CA1292978C - Catalyst system for high-temperature (co)polymerization of ethylene - Google Patents

Abstract

ABSTRACT

A catalyst system that is a combination of at least two com-ponents A and B, which components comprise:
A : one or more titanium compounds and one or more vanadium com-pounds, mixed with one or more organoaluminium compounds in such an amount that the atomic ratio of aluminium to the sum of titanium and vanadium is at least 3, B : one or more organoaluminium compounds, one or both of components A and B containing a chloride, and which two components are fed, separately or in combination, direct to the reaction vessel in such an amount that the atomic ratio of the chlorine from components A and/or B to the sum of titanium and vanadium of component A is at least o, is suitable for (co)polymeri-zation of ethylene and optionally minor amounts of 1-alkenes and/or dienes at high polymerization temperatures.

Description

` BtL/WP/mhd lZ9Z978 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 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 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 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 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 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~

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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" l;zs;~s~7a Compara~ive example 1 The catalyst ~as composed as sho~n ;n Table 3, and polymeri-zat;on ~as effected as ;n Example II.

. .
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.

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 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 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.

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.
:

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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Claims (32)

1. THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
   PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
   
   :1. A catalyst system for the polymerization of ethylene or copolymerization of ethylene with a minor amount of a l-alkene or diene at a temperature of at least 180°C, prepared from a combination of at least two components, A and B, which components comprise:
   A: one or more titanium compounds and one or more vanadium compounds, mixed with one or more organoaluminium compounds in such an amount that the atomic ratio of aluminium to the sum of titanium and vanadium is at least 3, B: one or more organoaluminium compounds, one or both of components A and B containing a chloride, and wherein the two components are combined for use in such an amount that the atomic ratio of the chlorine from components A
   and B to the sum of titanium and vanadium of component A is at least 6.
2. 2. A catalyst system according to claim 1, wherein the atomic ratio of aluminium from component A to the sum of titanium and vanadium is at least 5.
3. 3. A catalyst system according to claim 1, wherein the atomic ratio of chlorine to the sum of titanium and vanadium is at least 7.5.
4. 4. A catalyst system according to claim l, 2 or 3, wherein the atomic ratio of aluminium from component B to the sum of titanium and vanadium is at least 3.
5. 5. A catalyst system according to claim l, 2 or 3, wherein the atomic ratio of titanium to vanadium is less than or equal to 1.
6. 6. A catalyst system according to claim l, wherein the titanium compound is a compound of the general formula Ti(OR1)4-n X1nor Ti(OR2)3-mX2m, wherein R1 and R2 are the same or different and each represents a hydrocarbon residue with l-20 carbon atoms, X1 and X2 represent halogen atoms, 0 ? n ? and 0 ? m ? 3.
7. 7. A catalyst system according to claim 6, wherein the titanium compound is a titanic acid ester.
8. 8. A catalyst system according to claim 7, wherein the titanium compound is tetrabutoxytitanium.
9. 9. A catalyst system according to claim 1, wherein the vanadium compound is a compound of the general formula VO(OR3)3-p X3p, wherein each R3 is a hydrocarbon residue with 1-20 carbon atoms, each X represents a halogen atom and 0 ? p ? 3.
10. 10. A catalyst system according to claim 1 or 6, wherein the vanadium compound is vanadyl chloride or vanadylbutoxide.
11. 11. A catalyst system according to claim 1, 2 or 3, wherein the vanadium compound belongs to the compound of the general formula VX43 of VX44, where X represents a halogen atom.
12. 12. A catalyst system according to claim 1, 6 or 9, wherein at least half of the chlorine atoms present originate from component A.
13. 13. A catalyst system according to claim 1, 6 or 9, wherein component A further contains an additional chloride compound.
14. 14. A catalyst system according to claim 1, 6 or 9, wherein component A further contains an alkyl-, acyl- or aryl-chloride or a chloride of an element of group 3a or 4a of the Periodic Table.
15. 15. A catalyst system according to claim 1, 6 or 9, wherein component A or B further contain an electron donor.
16. 16. A catalyst system according to claim 1, 6 or 9, wherein the organoaluminium compound of component A is a compound of the general formula: R4qAlX3-q, wherein each R4 is the same or different and represents a hydrocarbon residue with 1-20 carbon atoms, X represents a halogen atom and 0 ? q ? 3.
17. 17. A catalyst system according to claim 1, 6 or 9, wherein the organoaluminium compound of component A is sesquiethyl-aluminium chloride or diethylaluminium chloride.
18. 18. A catalyst system according to claim 1, wherein the organoaluminium compound of component B is a compound of the general formula R5sAlY3-s, wherein each R5 is the same or different and represents a hydrocarbon residue with 1-20 carbon atoms, Y represents a hydrogen atom, a hydrocarbon residue with 1-20 carbon atoms, a group of the general formula -NR6 (wherein R6 is a hydrocarbon residue with 1-10 carbon atoms), or a group of the general formula -OR7 (wherein R7 is a hydrocarbon residue with 1-20 carbon atoms or a group of the general formula -Si(R8)3, wherein each R8 is the same or different and represents a hydrogen atom or a hydrocarbon residue with 1-20 carbon atoms), and 0 ? s ? 3.
19. 19. A catalyst system according to claim 18, wherein the organoaluminium compound of component B contains at least one aluminium-oxygen bond.
20. 20. A catalyst system according to claim 1, 6 or 9 wherein the organoaluminium compound of component B is a dialkylaluminium-alkoxide.
21. 21. A catalyst system according to claim 1, 6 or 9, wherein the organoaluminium compound of component B is an alkyl-aluminoxane.
22. 22. A catalyst system according to claim 1, 6 or g, wherein component B further contains a metal alkyl compound in addition to the organoaluminium compound.
23. 23. A catalyst system according to claim 1, 6 or 9, wherein in component A the titanium compound is a titanic acid ester, the vanadium compound is a vanadyl alkoxide or vanadyl halide, and the organoaluminium compound is an alkylaluminium halide, and in the compound B, the organoaluminium compound contains at least one aluminium atom bound to an oxygen atom, and an additional chloride compound is present which is fed to a reaction vessel for combination simultaneously with or prior to component A.
24. 24. A catalyst system according to claim 1, 6 or 9, wherein in component A the titanium compound is tetrabutoxy-titanium, the vanadium compound is vanadyl butoxide or vanadyl chloride, the organoaluminium compound is diethylaluminium chloride oquiethylaluminium chloride, and in component B
    the organoaluminium compound is alkylaluminoxane, dialkyl-aluminium alkoxide or a mixture of an electron donor with dialkyaluminium alkoxide or alkylsiloxalane, and component B
    additionally contains an alkyl, acyl or aryl chloride or chloride of an element of group 3a or 4a of the Periodic Table.
25. 25. A process for preparing a catalyst system according to claim l, comprising mixing the titanium and vanadium compounds with the organoaluminium compound from component A at a temperature below 125°C.
26. 26. A process according to claim 25 wherein the titanium compound is a compound of the general formula Ti(OR1)4-nX1n and/or Ti(OR2)3-mX2m, wherein each R1 and R2 is the same or different and represents a hydrocarbon residue with 1-20 carbon atoms, X1 and X2 represent halogen atoms, 0 ? n ? 4 and 0 ? m ? 3.
27. 27. A process according to claim 25 wherein the vanadium compound is a compound of the general formula VO(OR1)3-pX3p, wherein each R3 represents a hydrocarbon residue with 1-20 carbon atoms, each X represents a halogen atom and 0 ? p ? 3.
28. 28. A process according to claim 25, 26 or 27, wherein the titanium and vanadium compounds are mixed with the organoaluminium compound at a temperature below 75°C.
29. 29. A process for polymerizing ethylene or copolymerizing ethylene with a minor amount of a 1-alkene or diene comprising effecting the (co)polymerization at a temperature above 180°C
    in contact with a catalyst system according to claim 1.
30. 30. A process according to claim 29 wherein the titanium compound is a compound of the general formula Ti(OR1)4-nX1n and/or Ti(OR2)3-mX2m, wherein each R1 and R2 is the same or different and represents a hydrocarbon residue with 1-20 carbon atoms, X1 and X2 represent halogen atoms, 0 ? n ? 4 and 0 ? m ? 3.
31. 31. A process according to claim 29 wherein the vanadium compound is a compound of the general formula VO(OR3)3-pX3p, wherein each R3 represents a hydrocarbon residue with 1-20 carbon atoms, each X3 represents a halogen atom and 0 ? p ? 3.
32. 32. A process according to claim 29, 30 or 31, wherein polymerization is effected at a temperature above 200°C.