DE1770240A1 - Process for the polymerization of ethylene, possibly in a mixture with other? -Olefins - Google Patents

Description

VEBA ·· C IJ K η 1 F Akt j on. ¹ WuGlIi :; ch a ft

Process for the polymerization of ethylene, given from in the mixture rr.with other ./. "Olefins

The invention relates to a method for polymerization voti Ethylene, possibly in a mixture with other ./../ olefins: i, lt. Catalysts made on the one hand by means of aluminiuniorgani already compounds reduced titanium-vanadium compounds and organometallic compounds Compounds of I. to III. Group of the Periodic Table of the Elements on the other hand. The procedure is particular characterized in that the catalyst concentrations are very low and a certain ethylene partial pressure is observed viivd.

It has already been proposed to use the reaction mixture of titanium-vanadium compounds and organometallic compounds directly between the polymerization of - ', - olefins. An isolation of the reaction product and use of the same with another ^ - metal organic compound is not provided. The catalyst does not show any high activity, large amounts of transition.wcital.1 compound, approx. 600 mg / kg polyethylene, have been consumed.

It 3 egg. also known, the Polymerisat.Lon / on Ολο f inen in the presence of a Katalycatorsyste!; ic; : - '. u lead because :, from a by hedaction of a mixture of TiCl ,, and VOCJ-, with a Λ Ium Ii o;' - i-trialkyüj possibly in BPV atmosphere, obtained unl csl.1 without precipitation in quantities from 600 mg / l to an organometallic compound, c: e · Compound of a metal from groups I to 111 of the Pevi odcncy.-tci in amounts of at least 100 mg / l of the weighted grades for polymerization Solvent manufactures. The lower limit of Katalyr.atorvcr consumption of metal! Organic is about ¹ Verbinouiig ό g / kg

^ioly '^{> ithy} "^{; ri} · ^ 109841 / U28

Documents iArt 7 Ϊ1 Abe. 2 No. 1 Sau 3 de · Äiuküungeges. v. 4th ft, 186?)

6AD ORIGINAL

According to Vor. ;; - j hi age η weio'cn bei dor Po 'ymeri. .sr: ti on of olefins the kata! ; /~atorkonzentrv.t.ionen in: -bo more solid the amounts of titanium-Vanad.iι compound to be used iicoh wide ¹ "reduced.

However, the polymers produced in this way contain j. t, i'ci-u-sr i:; t in the manufacture: .- to.llung the polymer e- partly the Gegenev.v.rt the f3clr .. 'ieri ^ to be handled DortrijluorjdH necessary.

He; t'.Trdo now surprisingly round that in the polymerization of olefins untcM ¹ / mv / endunr =; middle press the metal or | _ ;? in.! cfil'.e Kompoiiente be l lowered not only below 100 RNSS / Tower, iiouat: rn while still a Vf rrini ;;; _r-un:; who will: JCatalyst consume or're.i ent. I3f \ l AbEenknt'i ^ the concentration of the inetallorganiiichen KnriipDUftte from 1000 fi \ £ / l to 50 nig, / l the catalyst consumption sank un -l ^r j '' [.. Eis v: ar not 7, u vervrarten that with this low con- · zcii'-i: .x'.ion to n; cti) l organic component still have a Po 1.> ίϊι '.- ■■ · i nation takes place!.

Oo = -; enr; .t,. 'Nd de? ¹ invention, is therefore a process for the polymerization of να; "? Ethylene, optionally in a mixture with other <L · olefins, under V? Fvcnduni; of b'nvj. ^ Λ-0 east catalysts suspended in inert diluents, which (Λ ) by reaction and reduction of Gtrni look titanium · (IV) and vanadium (V) compounds with alüir; Jmu; UJR />: uiineher; Vorbindungen the formula

Al W ₀ X

heiTX ■ - '* · ■' A It v / o ^ .ir. / i are, where R is a hydrocarbon with a C number 1 of °. bin C> and X is halogen, alkoxy, mercapto groups or hydrogen, and (B) organometallic compounds of I to III. Main group of the periodic table of the elements, characterized in that during the polymerization

a) the concentration of the titanium vanadium catalyst 0.1 to ? 5 mg / 1

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SAD ORIGJNAl

17702A0

b) the concentration cic.-rnc-tallorsani:; elu: n verb. ', riiung 10 bi 100 ma / 3

c) the iithyler partial pressure ';) to t'O kp / un "is.

As Titan- (I7) -Yerb5nciur>t> on :: ind inisbejondere TJ tantetraehl ογκ <uiu * / o'ior Titan. ^c viuretotracf3ter naeig-itit. From ciei>v> uiad: in-Serbingen is inr.t -soiiorro Vanadin. '»;=:;? ·. c} i.1nvjd £, cc "^ i) '.;! ..

The effect that with «« ->'Vorrijii erunr: der Konzcn ^ i-rai-ioa dor;: .- tr: l organic Koinpor) € nrc dcfs]; a1, rü ysalov ^. i .- '. üt bo-lcctonde iU.o ijcru der K: ita] .v.' ::. *. i.oraktivitilt enters, \ ji »"-; i in nash ver :: t) ii-kto: T · . "-. 'I ■ ?. observe-, v / cnn uiitcr Aur. £? c-hjuii by V. ^! :; o: -fr: 3koi'f i; a rbt; äi - .: t i .-. ir'i.

After.! eri'indnn ^ rj ^ .anr.ficn procedure with the claimed] '. atfäly ~ satorkon.ient .. 'tit ions result in t tv.-Λ fblr, · "^ · *: · tierin ^ uro Katni vsatoivorbräuoln "":

about 1.13 to 94 RUi &quot;boryanKSiretanvt.-i'oin iunj / l: ^, polyethylene about 180 to 870 mi. netalloiViarn srhe Vcrrbjnduii-ykp, Po? .yMt / i ;;. 1 ^ n

r>.-;; ^: . errindui! ßr .. ^f 5crnäi3e Vcri'olu ti = 3. "t before-tcilhr.l't Γ.ον. ^τ ο · ': 1 hj. similar to the polymerization as well as the egg':; ieH: c: i Products.

For the Polymerisatjonsveri> .hren koinrncn rr-.iv gerlnr.cte Mer-fx-n cn metallor ^ anisohcr connection and Übermal · j; s - etall vi.vb üidun; ^ -zu · -. Income. The catalyst zQ-i ^ v. trot: 5clf .- ;: i hono activity, the resulting polymers contain only extremely ^ evirif-c Ivat-il; ·. ' ¹ : - '' torrent ο, an "aehbPhandJu'.ij ;;;: wr Enti'cm'.ir ^". the K "taly.v-atoron au .: dem Polyr: o." isat is above all researchable. At '. \ ^T e-, f';; li joglj nlv :: r Aufarbeitun ^ snr.Snainnort result nioh miniiir.'U? Gthaltn ί.η Kataly ^ itorresten.

The polymerization products Neir; ea at / the presowing an increased resistance to aging sov, ie a good FarbstaVo.licät. In the processing pp .- 'vschinor. If there is no corrosion <iU ^r , then rla.1 · cebräuchliclie 7 / αΰ'11ζν to prevent coviosion. v; ie 7 .. B. Calciunstearate, the ci't for disturbances /'n?.ass £ cne:>, omitted

109841 / U28

BAD ORiülNAL

&> .- ■ :. iC-ri.

Ivin v.Yjxterer advantage can be seen in the fact that by lesser EAn:;?.! ^; ee-v expensive aluminum alkyl compounds "more economical can be worked.

ίί '.: i do ») method according to the invention can. ^ ur regulation of the Mo Igevjjeht ::. the agents commonly used in Ziegler polymerizations v.'f: rden, such as B. hydrogen, zinc alkyl compounds, etc. ?.

Ali; Vordiinjinn-.nviittcl v.'erdon the inert ones known for this purpose Liquids, such as B. aliphatic, cycloaliphatic and aro :: iat 1 üche KoIiI enwa siior Ht ο ff e ingoset zt.

The raging Boiopielo are supposed to: explain the procedure in more detail without ice on it? .u boüohr-änkcn.

l} £ ij £ 3 c 1_J_

The catalyst used for polyncricion was prepared as follows: 1 mol of n-propyltanate and 3 hole vanadinox.v chlorine were diluted in 1.5, 3 heptane and then refluxed for 2 hours. IJaoli cooling of the mixture were 8 hole diethylalu-iiiniu'nchloj'Jd, ^ elür.t in '5 1 heptane, at approx. X) ⁰ C over 9 nt and on lani ^ am ζνύοχί ert i; iedcr-u: hla ;; ''. 'was filtered off, (', ev / asohen and resuspended. The suspension obtained was used; after addition of triethylaluminum oxide, it was used to make the polymer.

In egg; ie: niantolK ^ stirring drills were continuously cooled from the start 100 1 / h dor, Iu} I (jxan diluted catal.vsatorgemlsches pumped. Dor riüsnji'.kcj tsötfind in the container of 100 1 was with a Co-60 emitters ^ c ^ ö ^ lt. .The vcrlaor.enue polymer j sat the container - su opens ion was relaxed in a downstream mixer filter and from there, put on a centrifuge. The centrifu ^ enfeuclite Pulvti 'v.' Was dried thinly at approx. 80 ° C in a vacuum.

Do j Konzen ^ rai-: λ; ι of IY, 3 mg / l dos above btsohri flat transition metal ver-jinJui; ^ :: -: c :: 'ii :: c] H ?:' and a) 1000 mg / 1 b) 50 mg / 1 Triiithvl-

'j -

ßAD ORIGINAL

J5.2 ata polymerized. The yield in case a) was 10.0 kg PE / hour and in the ball b) 1.8.6 kg PE / hour.

This corresponds to catalyst consumption of:

a) 175 mg / kg PK transitional connections and 9980 mg / kg PE triethylaluminium

b) 9 ^ nig / kg PK Ubergangsir.ietall verb indungen and 270 mg / kg Pi: triethylaluminium

_{The melt index i r} (according to ASTM D 10) of the polymers, regulated with a hydrogen partial pressure of 4.8 ata, was about 21 in both cases.

The consumption of heavy metal compound kennte alno by reducing the concentration of the organometallic component of lOOÖ mg / 1 to 50 mg / 1 and ^l \ ^l j% are reduced. The consumption of triethylaluminum in the example according to the invention was only about 3 % of that in the comparison experiment.

Example ?

The flat catalyst in Example 1 was used in the same apparatus ethylene at partial pressures of 1; 3.0 ata ethylene and i? 2 ata V / water polymerized.

The catalyst concentration was:

• 6 mg / l general-purpose snap compounds ^ 50 mg / 1 tri-ethylaluminum

There were 150 l / h. Catalyst suspension used with a LüoSiGkeitssfcand of JOO 1 in the stirred tank. This gave j 11 of the 15th and 16th hours of the test 49.1 kg of polyethylene with a Schwelζindex I ₅ of 10 (ASTM D 1538). This corresponds to catalyst consumption of:

36 mg / l ^f PE heavy metal compounds 180 mg / 1 PE trlllthy! Aluminum

-G-

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BATH ORIGINAL

-G-

The content in the polymer hetvsir-. 40 ρρ * η.

Example j

Similar to example 2 vmrde Äthylen be j cjiif !: "Äthylenpart i.'i.ldruck of 18.2 ata and a WasEerstofipa.tialuruck of 16.3 ots. polymerized with the catalyst described above.

The following catalyst concentrations were used:

1 nig / 1 uber ^. 'Mgsmotall compounds 50 mg / 1 triethylaluminium

In the 15th and 16th hours, 19 »B polyethylene with a melt index I ₁ -. made by l, h .

This results in catalyst consumption of:

15 mg / kg PE Ubörgar. ^^ motallverbindungen 760 mg / kg PE Triüthy; ¹ aluminum

The ash content in the polymer was 100 ppm.

Example 4

To prepare the catalyst, 5.6 moles of diisobutylaluminum fluoride in 14 l of heptane were initially charged. To this end, a mixture of 1.6 mol of titanium tetrachloride and 1.4 mol of vanadium oxychloride is metered in at - 30 ° C. The precipitate which precipitated out was filtered off, washed and then suspended. This suspension was used as a catalyst component.

For the polymerization of ethylene at an ethylene partial pressure of 'YA ata with the addition of 6 Gev; .- # Butylene, based on ethylene and a Wacscrstoffpartia] pressure of 11.5 ata, in the Appru'atur v.'urde described in Example 2 by the ¹ catalyst described above used a concentration of 0.67 njg / l. Triethylaluminum in a concentration of 50 mg / l is used as the organometallic component. This means that in the? 1. and? 3. Hour dos Vfci'Kuclies 17, ^ leg polyethylene with a Solunelzindex i- of 2.1 (ASTH D 12} 8) obtained.

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SAD ORIGJNAk

Dar · «! ·; -, gives Giüi cjn]".; - /; a1ysat-cvvci-i) rauoli from:

3V'C, 0 r. ^ -. / K ;;: FE Vr. \; Ith \ ·] aluminum

The A ^ elK ^ ehnl t .im rolyi! K: .- ir.at Lcbrur: ne.I waiver of any Kfit; ■>. ■! , yiiatüi ^ avuivjruu'him !; 70 wn.

Dei π pic 2_ J,

With thorn in Bo ^ ßpinl 1 bekohl * 3ebenen Kital.vr.ator, ethylene was at elrj '.:.:! Ktiiyi cnpart.ialdT'ucic from y-. ata under Aur ^ oiluß by V.'asier-G t O Γ Γ pol yülOI L 3 J. 01 Ii.

Di c K at · "3 ;, sat ort>u;, r i ons -nti'at b ^ Ti'n f _η.!.!:

0, ° tnj / 1 tibeVi.i.Mng .'- nrl r: rlvcrbi.H'.lir.'rii £; erni3Gh 30.0 Ia ^ / 1 Tri; iti);: lolvw; in: ai »; i

Thus'. »Urcien in Ueν 9 · νΐπ: Ι 10. Sturicif. ^{1 of} the. Try ~ 5 $, 6 kc Γ3 get ί'-c; · " ¹ -.

This corresponds to catorvci'bi-equations of: PE

1 » ^r '''i £ i / kß transition meta Xi vorb Ind 3S0 mg / kg PIi Triäthy3 aluminum

109841/14? 8 BATH ORIGINAL

Claims (1)

ü jlJL-I- ¹ LJ 'ü i_ ^r J "* ^r !. * ü-J? I- ]. Piping for the polymerization of ethylene, if necessary in a mixture with other .y .. olefins., Using suspension or v. In inert diluents. dissolved catalysts, which (A) by. Implementation and reduction of mixtures of titanium (IV) and vanadium (V / compounds with organoaluminum compounds of the formula ¹ Λ1 Rp X Binding, where R is a hydrocarbon with one O - ?, ahl of? to 6 and X halogen, alkoxy, mercapto φ groups or hydrogen means, and (D) organometallic compounds of 1. to III, main group of the periodic table of the elements, characterized in that the polymer ion a) the concentration of the titanium-vnnadine catalyst 0> 1 to 25 mg / 1 b) the concentration of the organometallic compound OK to 100 mg / l c) the ethylene partial pressure is 3 to 60 kp / crrT, ?. The method according to claim 1, characterized in that as Titanium (IV) compound titanium tetrachloride and / or titanic acid ™ tetraester can be used. 3. Process according to Claim 1 and "?., Characterized in that vanadium oxychloride is used as the vanadium compound. 4. The method according to claim 1, characterized in that the organometallic compound of I. to III. Main group of Periodic table organoaluminum and / or organozinc 'compounds are used. New U η l layers ιαλ. 711 ν ». 2 No. ι 10 9 841 / 1U SAD ORIGINAL