derivatives thereof not
inaCtivatil1cJ ~ieJle~ ype catalysts are usua]ly employ-
able. E~arnples are various saturate(1 aliphatic hy(7ro-
carbol1s aromat:ic hyc1rocarbons cand alicycllc hydro-
CarbOllS S~lCh as propane hutal1e pentane hexane
l-eptane octane benzel1e to:luene xylene and cyclo-
~1e~ane as well as alcohols ether.c. and esters such
'as etllallol, diethyl ether, tetrahyclrofuran, etllyl
9~
acetate and ethyl benzoate.
The apparat:us to be used for the co-
plllver:izati.on i-s not specially limi.ted. Usually, a
ball mill, a vibration mill, a rod mill or an impact
mill is l1sed. Conditions for the co-pu.1.veri.zation
such as temperat~lre and ti.lne can be deci.ded easi.ly
~y tl~os~ skilled in the art according to the co-
p~llveLization method used. In general, the co-
pll1ve~r:iza~.ion .is carried out at a temperature i.n the
l0 r(1l1cle oE 0 to 200C, preferably 20 to 100C, :Eor a
pe:r.iocl o.E time .in the range of 0.5 to 50 hours,
preEerably 1 to 30 hours. Of course, the co-
p~l:lv~r.izlnc~ operation should be performed in an inert
gas atmosphere, and moisture should be avo.ided.
~s to the reaction ra-tio of the magnesium
halide and the titanium compound and/or vanadium
compound, it is most preferable -to adjust i-t so that
the amount of titanium and/or vanadium contained in
the catalyst component [I~ is in the range of 0.5 to
20 20 wt.%. The range of 1 to 10 wt.~ is particularly
preEerred in orcler to atta:in a well-balanced activity
per titanillm al1d/or val1adium and that per solid.
In preparing the catalyst component [I~ in
the present in~entioll, moreover, a member or members
?5 se.lectecl :Erom t.l-le cJroup consisting of compounds of the
c3eneral formula Me(OR) X wherein Me is an elelnel1t
p z--p
L99~ -
selected from Groups I -through VIII in the Periodic
Table, provided titanium and vanadium are excluded,
R .is a l1ydrocar-~on radical having 1 -to 24 carbon
atoms, X is a haloc3en atom, z is the valence of Me
and p is 0 C p < z, orgal1ic halides, ha]ogenating
ac3ents, phosp]loric esters, electron donors and poly-
cycl:ic al^omatic coml~o~lnds~ may alc,o pre~elably be
llsecl as c0lnl~01lellt (c~) in (lclcli tion to t}le mac3nesium
i~al i.de (:i) alld t:lle t.i.l:aniuJn compound al~d/or vanadiuln
colllpo~ d (.i-i). The compol1ent (cx) may be u~ed in an
allloullt o~ 0.01 to 5 moles, preferably 0.05 to 2 moles,
per Illole oE the magnesium halide (i).
Fxamples of compounds of the general formula
Me(OR)pXz p which may be used in the present inven-tion
include the followincJ compounds: NaOR, Mg(OR)2,
Mg(OR)X, Ca(OR)2, Zn(OR)2, Zn(OR)X, Cd(OR)2, ~l(OR)3,
A1 (OR) 2X, B (OR) 3, ~ (OR) 2X, Ga (OR) 3, Ge(OR)4, Sn (OR) 4,
P(OR)3, Cr (OR) 2~ Mn(OR)2, Fe(OR)2, Fe(OR) 3, Co (OR12
and Ni(OR)2. ~s more concrete preferable examples
tl1ere may ~e mentiol1ed the Eollowinc3 compounds:
NaOC 1I NaOC,~119, M9 (OC113) 2 ~ Mc3 (0C21 5) 2 ~ 3 3 7 2
(C2~l5)2' Zl~(oc2llsl2~ Zn(OC2ll5)Cl~ ~l (OC113 ) 3,
~l(oc H5)3~ ~l(OC2lls)2cl, ~l (OC3M7) 3, 4 9 3
6 5 ) 3 ~ B (C2ll5 ) 3 ~ B (OC2~]5 ) 2Cl ~ E' (OC2115) 3,
25P(OC6115)3 and Fe(OC4119)3. Particularly, compounds
represented by the cJel1eral :~ormulae Mc) (OR) X2_ ,
- 10
Al~OR) X3 an~ B~OR) X3 are preferred. ~s the
substituent R, C1 to C4 alkyl groups and phenyl are
preferred.
Or~anic ha].ldes which may be used i.n the
5_
present invelltion are partially ha]o~en-sllbstitllted,
saturated or unsaturated alipha-tic and aromati.c llydro-
carbons, inclucling mono-, di- and tri-~ubs-tltuted
colllpoull(ls. 'l`lle llalo~en may be any of :Eluorine,
clllorlne, bromlne and iodine.
amp].es o.E s~ch organic halides :include
nlc~thyl.ene ch:Lorlde, cllloro:Form, carbon tetrachloride,
bromochlorometllane, dlchlorodifluoromethane, 1-bromo-
2-chloroel:llane, chloroethane, 1,2-dibromo-l,1-
~ichloroethalle, 1,1-dichloroethane, 1,2-
dichloroethane, 1,2-dichloro-1,1,2,2-tetraEluoroe-thane,
hexachloroethalle, pentachloroethane, 1,1,1,2-
-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,1,1-
trlchloroethane, 1,1,2-trichloroe-thane, 1-chloropropane,
2-chloropropane, 1,2-dich:Loropropane, 1,3-dichloropropane,
2,2-dichloropropane, 1,1,1,2,2,3,3-heptacllloropropane,
1 r -1 ~ 2,2,3,3-hexachloropropane, octachloropropane,
l,1,2-trichloropropane, 1-chlorobutane, 2-
clllorobutalle, 1-chloro-2--methylpropane, 2-chloro-
2-methylpropane, 1,2-dichlorobutane, 1,3-dich1orobutane,
:'5 1,4-dichlorobutane, 2,2^dicll1Orobutalle, 1-chlorodecane,
vinyl ch]orlde, I,1-dichloroethylene, 1,2-
dichloroethylene, tetrachloroethylene, 3-ch].oro-1-
propene, 1,~-dichloropropene, chloroprene, oleyl
chl.or:ide, chlorobenzene, chloronaph-thalene, benzyl
chlori.cl~, ben~ylidene ch.]oride, chloroethylbenzene,
styrene dichlori.de and ~-chlorocumene.
Examp]es c~f i1alocIenating a~erIts W}l;.C}l may
be used in the ~resent invention include halides
oE nonme~als such a~ sulfur chloride, PCl3, PCl5
and SiCl4, as wel~ s oxyhalides of no~ etals s~Ic:I
'~5 I'OCl3, COC1.2, NOCl2, SOCl2 and S02C12.
I() Phosp11oric esters which may be used in
the present invention are compounds represen-ted by
OR
the cJeneral Eormula P - OR wherein R, which may be
Il \
O 01~
alike or diEferent, is a hydrocarbon radical havinq
1 to 29 carbon atoms. Examples of such compounds
are triethyl phosphate, tri-n-butyl phosphate, triphenyl
phosphate, tribenzyl phosphate, trioctyl phosphate,
tricresyl phosphate, tritolyl pl1osphate, trixylyl
phosphate and c1iphenylxylenyl phosphate.
~xamples o:E electron donors which may be
2n ~Ised in the present invention are alcohols, ethers,
ketones, aldehycles, organic acids, organic acid esters,
acid halides, acicl amic1es, amines and nitriles.
~ s alcoI1ols there may be used, for example,
~tIIose haviIlcJ 1 -to 18 carboIl atoms SUCll as methyl
aleohol, ethyl aleohol, n-propyl aleohol, isopropyl
aleohol, allyl aleohol, n-bu-tyl aleohol, isobutyl
aleoilol, see-butyl aleohol, t-butyl alcohol, n-amyl
aleohol, n-hexyl aleohol, eyelohexyl aleohol, deeyl
alcohol, lauryl alcohol, myristyl alcohol, ce-tyl
alcohol, stearyl aleohol, oleyl aleohol, benzyl aleohol,
na~ tllyl aleohol, phenol and eresol.
~ s ethers there may be used, Eor example,
tI1OSe 11~Vil1C~ 2 to 20 earbon atoms sueh as climetllyl
l~ etller, d.;etllyl ethcr, dibutyl ether, isoamy:L ether,
an.isole, phenetole, diphenyl ether, phenylallyl ether
and benzofuran.
~ s ketones there may be used, for example,
those having 3 to 18 earbon atoms such as aee-tone,
methyl ethyl ketone, methyl isobutyl ketone, me-thyl
phenyl ke-tone, ethyl phenyl ketone and diphenyl ketone.
~ s aldellydes there may be used, for example,
those havin~ 2 to 15 carbon a-toms such as acetaldehyde,
propinaldehyde, oetylaldehyde, benzaldehyde and
naplltllaldehyde.
~ s or~ani.e acids tllere may be used, for
example, those havinc~ 1 to 29 earbon atoms such as
formie, aeetie, propionie, bu-tyrie, valeric, pivalic,
caproic, eaprylic, stearic, oxalic, malonic, succinic,
adipiel methaeryli.c, berlzoic, toluic, anisic, oleic,
`linolei.c and lino.l.~llie acids.
_ 13
~L2~9g~ '
~ s organic esters there may be used, for
example, those having 2 to 30 carbon atoms such as
metllyl :Eormate,-methyl acetate, ethyl acetate, propyl
acetate, octyl acetate, e-thyl propionate, methyl
butyrate, ethyl va]cl-ate, methyl methacry]ate, met}lyl
benzoate, ethyl benzoate, propyl benzoate, octyl
len7.0ate, phelly:l bel~zoate, benzyl ben7.0ate, butyl
etl~o.~ybenzoate, methyl toluylate, ethyl. toluylate,
e~ yl. e~l~yll~en~oa~e~ met}lyl. salitylate, phellyl sality-
1~) la~:e, Inetlly:l napllthoate, etllyl napllthoate and ethyl
all.isate~
~ s ac:i.d hal:i.des there may be used, forexamp:le, those having 2 to 15 carbon a-toms such as
acetyl chloride,benzoyl chloride, -toluoyl chloride
15 and anisoyl chloride.
As acid amides there may be used, for example,
acetamide, benzoylamide and toluoylamide.
~ s amines there may be used, for example,
methylamine, ethylamille, diethylamine, tributylamine,
piperidine, tribenzy:lam:ine, aniline, pyridine, picoline
and tetrametllylened:iamil-~e.
~ s nitril.es there may be used, Lor e~ample,
acetonitrile, bell7.0nitrile and tolunitrile.
E~amp].es of polycyclic aromatic compoullds
'5 whi.ch may be used in the present invention inc~.ude
napllthalene, pheJlanthrene, triphenylene, chrysene,
3,4-benzophenanthrene, 1,2-benzochrysene, picene,
anthracene, tetraphene, 1,2,3,4-dibenzan-thracene,
per)taphene, 3,4-benzopentaphene, tethracene, 1,2-
benzotethracer1e, hexaphene, heptaphene, diphenyl,
'~Luorene, biphenyler1e, perylene, coronene, bisantene,
ovalene, pyrene and perinapl1thene, as well as halogen-
al1d a]kyl-substituted derivatives thereof
Tl1e catalyst component ~I~ thus obtained may
be su~portec1 on al1 oxide of a metal selected from
~,roups XI through IV in the Periodic Table. This
mode oE use is also pre~erable in the present invention.
In t]liS case, not only o~ides oE Group II-IV metals
eacl~ alone bu-t also double oxides of these metals,
as well as mixtures thereoE, are employable Examples
of such metal oxides are M~O, CaO, ZnO, BaO, SiO2,
2' 23~ MgO-~l2O3, SiO2-~l2O3, MgO-SiO
MgO CaO-Al2O3 and ~l2O3 CaO. Par-ticularly preferred
2' ~l23~ SiO2-~l2O3 and MgO-A12o
The method of supporting -the catalyst
component ~I~ on an oxide of a Group II-IV metal in
the Periodic l~a~le is nol: specially limited, but ~s
a preferred exarnple t}lel^e may be mentioned a method
wherein the components (i) and (ii), and the component
(~) if required, are allowed to react under h~at-in~,
2~ for example in an etller compound as solvent in the
presence of the said me-tal oxide and then the liquid
- 15
~19~
phase portion is removed.
Examples o:E the compound of the general
fo.rlrlu.1.a R1mSi(~l~ )4 m used in the present invention
include monornethyl trimethoxy silane, monome-thyl
triethoxy silane, monolnethyl tri-n-buto~y silane,
monomethyl tri-sec-butoxy silane, monornethyl
tr:iisopropoxy silane, monomethyl tripen-toxy silane r
monolrlet:l1yl t.rioctoxy s:ilane, monometl1yl tristearoxy
si.lal~o, nlor1olnetllyl tr:iphenoxy silane, dime~l1yl c1lmetl1oxy
1~ s:i.1.ane, d.im~thyl diethoxy silane, dimethyl diisopropoxy
silane, c1imethyl diphenoxy silane, trime-thyl monomethoxy
s:ik~l1e, trLmethyl molloethoxy silane, trime-thyl mono-
isopropo~y silane, trimethyl monophenoxy silane,
monoethyl trimethoxy silane, monoe-thyl triethoxy
silane, monoethyl triisopropoxy silane, monoe-thyl
triphenoxy silane, diethyl dimethoxy silane, diethyl
diethoxy silane, diethyl diphenoxy silane, triethyl
monomethoxy silane, triethyl monoethoxy silane, -trie-thyl
monop}lenoxy silane, monoi.sopropyl tr.i.methoxy silane,
mono-n-butyl trimethoxy silane, mono-n-butyl triethoxy
silane, mono-sec-butyl -triethoxy silane, monophenyl
tr.ietl1o~y si.lal1e~ di.pl1enyl diethoxy silal1e, tetra-
ethoxy silalle and te-traisopropoxy si].ane.
If tl1e amount of the compound of the ~JeneLa:l.
formula R1mSi(OR )4 m used in the present invention is
too large or too small, its effect oE addition cannot
_ ~6
be expec-ted. Usually, its amount is in the range
of 0.1 to 100 moles, preferably 0.3 to 2n moles,
per mole o:E the ti-tanium ~ompound and/or vànadium
compound .in the catalyst component ~
~s examp1es o:E the compo~ d o:E the general
formula R3 ~l~OR )3_ used in -tl1e present invention,
mention may be ma~e o:E the :Eol.lowin~: dimethylaluminum
monoethc),Y.icle, dim(?thylaluminum monoisopropoxide,
cl:imc?t.lly:l.a,l~lmillunl mollo-ll-l)ul:oxide, dimetllylalumillum
In sec-bu ~:oxide, climetllylaluminum monophenoxlde, diethyl-
a~ lin~lm mollolnethoxide, diethylalumlnum monoethoxide,
diethylaluminum monoisopropoxide, diethylaluminum
mol1o~ butoxide, diethylaluminum sec-butoxide,
diethylaluminum monophenoxide, diethylaluminum mono-
octoxide, diethylaluminum monos-tearyloxide, diisobutyl-
aluminum monoethoxide, methylaluminum dimethoxide,
methylaluminum diethoxide, e-thylaluminum dlmethoxide,
ethylaluminum die-thoxide, ethylaluminum diisopropoxi.de,
ethylaluminum di-n-butoxide, ethylaluminum phenoxide,
isobutylaluminum dimetl1oxide and isobutylaluminum
d:iethoxlcle.
~ s to the amount of -the coml~ouncl o:~ the
~eneral :Eormula R41l~l(OR4)3 used in the present
invention, both a too 1.ar~e amount and a too small
amoul1t would not be e:Efective. Its amoul1t i.s in
.the ran~e oE 0.01 to 10 moles, preferably 0.05 to 2
~Z~
moles, per mole of the silicon compound in the catalyst
coml~onent [II~.
~ s e~amp:les of -the organomet~]lic compound
used in -the present invention, there may be mentioned
orcJanometallic compoullds of Group I-IV me-tals in
the Periodic Table knowll as a component of Ziegler
type cacalysts, but orcJanoaluMillum compounds and
or~anozil~c compounds are particularly preferred,
ror e~alllr):le, or~anoal~lmillum compounds of the c~eneral
1() ~o~ e ~3~1, R2~1X, RAlX2 and R3A12X3 wllerei~l R,
which may be alike or different, is an alkyl or aryl
cJroup having 1 to 20 carbon atoms and X is a halogen
atoln, and organoz:inc compounds of the general formula
R2Z wherein R, which may be alike or different,
is an alkyl group having 1 to 20 carbon atoms, such
as triethylaluminum, triisopropylaluminum, triisobutyl-
aluminum, tri-sec-butylaluminum, tri-tert-
butylaluminum, trihexylaluminum, trioctylaluminum,
tridecylaluminum, diethy]aluminum chloride, diiso-
propylaluminum chloride, et~lylaluminum sesquichloride,
diethylzillc, and mixtures thereof. TocJether with
tilese or~anometallic compounds there may be used
orgallocarboxylic acid esters such as ethyl benzoate,
ethyl toluylate and ethyl anlsate. The or~anometallic
2r compoulld may be used in an amount of 0.1 to 1,000 moles
per mole of the titanium compound and/or vanadium
- 18
compound in the catalyst component [I~.
The olefin polymerization using the catalyst
oE the present -invention may be carried out by slurry
po1ylnerizat:io1l, solution polymerization or vapor phase
polyl1lerization. Particularly, slurry polymerization
and vapor phase polymerization are preferred. The
polymerlzatioll reaction is carried ou-t ln the same
way as in t1ie co~1vent;o3lal olefin polymerl2atlo1l
reaCtiOIl USillg a Zie~ler type ca-talyst. ~'hat is, the
-10 reactiot1 :is perEormed in a substan-tially oxygen- and
wal:er-~1^ee conditior1 and in the presence or absence
o~ ~n inert hydrocarbon. Olefin polymerizing condi-tions
involve temperatures in the range of 20 to 120DC,
pre~erably 50 to 100C, and pressures in the range of
atmospheric pressure to 70 kg/cm2, preferably 2 to 60
kg/cm2. Adjustment of the molecular weight can be
made to some extent by changing polymerization condi-
tions such as the polymerization -temperature and
the catalyst mole ratio, but the addition of hydrogen
2n into the polymerization sys-tem is more effective for
this purpose. Of course, usin~ the catalyst of the
present invention, two or more mu:Lti-staae polymeriza-
tion reactiorls l1aving different polymerization condi-
tions sucll as differer1t hydrogen concer1trations and
different polylnerization temperatures can be performed
~i~ho~1t any trol~le.
~ 19
The process of the present invention is
applicable to the polymerization of all olefins that
are polymerizable with a Ziegler type catalys-t. Parti-
cularly, ~-oleEins having 2 to 12 carbon atoms are
preferred. For example, the process of the presellt
invention is suitable for the homopolymerization
of such ~-olefins as ethylene, propylene, butene-1,
hexene-1, 4-methylI)elltene-1 and octene--1, the copolymer-
ization oE etl-ylene/propylene, ethy]elle/butelle-1,
10 etllylc!ne/l-~exene-l, ethylene/4-metllylpentene~1,
etllylene/octene-1 and propylene/butene-1, as well
as the copolymerization oE ethylene and other -two or
more ~-oleEins.
Copolymerization with dienes Eor the modifica-
tion of polyolefins is also preferable. As dienesthere may be used, for example, bu-tadiene, 1,4-
hexadiene, ethylidene norbornene and dicyclopentadiene.
The following examples are given to fur-ther
illustrate -the present inven-tion, bu-t i-t ls to be
understood -that the invention is not llmited thereto.
Example 1
(a) Preparation of Solid Ca-talyst Componen-t rI~
10 g. o~ a comlllercially availab]e anhydrous
magnesiu]n chloride, 2.3 g. of aluminum triethoxide
`and 2.5 g, of titanium tetrachloride were placed in
- 20
a stainless steel pot having a con-tent volume of
400 ml. and containing 25 stainless s-teel balls each
1/2 inch .in diameter, and ball-milled for 16 hours
at room telnperature in a nitrogen a-tmosphere, to
obtain a solid catalyst component LI~ COI1taining
- 41 mg of titanium per yram -thereof.
(b) Polymeriza-tion
~ 2-liter stainless steel autoclave equipped
Wit]1 al~ duction stirrer was puryed wlth nitroyen
1() and tl1en cl1aryed w:it.h l,000 ml. oE hexane, then 1
Inlllol. o.~ trietl1ylaluminum, 0.05 mmol. of diethyl
c1:ieti-loxy silane, 0.01 mmol. of diethylaluminum mono-
ethoxide and 10 mg. of the above solid catalyst com-
ponent LI} were added and t~le tempera-ture was raised
-l5 to 90C under stirring. Wi-th -the vapor pressure of
hexane, the system was pressurized to 2 ky/cm2-G.
Then, hydrogen was introduced up to a total pressure
of 4.8 kg/cm2-G and -then ethylene was in-troduced up
to a tota] pressure of 10 k.g/cm G. In this state,
polymerization was allowed to star-t, which was continued
for 1 hour while mail1taining the internal pressure of
the autoclave at 10 kg/cm G. Thereaf-ter, the polymer
slurry w~s transferred in-to a beaker and hexane was
removed under reduced pressure to obtain 175 g. o.E a
~5 white polyethylene having a melt index o:E 1.1 and a
bulk density of 0.38. Cataly-tic acti.vi-ty was
82,100g.polyethylene/g.Ti-hr-C21l4 pressure,
3,370g.polyethylene/g.solld~hr C2H4 pressure.
F.R.-value of the polyethylene thus obtained
was 7.5. The molecular wei~ht distribu-tion was extremely
narrow as compared with the following Comparative
Example 1.
* F.R. value represents the extent of
molecular weight distribution and is
ca:Lculated as Eollows:
I n F.R. = melt index at 10 kg. load/
mel-t index at 2.16 kg. load
The melt index was measured according
to ASTM D-1238.
Comparative Example 1
Polymerization o: ethylene was carried out
in the same way as in Example 1 excep-t that the
diethylaluminum monoethoxide was not used, to ob-tain
140 g. of a white polyethylene having a bulk density
of 0.33 and a melt index of 1Ø Catalytic activity
was 65~700g.polyet11ylene/g.Ti~hr C2ll4 pressure,
2,700g.polyethylel1e/g.solid-hr-C2~l4 pressure. The
F.R. value of the polyethylene was 8Ø
ample 2
Polymerization of ethylene was carried out
- 22
in the same way as in Example 1 excep-t that 0.05
mmol. oE monoethyl triethoxy silane was used in place
oE the diethyl diethoxy silane and -that the amount
oE th~ d:iethylaluminum monoethoxide was changed to
0.02 mrnol. As a result, there was obtained 163 g.
of a white polyethylene having a melt index of 0.9
atld a bulk density oE 0.41. Cataly-tic activity was
76,500g.polyethylelle/g.Ti hr C2ll4 pressure,
3,130~.polyeilly]elle/~.solld hr C2l-l4 pressure.
The l;'.R. value oE the polyethylene thus
obtailled was 7.4. 'l'he molecular weigh-t distribu-tion
was extremely narrow as compared with -the following
Comparative Flxample 2.
Comparative ~xample 2
Polymeriza-tion of e-thylene was carried out
in the same way as in Example 2 except tlla-t the
diethylaluminum monoethoxide was not used. As a
result, there was obtained 121 g. of a white poly-
e-thylelle havillg a mel-t index of 1.1 and a bulk density
of 0.32. Cataly-tic activ:ity was 5~,800g.polyethylene/
.II`i-hr C2]14 pressure, 2,330g.polyethylene/g.solid hr
C2ll4 pressure. The F.R. value oE -the polyethylene
was 8.1.
E'~alllple 3
Polymeriza-tion of ethylene was carried ou-t
- 23
in the same way as in Example 1 excep-t that 0.1 mmol.
of diphenyl diethoxy silane and 0.02 mmol. of ethyl-
alulninum diphenoxide were used in place of the die-thyl
c1ietl1oxy sllane and diethylaluminum monoeti1oxide,
respectively. ~s a result, there was obtained 181 g.
of a white polyethylene having a melt index of 1.3
and a bulk density o:E 0.39~ Ca-talytic activity was
~,900~.polyethylene/~.Ti-}1r C2H4 pressure, 3,430g.
~olye~l1ylene/~solid~l1r C2~l4 pressure. The F.R.
I() va~ale ~E thc polyethylene was 7.5. The molecular
wei(lllt clistribut:iol1 was extremely narrow as compared
~it-i1 the following Compara~ive ~ample 3.
Comparative Example 3
Polymerization of ethylene was carried out
in the same way as ïn Example 3 except -that the ethyl-
aluminum diphenoxide was no-t used. As a result,
there was obtained 133 ~. of a white polyethylene
having a melt inde~ of 1.0 and a bulk densi-ty of
0.33. Catalytic activity ~-~Jas 62,400g.polyethylene/g
Ti-hr-C2l~4 pressllre, 2,560g.polyethylene/g.solid hr C2ll4
pressure. The F.R. value oE the polyethylene was
~Ø
E.~ample 4
(a) Preparation of Solid Catalys-t Component [I~
_ 24
10 g. of a commercially available magnesium
chloride and 4.2 ~. of aluminum triethoxide were
placed in a stainless steel po-t having a content
vo1ume oE 400 ml. ancl containing 25 stainless steel
~ci-lls each 1~2 inch in diallleter, and ball-milled
for 16 hours at room temperature in a ni-trogen atmos-
phere to ob-tain a reac-tion product. Then, a -three-
necked f:lask equipl~ed with a stirrer and a reflux
condel1ser was purc~ed with nitrogen and thel1 charged
-lO witl1 5 ~J. of the a~ove reaction product and 5 g. of
silica (/~52, a product o~ Fuji-Davlson) which had
~)eell calcined at ~00C. ~ en, 100 ml. of -tetrahydro-
Euran was aclded and reaction was allowed -to take
p]ace at G0C Eor 2 hours. Thereafter, -tetrahydrofuran
was removed by drying at 120C under reduced pressure.
Then, 50 ~IIl. of hexane was added, and after s-tirring,
1.1 ml. of titanium te-trachloride was added and reac-tion
was allowed to take place for 2 hours under reflux
of hexane to give a solid powder (~) containing 40
mg. of titanium ~er gram thereof.
The solid powder (A) was added into 50
ml. of hexane, then 1 ml. of tetraethoxy silane was
added and reaction was allowed -to take place for
2 hours undel- reElux of hexane -to obtain a solid
catalyst component ~
-- 25
~99~
(b) Polymeriza-tion
2-liter stainless steel autoclave equipped
~i.th an inductlon stirrer was purged wi-th nitrogen
and then charged with 1,000 ml. oE hexane, -then 1
mrn^~l. of -triethylal.uminum, 0.05 mmol. of dimethyl
diethoxy silane, 0.01 mmol. of diethylaluminum mono-
ethoxide and 10 mg. of the above solid catalyst compo-
ne1lt ~I~ were added and the temperature was raised
to 90C und~r stirring. ~ith the vapor pressure
1() o~ hexclne, the syste1ll was pressurized -to 2 kg/cm -G.
, hydrogen was introduced up to a total pressure
oE ~.8 kg/cm2-G and then ethylene was introduced up
to a total pressure oE 10 kg/cm2 G. In this state,
~olymerization was allowed to start, which was continued
Eor 1 hour while maintaining the internal pressure
o the autoclave at 10 kg/cm2 G. Thereafter, the
polymer slurry was transEerred into a beaker and
hexane was removed under reduced pressure to give
60 g. of a white polyethylene having a melt index
of 0.7 and a bulk density of 0.42. Catalytic activity
was 28,800cJ.polyethyleile/~.Ti-hr C21~4 pressure,
1,150g.polyet11ylene/c~.solid ilr-C2114 pressure. The
F.R. value of t11e polye-thylene was 7.4. The molecular
wei~ht distribution was extremely narrow as compared
with the following Comparative Example 4. Further,
the polymer particles proved to be superior in fluidity
- 26
and have an average particle diameter of 730~m.
Compara~.ive Example 4
Polymeriæation of ethylene was carried
ou~ in ti1e salne ~ay as in Example 4 except that the
diethylalumil1um monoet]-loxide was nQt used. ~s a
result, there was obtained 48 g. of polye-tl1ylene
having a melt ill(]eX of ().9 and a bulk density of
0.3~. Catalytic activity was 23,100g.po1yethylene/g.
'l'i~hr.C2Tl4 pressure, 920g.polyethylene/g.solid-hr-C2H~
l~ pres:~lre. 'I`hc F.~. value o~ the polyeth~lene was
. 1 .
~ample 5
(a) Preparation of Solid Catalyst Component ~I~
10 g. of a commercially available anhydrous
magnesium chloride, 2.0 g. of -titanium tetraisopropoxide
and 1.7 g. of isopropyl chloride were placed in a
stainless steel pot having a content volume of 400
ml. and containinc3 25 stainless steel ba]ls each 1/2
inch in diameter, and ball-milled for 16 hours at
2n room temperature in a nitrogen atrnosphere, to give
a solid ca-talyst component [I] containing 25 mg.
of titanium per gram thereof.
(b) Polyme1^ization
A 2-liter stainless steel autoclave equipped
27
with an induction stirrer was purged wlth nitrogen
ancl then charged with 1,000 lnl. of hexane, then 1
mlnol. oE trie~hylaluminum, 0.1 mmol. o~ diphenyl
diethoxy silane, 0.05 mmol. of diethylaluminum mono-
etl1oxide and 10 Ing. of t-lle above solid catalyst
component ~I~ were adcled and the temperature was
raised to 90C under stirring. With the vapor pressure
oC hexane, the system was pressurized to 2 kg/cm2-G.
'l`l1e~ ydl-oclel1 was :introduced up to a total pressure
l() Or 4.8 Icg/cm2-G and then ethylel1e was introduced up
to a tota:l pressure of 10 kg/cm2 G. In -this s-tate,
~olymerization was allowed to start, which was con-tinued
for 1 hour while maintaining -the -total pressure at
10 kg/cm G. Thereafter, -the polymer slurry was
transferred in-to a beaker and hexane was removed
under reduced pressure to afford 44 g. of a white
polyethylene having a melt index of 1.1 and a bulk
density of 0.38 Catalytic activity was 33,700g.
polyethylene/g.Ti-hr-C2ll4 pressure, 850g.polyethylene/g.
solid-hr-C2ll4 pressure. The F.R. value was 7.6 and
thus the molecular weigi1-t distribution was narrow.
Comparative ~xample 5
Polymeriza-tion of ethylene was carried out
in the same way as in ~xample 5 except that the
diethylaluminum monoethoxide was not used. As a
- 28
result, there was obtained 3S g. of polyethylene
having a me1t index of 0.9 and a bul]c densi-ty of
0.31. Catalytic activi-ty was 26,800g.polye-thylene/g.
Ti.hr.C2ll4 pr~ssure, 670~.polyethylene/g.solid-hr-C2H~
pressure. rl`he ~'.R. value was 8.2.
Example 6
~ vapor-pl1ase polymerization was carried
out Usil1g the solid catalys-t componen-t LI~ obtained
ill L;:~alllple 1. ~s the vapor-phase polymerization
I n aE~parcltus there was used a stainless steel autoclave,
ancl a loop was Eormed by a blower, a flow control
clev:ice and a dry cyclone. The temperature of -the
autoclave was adjusted by passing warm water through
its jacket.
Into the autoclave adjus-ted to 80C were
fed the solid catalys-t component ~I~ obtained in
Example 1, diethyl die-thoxy silane, diethylaluminum
monoethoxide and triethylaluminum at rat-s of 50
mq/hr, 0.25 mmol/hr, 0.05 mmol/hr and 5 mmol/hr,
respectively. Further, hydrogen and ethylene were
introduced while making an adjustment so as to ~ive
a hydro~en/ethylene mol ra-tio of 0.45 in the vapor
phase in the autoclave. ~t -the same time, the intra-
system ~ases were circulated by means of the blower
to maintain -the total pressure at 10 k~/cm G.
_ 29
Polymerization was carried out under these conditions
to give polyethylene having a bulk density of 0.36
and a melt index of 0.9. Ca-talytic acitivyt was
38~,000g.polyethylene/g.Ti. The F.R. value was 7.6.
Example 7
(a) Preparation of Solid Catalyst Component rI~
6.5 g. of a commercially available anhydrous
ma~nesium chloride, 1.5 g. of boron -triethoxide and
1.5 g. o;E titanium te-trachloride were placed in a
st~inless steel pot having a content volume of 400
ml. and con-taining 25 stainless steel ball each 1/2
inch in diameter, and ball-milled for 16 hours at
room temperature in a ni-trogen atmosphere, to obtain
a solid catalyst component LI~ containing 40 mg.
of titanium per gram thereof.
(b) Polymeriza-tion
Polymerization of ethylene was carried out
in the same way as in Example 1 except that 10 mg.
of the solid catalyst component tI~ prepared just
ahove was used.
As a result, there was obtained 166 g.
of a white polye-thylene having a melt index of 1.3
and a bulk density of 0.30. Cataly-tic activity was
79,800g.polye-thylene/g.Ti-hr C2H4 pressure, 3,190g.
polyethylene/g.solid hr-C2H4 pressure. The F.R.
3~ _
value of the polyethylene was 7.6.
Example 8
The ball mill pot of the same type described
:In ~Yample 7 was charyed with 10 g. of a commercially
available anhydrous magnesium chloride, 2.2 g. of
magnesium diethoxide and 2.3 g. of titanium -tetra-
chloride. The admixture was ball-milled for 16 hours
at room tempera-ture in a nitrogen atmosphere to obtain
a solid catalyst component ~I~ containing 40 mg.
oE titanlum per gram thereof.
Polymeriza-tion of ethylene was carried out
in the same way as in Example 1 except that 10 mg.
of the solid catalyst component ~I~ prepared just
above was used.
As a result, there was obtained 88.4 g.
of a white polyethylene having a mel-t index of 0.95
and a bulk density of 0.28. Catalytic activity was
42t500g.polyethylene/g.Ti-hr-C2H4 pressure, 1,700g.
polyethylene/g.solid hr C2H4 pressure. The F.R.
value of the polyethylene was 7.6.
_ 31
