Note: Descriptions are shown in the official language in which they were submitted.
` BtL/WP/mhd
lZ9Z978
-1- AE 3687
CATALYST SYSTEM FOR HIGH-TEMPERATURE
(CO)POLYMERIZATION OF ETHYLENE
The ;nvent;on relates to a catalyst system for the
~co)polymerizat;on of ethylene and opt;onally minor amounts of
1-alkenes and/or d;enes, to the preparat;on of this catalyst system
and to the (co)polymer;zat;on of ethylene and opt;onally m;nor amounts
of 1-alkenes and~or d;enes.
There are numerous cataLyst systems that are capable of
br;ng;ng about polymer;zat;on of ethylene and/or 1-alkenes. Thus, for
instance, so-called Phill;ps and Z;egler-Natta systems can be d;s-
tingu;shed. Of these, a number relate to polymer;zat;on in the gas
phase. Oth~r~ aim at polymerization in the presence of a liquid dis-
persant. The latter can be subdivided into the so-called suspens10n
system, ~ith polymerization taking place at temperatures that are
bolo~ the temperature at which polyethylene dissolves, and the so-
called solution system, with a polymerizat;on temperature that ;s
h1gher than the temperatùre at wh;ch the formed polyethylene
d;ssolves. Solut;on polymerization requires spec;al catalyst systems
as the catalyst activ;ty and the molecular we;ght of the produced
polymer generally decrease ~;th increasing polymer;zat~on temperature.
It ~as not unt;l the end of the s;xt;es that a catalyst was developed
the act;vity of ~hich ~as such that solution polymeri2ation of ethy-
lene could be effected ~;thout having to remove catalyst residues from
o~b/~sJ~ J~ e q /9~1
1~ the product ~GB-A 1,235,062~
In general, polymerization takes place at temperatures that
are only l;ttle above the temperature at ~h1ch polyethylene dissolves,
because the act;vity of catalysts customar;ly appl;ed so far decreases
at h;gh polymer;zation temperatures. At unchanged residence t;me, thls
means that the polymer y;eld decreases, as a result of which the
129Z9 ~8
- 2 - 22772-1084
amounts of catalyst residues in the polymer increase and it soon
becomes necessary to wash out the polymer.
A problem in this exothermic polymerization reaction is
the dissipation of the heat of polymerization. Cooling through
the wall or by cooling devices in the reactor may easily lead to
polymer deposition on the cooling surfaces, especially at cooling
agent temperatures below 150C. For this reason, strong cooling
of the reactor feed was preferred. This, however, costs much
energy and will become more expensive as fuel prices rise.
Polymerization at high temperatures would entail energy
advantages also in another respect: not only can the strong cool-
ing of the reactor feed be reduced or even be done without, in
addition there no longer is any need to heat the product during
processing of the polymer in order to evaporate the solvent. The
rea~on ~or thi~ is that the heat of evaporation decreases or even
becomes zero as the solution temperature is higher and approaches
or even reaches or exceeds the critical temperature of the sol-
vent, and as a result the enthalpy of evaporation becomes mini-
mal.
For the above reasons there is much demand for high-
temperature catalysts. These catalysts should be so active as to
retain sufficient activity also at very high polymerization
temperatures (in excess of 180C). This requirement is rendered
even more severe by modern legislation, which imposes clear-cut
limits as regards the concentration of transition metals in
products. Moreover, the polymer produced is to meet the customary
-` iZ92~78
- 2a - 22772-1084
requirements as regards processability and applicability, which
implies the molecular weight must be sufficiently high, or the
melt index sufficiently low.
European patent applications EP-A 57050 and EP-A 131 420
(published August 4, 1982 and January 16, 1985 respectively)
describe catalyst systems that are active at very high polymeri-
zation temperatures.
The catalyst system of EP-A 57050 comprises the combina-
tion of two components, the first of which is prepared by heating
an organoaluminium compound, titanium tetrahalide and, optionally,
vanadium oxytrihalide for at least 5 seconds to at least 150C,
and the second of which is an organoaluminium compound. In EP-A
131 420 the first
- lZ92~;8
--3--
component is the same as in EP-A 57050, while the second is an alkyl
siloxalane. The various components of these catalyst systems are mixed
such that ;n the f;rst component the atom;c rat;o of alum;nium to
t;tanium plus vanadium is bet~een 0.2 and 2.0, and preferably more
titan;um than vanad;um is present. The optimum titanium : vanadium
ratio is 85 : 15. The atomic ratio of the alum;n;um from the second
component to t;tan;um plus vanadium ;s at most 3.
A d;sadvantage of these catalysts is that heating of the
first component or a portion thereof pr;or to comb;nat;on w;th the
second component requ;res extra energy and ;s labor;ous. For
;ndustr;al-scale polymer;zat;on, streaml;n;ng of the process ;s of
pr;me ;mportance. Intermed;ate heat;ng of a port;on of the catalyst
system ~ould ;nterfere w;th this objective. In addit;on, a precipitate
is formed on such heating, ~hich may result ;n problems w;th the cata-
lyst feed to the reactor~
The ;nvent;on aims to f;nd a cata~yst system not having theabove-ment;oned d;sadvantages ~ithout sacrific;ng act;v;ty or the
capability of form;ng large polymer molecules at very high polymer~za-
tion temperatures.
It has, ~urpris;ngly, been found tha~ a catalyst system that
i5 a comb;nation of at least t~o components, A and B, ~hich components
compr;se:
A : one or more t;tan;um compounds and one or more vanad;um compounds,
m;xed ~;th one or more organoalum;n;um compounds ;n ~uch an amount
that the atomic ratio of alum;n;um to the sum of t~tan;um and
vanad;um ;s at least 3,
B : one or more organoalum;n;um compounds,
one or both of components A and B conta;ning a chloride, and ~hich t~o
components are fed, separate~y or ;n combinat;on, direct to the reac-
tion vessel ;n such an amount that the atom;c rat;o of the chlorlne
from components A and/or B to the sum of titanium and vanadium of com-
ponent A is at least 6, is su;table for ~co)polymerizat;on of ethylene
and optionally minor amounts of 1-alkenes and/or dienes at very h;gh
- polymer;zat;on temperatures.
lZ9Z9 78
- 4 - 22772-1084
An advantage of a catalyst system according to the in-
vention is that very high temperatures can be used to produce
poLyethylene that meets the customary requirements as regards
processability and applicability and that contains such a small
amount of catalyst residues that washing out of the product is not
necessary.
The catalysts according to the present invention not
only are very active, but also very rapid, so that very short
residence times will suffice. A short residence time has the
great advantage that a small reactor may be used. Thus, in a 5 m3
reactor an annual production of more than 50,000 ton can be reach-
ed when using the catalysts according to the invention.
Using the 6ubject cataly~t~, re~idence times of 10
minutes or less will ~uffice. At re idence times of 5 minutes the
yields still are so high that no treatment for washing out the
catalyst residues need be applied.
Yet another advantage is that components A and B are fed
direct to the reaction vessel, that is, without further heating
above 150C or recovery of a precipitate. Such additional opera-
tions even have an adverse effect on the catalyst system accordingto the invention.
The residence time of the various catalyst components in
the feed lines on the whole is sufficient for obtaining an active
catalyst system. In most cases this residence time will not be
more than some, for instance 5, minutes; often it will even be
less, for instance less than 3 or even less than 1 minute.
lZ9Z978
- 4a - 22772-1084
However, a longer residence time, though economically
unattractive, in itself is not disadvantageous for the catalyst
according to the invention. If for certain reasons it should be
desirable to allow the combined catalyst components to stand for
some time, for instance in the case of batch-wise polymerization,
this does not entail a reduction of activity.
Catalysts that are built up of two components are des-
cribed in for instance, DE-A 2600336 and DE-A 1934677 (published
July 21, 1977 and January 29, 1970 respectively). In both of
these patent applications the component containing transition
metals is prepared via complicated intermediate steps, after which
the precipitate
29~8
formed is recovered and thoroughly washed. These catalysts are
intended for suspension polymerization and they are hardly active
at polymerization temperatures in excess of 180C. The polymers
produced using these catalysts, in addition, have such a high
transition metal content as to necessitate washing out of the
product. The catalyst systems according to the invention not only
take less time to prepare, they also have a higher activity, with
all associated advantages.
Catalyst systems according to the invention are most
active at an atomic ratio of aluminium from component A to the sum
of titanium and vanadium of at least 5. It is to be recommended
for the atomi~ ratio of chlorine to the sum of titanium and
vanadium to be at least 7.5, in partiaular at least 9. A further
increase in activity is achieved at an atomic ratio of aluminium
from component B to the sum of titanium and vanadium of at least 3.
Further, an atomic ratio of titanium to vanadium of at most 1, and
in particular of at most 0.8, is to be preferred.
Usually, the atomic ratios of aluminium to the sum of
titanium and vanadium, of chlorine to the sum of titanium and
vanadium and of aluminium from component B to the sum of titanium
and vanadium will not exceed 100:1, in particular 50:1, The
atomic ratio of titanium to vanadium will usually be at least
0.001 : 1, in particular, 0.01 : l.
As titanium compounds, both trivalent and tetravalent
compounds of the general formula Ti(ORl)4 nXln and Ti(OR )3 mX2m,
respectively, in which Rl and R2 are equal or different and
represent hydrocarbon residues with 1-20 carbon atoms, X and X
-`" 1;29Z9~78
- 5a -
halogen atoms, O $ n ~ 4 and O ~ m S 3, ~ield good results. Of
these compounds, titanic acid esters such as tetrabutoxytitanium
are to be preferred. Titanium complexes such as, for instance,
TiCl3.3 decanol, TBT.AlCl3, TBTØ2 Cr(acac)2, TBT. x CrO3 and
TBT.x diethylzinc (O ~ x ~ l) can also be applied. (see list
of abbreviations on p. ll).
Likewise, use can be made of compounds such as, for
instance, cresyl titanate polymer ~CH3C6H4[Ti(OC6H4CH3)20]aC6H4
CH3, a ~ 1).
As vanadium compounds, use can be made of compounds of
the general ~ormula VO(OR )3 X , where R3 represents a hydro-
carbon residue with 1-20 carbon atoms, X3 a halogen atom,and
0~ p ~ 3, in particular vanadyl chloride and/or vanadyl butoxide.
It ts also possible to use vanadium compounds of the general
ormula VX43 or VX44, where X4 represents a halogen atom. X4
preferably is a chlorine atom. Mixtures of titanium compounds
or vanadium compounds can also be used as catalyst ingredients,
-6- 129Z~
The role played by chlor;de in th;s complicated catalyst system is not
quite clear. Optionally a predominant portion of the chlorine atoms
or;ginates from component B, but it has been found that the catalyst
yields better results ~hen at least half of the total amount of
chlorine atoms present originates from component A. For this reason,
;t is to be recommended that component A also comprises one or more
chlorides. These are, for instance, alkyl chlor;des, acyl chlor;des,
aryl chlor;des, inorganic chlorides, or comb;nations thereof. Pre-
ference is to be given to isopropyl chloride, benzyl chloride and/or
chlorides of elements of the groups 3a and 4a of the Periodic System
(Handbook of Chemistry and Physics, 52nd ed.), in particular SiCl4 and
BCl3 An active catalyst yielding a high polymer molecular ~eight,
also at very high polymerization temperatures, is also formed ~hen
component A furthermore compr;ses one or more electron donors (Le~is
bases) such as, for instance, DEA, EB, IPA, acetyl acetone and/or MPT.
(Reference is made to the list of abbreviations used, ~hich is given
on page 11).
The organoalum;nium compound of component A may be chosen from a large
~roup of compoùnds, 1ncluding alkyl siloxalanes. Preference is g1ven
to an organo-alumin~um compound hav~ng the general formula R4qAl
~here the symbols R4 are equal or different and represent a hydrocar-
bon res;due w;th 1-20 carbon atoms, ;n part;cular alkyl, X5 represents
a halogen atom, in part;cular chlorine, and û ~ q ~ 3. M;xtures may
also be applied. ~hen applying, for instance, trialkyl aluminium com-
Z5 pounds ;t i5 recommendable to increase the chlor;ne content of com-
ponent A by add;t;on of a chlor;de and/or by selecting the titaniumand/or vanadium compounds such that these can serve as chlor;ne
source.
Examples of organoa~uminium compounds of component A are
DADHMS, DADS, DEAC, MEAC, MMAC, SEAC, SMAC, TEA, TIBA, TMA. In par-
ticular DEAC and/or SEAC y;eld good results. (See list of abbre-
viat;ons on page 1~.
The organoaluminium compound of component B may be the same
as that of component A, but th;s need not be so. A good result is
obtained ~hen applying compounds ~ith the general formula R5sAlY3_S,
l~9Z978
where the symbols R5 are equal or different and represent a hydrocar-
bon residue ~ith 1-20 carbon atoms, Y represents a hydrogen atom, a
~ ~f c ~e~a~ / o~
hydrocarbon residue ~ith 1-20~carbon atoms, a group having the general
formula -NR6 ~here R6 ;s a hydrocarbon residue ~ith 1-20 carbon
atoms), or a group having the general formula -oR7 (~here R7 is a
hydrocarbon res;due uith 1-20 carbon atoms or a group having the
general formula -Si~R8)3, ~here the symbols R8 are equal or different
and represent a hydrogen atom and/or a hydrocarbon residue ~ith 1-20
carbon atoms), and o ~ s ~ 3.
In part;cular compounds ~ith an alumin;um-oxygen bond have a
good activity. In addition, an alkyl aluminoxane ~a compound of the
general formula R2Al-COAl(R)~b-OAlR2, ~here the symbols R are equal or
different and represent a hydrocarbon residue ~ith 1-10 carbon atoms,
and b ~ O) can also be applied as component B ~ith good results. Mix-
tures may also yield good results.
A further increase ;n act;vity is achieved ;f, besides the
organoaluminiu~ compound~), one or more other metal alkyls are added
to component B such a~, for instance, d;alkyl^magnesiu~-, d;alkyl
zinc-, trialkylboron-, al~yl l;thium compounds. Examples of organoalu-
minium compounds of component B are: methylaluminoxane, DADHMS, DADS,DATPS, DEAC, DEAH, DEALOX, IPRA, MEAC, SEAC, TEA, TIBA, TIBAO, DIBBA,
DIBAH, TOA. tSee the list of abbreviations on page 11)~
600d results are obtained especially when component B in addit;on
comprises one or more electron donors (Lewis bases) such as E~, IPA,
MPT, decanol, PMHS.
If desired, a chloride may also be added to component B.
Catalyst systems according to the reactor may be fed to the
reactor separately or in comb;nation. Ho~ever, a better result is
obtained ~hen components A and B are separately fed to the reactor.
When components A and B are fed separately to the reactor, it is imma-
terial in ~hat order this ;s done. The sequence ;n wh;ch the ingre-
dients of the components themselves are m;xed ;s not-very ;mportant,
eitherO
As regards component A, for insSance, first a titan;um and a
vanadium compound can be mixed, then an organoalum;nium compound can
`" ~Z92978
-8-
be added and finally, optionally, a chloride and/or an electron donor.
The organoaluminium compound may also first be mixed ~ith a chloride
and subsequently ~;th a titanium and a vanadium compound. It is also
possible to add the organoalum;nium compound to one of the transition
metal compounds before the second transition metal compound is added.
It may be preferable to mix the vanadium and t;tan;um compounds ;n
advance, especially ~hen on of them ;s less stable, such as VOCl3.
It ;s recommendable to m;x the trans;t;on metal compounds
~;th the organoalumin;um compound at a temperature belo~ 125~C, ;n
part;cular belo~ 75~C, more ;n part;cular belo~ 50~C. In general the
temperature ~;ll not be below -60~C.
As regards component 3, here too the sequence of m;x;ng, ;f
any, can freely be determ;ned, ~ithout the g;v;ng r;se to a s;gn;f;-
cant deter;orat;on of catalyst activ;ty.
It can be sa;d for both component A and component B that the
presence of absence of monomer~s) during m;x;ng of the catalyst ;ngre-
d;ents has little effect on the catalyst act;v;ty.
It ;s also poss;ble to feed a th1rd component to the reactor
bes;de~ component~ A and 8. Th;s th~rd component may be a chloride
and/or electron donor, in particular a chlor;de or aryl or alkyl or an
element of groups 3a and 4a of the Periodic System, or an organoalumi-
n;um chlor;de.
The ;nvent;on a~so relates to polymers obta;ned by means of a
catalyst accord;ng to the ;nvent;on. These polymers compr;se ethylene,
one or more 1-alkenes with 3 to 18 carbon atoms ;n an amount of O to
15 mole.X relative to the total polymer, and one or more dienes ~ith
at least 7 carbon atoms in an amount of O to 10 mole.X relative to the
total polymer. In particular polymers ;n ~h;ch the dienes contain at
least t~o non-conjugated double bonds capable of be;ng polymer;zed by
means of trans;t;on metal catalysts, and in ~h;ch the amount of d;enes
does not exceed 0.1 mole.% relative to the total polymer, have good
properties.
Polymers according to the ;nvent;on may conta;n the customary
addit;ves, such as stab;l;zers, lubr;cants, etc., and also, for
;nstance, crossl;nk;ng agents and f;llers.
129Z~ ~8
_9_
Polymers obtained by means of a catalyst according to the
invention possess the customary propert;es that are commercially
des;red, such as a sufficiently high molecular ~eight tlow melt index)
and good processability. They can be used for the preparation of cast
f;lm and blo~n f;lm having good mechan;cal and opt;cal properties,
~hile also the rheological and ~elding properties meet the normal
- requirements. The polymers are also suitable for many other customary
applications, e.g. injection mould;ng and rotational moulding.
Polymerization can be effected in a manner kno~n in itself,
both batchwise and continuous. ~n general the catalyst components,
prepared in advance, are added in such amounts that the amount of
titanium in the polymerization medium is 0.001 to 4 mmol/l, preferably
O.OOS to 0.5 mmol/l, and more in particular 0.01 to O.OS mmol/l.
As dispersing agent, both ;n the catalyst preparation and in
the polymerization, use can be made of any liquid that is inert rela-
tive to the catalyst system, for instance one or more saturated,stra;ght or branched al;phat;c hydrocarbons, such as butanes, pen-
tanes, hexanes, heptane~, pentamethylheptane or petroleum fractionssuch as light or regular-grade petrol, ;sopar, naphtha, kerosine, gas
oil. Aromatic hydrocarbons, for ;nstance benzene or toluene, can be
used, but both because of the cost price and for safety considerations
such solvents ~ill generally not be applied in technical-scale
production. By preference, therefore, ;n technical-scale polymer;za-
tions as solvent use is made of the cheap al;phat;c hydrocarbons or
m;xtures thereof, as marketed by the petrochem;cal ;ndustry. Pretreat-
ment of such solvents, for instance drying or pur;ficat;on, is oftenrequired. This ~ill present no problems ~hatsoever to the average per-
son skilled in the art. Cyclic hydrocarbons, such as cyclohexane, canof course also be used as solvent.
By preference the polymerization is effected at temperatures
above 18ouc~ especially above 200~C, and more in particular at tem-
peratures above 220~C. For practical cons;derat;ons the temperature
~ill generally not be higher than 300~C.
The polymer solut;on obtained upon polymerizat;on can subse-
quently be recovered ;n a way kno~n ;n itself, the catalyst generally
1~9Z~78
-10-
be;ng deact;vated at some stage of the recovery. Deactivation can be
effected in a ~ay kno~n ;n itself. The catalysts accord;ng to the pre-
sent ;nvent;on are so active that the amount of catalyst ;n the
polymer, notably the trans;t;on metal content, ;s so lo~ that removal
of catalyst res;dues can be done ~;thout. Of course the polymer can be
subjected to a ~ashing treatment so as to further reduce the residual
content of catalyst components, ;f th;s is deemed necessary.
Polymer;zat;on can be effected under atmospher;c pressure,
but also at elevated pressure, up to about 1000 bar, or even h;gher,
both ;n cont;nuous and ;n d;scont;nuous manner. By effecting the polyo
mer;zat;on under pressure, the polymer y;eld can be ;ncreased further,
~hich may contribute to the preparation of a polymer having very lo~
contents of catalyst residues. It is preferred to polymerize at
pressures of 1-200 bar, and more in part;cular of 10-100 bar.
Pressures ;n excess of 100 bar soon g;ve rise to tech-
nological objections. Much h;gher pressures, of 1000 bar and more, can
ho~eve~ be used if polymeri2ation ;5 effected ;n so-called h;gh-
prossure reactors.
In the sub~ect process mod;fications kno~n ;n ;tself can be
appl~ed. Thus, for ;nstance, the molecular ~eight can be controlled byadd~tion of hydrogen or other customary modifying agents. Polymeriza-
tion can also be effected ;n various stages, connected e;ther inparallel or in ser;es, ;n wh;ch, ;f des;red, d;ffer;ng catalyst com-
pos;t;ons, temperatures, res;dence t;mes, pressures, hydrogen con-
centrat;ons, etc. are appl;ed. Products with a broad molecular ~eight
distribut;on, for instance, can be prepared by select;ng the con-
ditions in one stage, for instance pressure, temperature and hydrogen
concentrat;on, such that a polymer ~ith a high molecular ~eight ;s
formed, ~h;le the cond;tions ;n another stage are selected such that a
polymer ~ith a lo~er molecular ~e;ght ;s formed.
The ;nvention ~ill no~ be elucidated ~;th reference to some
examples, w;thout, ho~ever, be;ng restr;cted thereto.
129297~
-11-
L;st of abbreviat;ons used:
- Acac = acetyl acetonate
- Alox = methylaluminoxane
- BP = benzophenone
- BzCl = benzyl chlor1de
- DADHMS = diethylalumin;um d;hydromethyls;loxide
- DADS = d;ethylalumin;umdimethylethylsi~oxide
- DATPS = diethylalum;nium triphenylsiloxide
- DEA = diethy~amine
- DEAC = diethylaluminium chloride
- DEAH = diethyla~uminium hydride
- DEALOX = diethyla~uminium ethoxide
- DEZ = diethyLzinc
- DPDMS = diphenyldimethoxysi~ane
- DIBAH = d;isobutylalum;nium hydride
- DIB8A = diisobuty~-1-buten-1-ylaluminium
- EB = ethyl benzoate
- EN 2 ethylenediam1ne
- IPA - i w propyl alcohol
- IPCl 5 i w propyl chloride
- IPRA - ;soprenyl alumin;um
- MEAC ~ monoethyl aluminiumd;chloride
- MMAC = monomethyl aluminiumdichloride
- MPT = methylparatoluate
- PMHS = polymethylhydros;loxane
- SEAC = sesquiethylaluminiumch~oride ~ethyl1~sAlc~1 5)
- SMAC = sesquimethyla~uminium chloride (methyl1,sAlC~1,5)
- TaOT = tributoxyoleyLtitanate
- TBT = tetrabutoxytitanium
- TEA = triethylaluminium
- TEB = triethyl boron
- TPS ~ triphenylsilano~
- TIBA ~ tr;;sobutylaluminium
- TIBAO = tetraisobutylaluminoxane
35 - TIPT = tetraisopropoxytitanium
- TMA = trimethylaluminium
- TOA = trioctylalum;n;um
- YB = vanadyl butoxide
-12- 129~9 f ~
Fxample I
Polymerizat;on exper;ments ~ere conducted at 24û~C ;n a
1-litre gas-l;quid reactor ~ith 500 ml purif;ed and dried pen-
t.amethylheptane (PMH) as d;spers;ng agent and ethylene to a reactor
pressure of 17 bar. The ;ngred;ents of the catalyst components were
separately prem;xed ~n PMH at 25~C during 1 minute, and subsequently
the catalyst components were separately pumped into the reactor
~unless ;nd;cated otherw;se). Table 1 sho~s the sequence in which the
ingrédients of the catalyst components ~ere mixed and in what con-
centrat;on they were present dur;ng polymerizat;on t;n mmol/l). Thepolymer;zat;on t;me was 10 minutes. The polymer ~as stabilized, if
necessary, dr;ed and ~eighed. The result ~as expressed in 9 polymer
per mmol titan;um ~ vanadium. The act;v;ty a of the catalyst system ;s
expressed as g PE/mmol ~T; ~ V). 10 m;n.
The melt ;ndex ~M.I.) of the polymer, expressed ;n dg/min, ;s deter-
mined in accordance with ASTM D 1238, cond. E.
The catalyst components were m~xed as ind~cated ;n Table 2.
The catalyst preparat~on and the polymerization were effected ;n the
same way as ~n Example I, no~ however at a reactor pressure of 8 bar.
Notes ;n the tables:
1) Component B was f;rst fed to the reactor, then component A.
2) Components A and B were m;xed pr;or to being fed to the reactor.
3) Et stands for ethyl.
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-17-
Compara~ive example 1
The catalyst ~as composed as sho~n ;n Table 3, and polymeri-
zat;on ~as effected as ;n Example II.
TABLE 3
. .
5 Exp.No Component A Component B a MI
,, . . .. _ . . . _
1 0.1 DEAC/(0.075 T;Cl4 ~ 0.025 VOCl3) 0.28 TEA 374 0.46
2 0.1 DEACI(0.04 T;Cl4 ~ 0.06 VOCl3) 0.28 TEA 347 0.72
3 0.1 DEAC/(0.075 TBT + 0.025 VOCl3) O.Z8 TEA ~ 50
4 0.2 DEAC/(0.075 TBT + 0.025 VOCl3) 0.28 TEA 152
0.1 DEAC/(0.04 TBT ~ 0.06 VOCl3) 0.28 DADS -~ 50
--- 6 0.2 SEAC/0.04 TBT/0.06 VB/0.2 BzCl 0.4 DADS C 50
Comparative example 2
Component A ~as prepared by stirring 9 mmol TiCl4 and 9 mmol
VB dur~ng 2 hours in 10 m~ PMH ~n a ~lass ves~el under nitro~en, the
temperature be~n~ 60~C. Subsequently 27 mmol SEAC ~as added drop~ise
at 20~C, and the m;xture wa~ st~rred dur1ng three hours at 20~C. After
decantat10n, the precipitate ~as ~a~hed 6 times ~ith 40 ml PMH.
Of th;s suspens~on such an amount ~as fed to the reactor that
the tota~ concentration of transition metals ~as about 0.1 mmol/l.
Polymerization was further effected as ;n Example II at 200~C and
240~C.
The results are presented in Table 4.
TABLE 4
Exp.No. Component B Temperature a ~.I.
1 0.4 TEA 200~C 185
2 0.4 TIBA 200~C 130
3 0.4 TEA/ROH 200~C 160
4 0.4 TIBA 240~C ~ 50
0.4 TEA/ROH 240~C ~ 50
9Z9'78
-18-
Comparative example 3
Component A was prepared by treating 9 mmol TBT, 9 mmol VOCl3
and 27 mmol SEAC as in Comparative example 2. With 0.4 mmol DEALOX as
component B and polymerizat;on cond;t;ons as ;n Example II, the cata-
lyst ~as not act;ve.
Comparat;ve example 4
Component A was prepared by treat;ng 4.5 mmol TiCl4, 4.5 mmol
VB and 54 mmol SEAC as in Comparative example 2. The catalyst, w;th
0.4 mmol/l DEALOX as component 3 and polymer;zation condit;ons as in
example II, was not act;ve.
Comparative example_5
Component A was prepared by treating ~2 mmol T8T ~ 3 mmol VB
+ 10 mmol BzCl) ahd 30 mmol SEAC as ;n Comparative example 2. With 0.4
mmol/l TEA as component B and polymerizat;on condit~ons as ;n Example
II, an ac~t~v~ty of 341 was ach~eved.
Comparat~ve example 6
Componen~ A was prepared by dropw;se add;t;on to 12 mmol SEAC
at 25~C of a soLut~on of 5 mmol T8T ~ 5 mmol VOCl3, which had been
aged for 4 days. The resultant suspens;on was f;ltered off and the
sol;d matter washed and dr;ed. After this, 2.73 9 of the sol;d was
added to 1.58 9 T;Cl4 in 10 ml hexane. The prec;p;tate formed after 3
hours' react;ng at 25~C was recovered, ~ashed, dried and resuspended.
Polymer;zat;on further was effected as in Example II, with
such an amount of the suspension that the totaL concentration of tran-
sition metals was about 0.1 mmol/l. As component B use was made of 0.4mmol/l TEA or 0.4 mmol/l DEALOX. In neither case was the catalyst
act;ve.
Comparative example 7
Component A was prepared by react;ng a t;tan;um and a vana-
d;um compound, as ind;cated in Table 5, ;n PMH at room temperaturewith DEAC. After m;x;ng for 40 seconds at room temperature, the m~x-
9Z9~78
-19-
ture ~as heated to 185~C for 1.5 m;nutes and fed to the reactor. Sub-
sequently TEA or DADS ~as fed to the reactor as component B, as indi-
cated ;n table 5. Polymerization further was effected as in Example
II.
TABLE 5
Exp.No. Component A Component B a MI
1 0.1 DEAC/tO.075 TiC 4 ~ 0.025 VOCl3) 0.28 TEA 450 0.45
2 0.1 DEAC/~0.04 TiCl4 ~ 0.06 VOCl3) 0.28 TEA 448 0.60
3 0.1 DEAC/Co.o4 TiCl4 ~ 0.06 VOCl3) 0.28 DADS 239
4 0.1 DEAC/~0.075 TBT ~ 0.025 VOCl3) 0.28 TEA ~ 50
0.1 DEAC/tO.075 TBT ~ 0.025 VOCl3) 0.28 DADS C 50
6 0.1 DEAC/~0.075 TBT ~ 0.025 VB) 0.28 TEA ~ 50
7 0.1 DEAC/~0.075 TaT ~ 0.025 VB) 0.28 DADS ~ 50
8 0.6 SEAC/tO.04 TiCl4 ~ 0.06 VOCl3) 0.2 TEA 255 0.8
9 0.6 SEAC/tO.04 T~Cl4 ~ 0.06 YOCl3) 0.4 TEA 352 0.5
0.6 SEAC/~0~04 T~Cl4 ~ 0.06 VOCl3~ 0.3 DADS 466 0.5
e III
Component A wss prepared by mixing the ;ngredients listed in
Table 6 at the temperatures sho~n in the same table. To this end, the
PMH in ~h;ch the in~redients were mixed ~as in advance brought at the
indicated temperature. Other~ise the process of Example 1 ~as adhered
to. As component B, 0.4 mmol/l DADS ~as used.
:
TABLE 6
Exp.No. Component A temperature ~C) a
__
1 0.6 SEAC/0.04 T8T/0.06 VB 30 1284
2 0.6 SEAC/0.04 T~T/0.06 VB 40 1100
3 0.6 SEAC/0.04 TBT/0.06 VB 50 844
4 0.6 SEAC/0.04 TBT/0.06 V8 60 838
0.6 SEAC/0.04 TBT/0.06 VB 70 ns
-' 129Z978
~ -20-
Examp~e IV
_
Using catalyst systems as listed in Table 7, ethylene-octene
copolymerizat;ons ~ere effected as in Exanple I. Pr;or to the ethy-
lene, t-octene ~as fed to the reactor in the amounts (;n ml) g;ven ;n
Table 7. The dens;ty of the polymer in kg/m3 ~as determined in accor-
dance ~ith ASTM D 1505.
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