DE1570352A1 - Process for the preparation of high molecular weight amorphous copolymers from 1-olefins alone or in a mixture with multiple olefins - Google Patents

Description

CHEMISCHE WERKE HÜLS AG 4370 Mari, August 1st, 1969 - Patent Department - 2O68 / G1

-r character: O.Z. I966

Process for the production of high molecular weight amorphous copolymers from 1-olefins alone or in a mixture with multiple olefins

It is known, 1-olefins and their mixtures and mixtures from 1-olefins and multiple olefins according to the low pressure process using organometallic mixed catalysts Compounds of the elements of I. to III. Main group of the periodic table on the one hand and IV. To VI. as well as VIII. Subgroup of the periodic table on the other hand to polymerize to high molecular weight substances.

For the production of amorphous copolymers are mixed catalyst components Vanadium compounds and alkyl aluminum halides particularly suitable, the solubility of the vanadium compound in the inert solvent in which the polymerization is made is advantageous.

The known processes have the disadvantage that the catalysts are used in relatively high concentrations nut, since the amount of polymer formed per contact unit is not

•: <; iiti documents ^ n. / g 1 from ₈ . a _no . 1 sau 3 ^ ₈ Ämiwu name .. v. «. s. '. .: 0 0 98 28/166 2 ÖAD ORIGINAL

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is particularly big. In addition, these catalysts have the major deficiency of only a very short duration of action. This is usually largely over after a few minutes. It is therefore necessary to use the monomers in very high concentrations in order to utilize the catalytic effect as extensively as possible. As a result, however, high heats of polymerization occur within a short time, which can only be controlled to a very limited extent, especially since experience has shown that heat dissipation in such solution polymerizations is already considerably impaired by polymer deposits on the reactor walls, which reduce the heat transfer through the reactor wall. All of these disadvantages limit the economics of these polymerization processes. Modified mixed catalysts have therefore already been proposed which contain one or more compounds which improve the effectiveness of the catalysts as the modifying component. Such substances are, for example, esters of chlorinated organic acids or halides of organic or inorganic sulfonic acids or sulfur-containing acids. With such additives, one achieves a better utilization of the effectiveness of these relatively short-lived catalyst systems, but does not solve the problem of heat dissipation in the very rapid polymerization which is still required for economical utilization of the catalyst life.

According to a method that does not belong to the state of the art, the activity of the catalyst can be increased by using one or more sulfur compounds of the general formula R-SO ₃ -X, R-SO-X, RSX, S _n X ₂ ,

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where R ■ alkyl, cycloalkyl ,. Aryl, halogenated alkyl, , alotfoniertce cycloalkyl, halogenated aryl or halogen, X ■ halogen and η ■ 1 or 2.

it has now been found that one is outwardly more advantageous. In this way, both excellent catalyst utilization and completely sufficient heat dissipation can be achieved "if, in the production of high-molecular amorphous. ·. organometallic compounds or metal hydrides of the elements of the I. to ΙΠ. main group of the periodic table on the one hand and compounds of the IV. to VI. or VIII, "subgroup de · periodic table · on the other hand in the presence of activating compounds of the general formula R - SCL -X, R-SO-X, RSX and SX ₀ , where R «is optionally chlorinated alkyl, cycloalkyl or aryl or halogen, X» is halogen and η 1 or 2, the activating additives of the polymerization solution only after at least partial consumption of the catalysts in one or several parts added.

A multistage process is used, with the polymerization being carried out in the first stage in the usual way Performs to the extent that the heat dissipation allows, and then the polymerization solution with their then for the most part already ineffective catalysts in one or more downstream process stages after entry only the activating additives continue to polymerize.

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1-olefins suitable for copolymerization are ethylene especially propylene, butene (l), pentene (l), hexene (l), decene (l). Also branched 1-olefins, z. B. 4-methyl-pentene- (l), can be used.

The process succeeds in the copolymerization of two or several of these olefins, which can be used in any molar ratio. Mixtures are preferred which contain ethylene, for example those made from ethylene and propylene or from ethylene and butene- (1), especially in the molar ratio between 1:10 and 10: 1 «because these are copolymers,

lead with optimal properties and are therefore of the greatest importance.

However , new copolymerization processes can also be used with advantage on mixtures which also contain a multiple olefin.

Multiple olefins suitable for copolymerization are %, B. hexadiene (1,4), hexadiene (1,5), pentadiene (1,4), 2-methylpentadiene (1,4), 3-methylhexadiene (l, 4), 4-methylhexadiene (1,4), decadiene-0.9), decatriene (1,4,9), trivinyl-cyclohexane, dicyclo-pentadiene, alkenylnorbornenes such as 5- (methylene) -norbornene -2, 5- (vinyl) -norbornen-2, 5- (2-methyl-buten-2-yl) -norbornen-2, 5- (buten-2-yl) -norbornen-2, 5- (3, 5-dimethyl-hexen-4-yD- -norbornen-2, 5- (cyclohexen-3-yl) -norbornen-2, norbornenedienes such as 2-allgrl-norbornene-2,5 and cyclodienes or cyclotrienes such as cyclooctadiene-ljS, mono - and disubstituted alkyl-1,5-cyclooctadiene and cyclododecatrienes.

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The molar ratio of the monomers used depends on the desired composition of the copolymer and is i.a. depending on the type of monomers.

Suitable mixed catalysts for the claimed process consist of compounds of the elements from I to IH. Main group of the periodic table that contains at least one hydrogen atom or contain an alkyl or aryl group attached to the "metal atom, and compounds of metals from IV. to VI. and the VIII, subgroup of the periodic table.

As compounds of I. to III. Groups of the periodic table that contain at least one hydrogen atom or one alkyl or aryl group bonded to the metal atom are suitable, for example amyl-sodium, butyl-lithium, diethylzinc, but especially aluminum compounds, for example trialkyl, triaryl and triaralkyl -Compounds such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triphenyl aluminum, tri- {ethylphenyl) aluminum and mixtures thereof, as well as dialkyl aluminum monohalides such as diethyl aluminum «monochloride and diethyl aluminum monobromide, and finally also monoalkyl aluminum dihalides, e.g. B. mono-ethyl-aluminum-dichloride, mono-ethyl-aluminum-dibromide and mono-methyl-aluminum-dichloride. The mixtures of equimolar amounts of dialky 1-aluminum mono halides and alkyl aluminum dihalides, for example ethyl aluminum sesquichloride or methyl aluminum ses, which are referred to as alkyl aluminum sesquihalides, can also be used with particular advantage. quichloride. In addition, also alkyl-aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride overall ^ä ·

suitable.

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Suitable compounds of metals from IV. To VI. In addition to the periodic table, titanium tetrachloride and chloro-titanium «. acid esters such as dichlorotitanic acid diethyl ester (Ti (OC ₃ Hg) gClg h .nfc especially vanadium compounds, for example vanadium trichloride, vanadium tetrachloride, vanadium oxy-trichloride, vanadium esters such as vanadium tri-acetate (V (C ₀ H ₀ O ₀ L j and vanadium triacetyl acetonate (V (CHO ₉ ) J,

The copolymerization in the liquefied monomers can, if appropriate, take place under pressure; the procedure is advantageous but in the presence of inert diluents, a. B. in charcoal that is liquid under the polymerization conditions: hydrogen or hydrocarbon mixtures such as butane, pentane, hexane, cyclohexane, isopropylcyclohexane, gasoline fractions such as petroleum ether, also benzene, toluene and xylene or chlorinated. Hydrocarbons such as chlorobenzene, tetraehloroethylene or Carbon tetrachloride and its mixtures «Ale special ge« a mixture of aliphatic and cycloaliphatic «! Hydrocarbons proven "

The reaction proceeds particularly smoothly if mixed catalysts which are soluble or colloidally distributed in the diluents used are used. Particularly suitable are the tlmsetaangeprodukte, obtained by contacting Vanadiumverbiadungen such as vanadium tetrachloride or -oxytrichlorid and Van ad ium esters with organometallic compounds of the Alyimniums such as triethyl aluminum, ^{trimethyl-aluminiMBS:} triisobutyl aluminum, tri-hexyl-aluminiuiB,

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-Chlorid «Dimethyl-aluminum-chi orid or At hy! -Aluminium-sealuiv.uorid and Mett ^ rl aluminum sesquichloride in an inert Thinner srhfilt.

The copolymerization takes place within a very wide temperature range. Temperatures between -30 and + 70 * C are particularly advantageous. The reaction succeeds without application of pressure with sufficient speed, but can also be carried out under pressure or a slight negative pressure.

The polymerization, which is preferably carried out continuously, is achieved by adding hydrogen-active substances such as water, Alcohols, Carbosieätsren or ketones canceled.

The polymer can be worked up in a manner known per se, for example by precipitation with alcohols or by evaporation of the diluent. Steam distillation,. '. . ' -; .. -

_{Sulfur compounds of the general formula R-SO 2} -X, R «SO. · X ₁ are initially suitable as activating additives, called promoters in the examples. ESX and SJ ^ ₂ *** fieringar amount, where R * is optionally chlorinated alkyl, cycloalkyl or aryl or halogen, X ■ halogen and η ■ 1 or 2 is.

Examples of compounds of this type are: sulfonic acid halides such as benzene sulfochloride, benzene sulfobromide, para-toluene sulfochloride, para-toluene sulfobromide, tetrapropylene benzene sulfochloride and other alkyl benzene sulfohalides, higher sulfochlorinated hydrocarbons, sulfinic acid halides such as

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chloric, p-toluoisulfinic acid chloride, sulfen-.ifl-.ivohlorido such as benzoluulfenyl chloride, p-toluene sulfenyl chloride, Trichloromethane sulfenyl chloride, suIfuryl halides such as Sulfuryl chloride, thionyl halides such as thionyl chloride and sulfur halides such as disulfur dichloride or sulfur dichloride.

It is preferred to wait until the rate of polymerization the first, possibly not activated, polymerization stage has subsided so far that the addition of the activating agent not too large, thermally difficult to control Further polymerization leads.

The activating additives are preferred in amounts from 0.1 to 99 5 to 85 mol percent, based on the metal-carbon or metal-hydride bonds of the organometallic compounds used bonds or the metal hydrides of the I. to HI. Chief group of the I. Periodic Table of the Elements.

These substances are preferably introduced in solution. As a solvent the solvents already mentioned above are suitable, in j; | where the polymerization takes place * i;

If desired, the exhausted mixed catalysts can be reactivated several times in succession in the manner described. This makes it possible to extend the service life in a highly advantageous manner of the mixed catalysts used with very high catalyst utilization.

The use of the catalyst is in the step-by-step reactivation of the polymer solution, which has already become inactive, by the

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Further reactivating agents in several consecutively connected Reactors better than if the entire activator is only added in the first reactor.

Pieser effect, through the sole addition of the active additives _e already largely or even completely ineffective for polymerization Making catalysts effective again is surprising especially because those used for the modification Substances used in larger quantities are known to destroy the catalyst.

The new process has the additional advantage that there are steps between the individual processes before the respective reactivation by adding the reactivating component an intermediate cooling of the polymerization solution can be carried out, so that the heat dissipation designed to be particularly efficient and very easy to control.

In contrast to the claimed process, intermediate cooling was possible in the processes known up to now, but the polymerization could then only be carried out by adding another catalyst or by adding at least one of the catalyst components essential for the formation of the catalyst (organometallic compounds of the elements from I. to XH. Main group of the periodic table or compounds of the elements of IV. To VI. Or the VIII. Subgroup of the periodic table). Such measures, however, worsen the economic viability of the process as a result of the increased expense for the catalysts. In addition, it is unfavorable that the

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as a result, the amount of polymer obtained is not proportional to the amount of catalyst added. The quality also decreases of the product due to an increase in the ash content.

example 1

The terpolymerization of ethylene, propylene and dicyclopentadiene is carried out in a laboratory apparatus with 3 2 1-glass units connected in series . reactors carried out continuously, it is first worked in all I, 3 reactors without the addition of promoters, then; the promoters only added in the second and third reactor. ; The catalyst components ethyl-Al-sesquichloride and VOCl ₃ are only added in the first reactor, the monomer supply * is kept in excess. A further increase of ^mono: merenangebots brings no solid increase. The experiment without the promoter addition (experiment 1) shows that the catalyst in the second and third reactor is already completely inactivated. As Experiments 2 to 4 show, the catalyst is only reactivated when the promoter is added in the equipment and the third reactor. .

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Test conditions:

0.5 mmol VOChJl hexane ο

6 mmol ethyl-Al-sesquichloride / l hexane Mole ratio ethylene: propylene ^ cyclopentadiene in the entry

1: 2: 0.075

Ethylene supply: 60 1 / hour pressure: 1 ata

Temperature: 3S ^# C

Average residence time in each of the 3 reactors: 1 hour

0 09823/1 ^ BAD ORIGINAL

ι. ο

t
I. σ Table 1 Reak
gate
No. Pestilence
content of
solution g polymer /
g VCCI, g polymer /
g ethyl-Al-
sesquichloride Type of rr.col
Promoters 1 Promot-or /:
Hexane I.
ί
i 1 σ
co Ver
search
No. 1 CD 1 2.2 173 20th - CO 1 2 2.2 173 20th - - 1 CD σ>
cn 3 2.2 173 20th 1 1. 1 2.2 173 20th «, ST-
S- ' 2 2 4.5 353 41 Thionyl chloride Γ " 3 6.3 495 58 Thionyl chloride 1 2.2 173 20th _- 3 2 4.3 338 39 p-toluenesulfo- 3 6.1 480 56 chloride

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The terpolymers produced in this way contain 4 to 5 double bonds per 1000 carbon atoms and between 47 * i ~ d 58 percent by weight propylene and are vul-

Kanioicrable.

The entire amount of promoter is only allowed in the first reactor ~ given, the solids contents are lower (4.8 to 5 percent by weight) than if the replenishment in the reactors 2 and 3 takes place, and is the same in all three reactors.

Example 2

The experimental setup is as in Example 1, but there will be four reactors connected in series are used. The experimental conditions are the same as given in Example 1, with the exception of those given in Table 2.

Table 2

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Table 2

Ver reactor 1 Type of mmole Promoter / Solid g Polyrr ../ 181 Z Polym./ search No. 2 Promoters 1 Hexane content of g VOCl, 181 :; ? *. thyl-Al- No. 5 solution J 181 ossquichloride 1 4th 2.5 181 21 1 - - 2.5 181 21 2 - - 2.5 550 21 5 - - 2.5 478 21 2 4th _- 2.5 575 21 1 Thionyl chloride 0.75 4.2 175 59 2 η 0.75 6.1 514 56 5 · ti 0.75 7.5 472 67 5 4th 2.2 558 20th p-toluenesulfonyl chloride 0.8 4.0 57 η 0.8 6.0 55 n ' 0.8 7.1 65

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Viro the entire amount of the promoter only in the first reactor -. Give, the solids contents in this reactor are between • t, 5 and 5 percent by weight and increase in reactors 2 and 3 no longer on. The terpolymers contain 4 to 5 double bonds per 1000 carbon atoms and between 45 and 50% by weight propylene. They can be vulcanized with sulfur.

If butene-1 is used instead of propylene, the

Conditions similar.

Example 3

The polymerization takes place as in Example 2, but instead of ethyl-Al-sesquichloride, methyl-Al-sesquichloride is used used,

Table 3

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Tabel

OZ 1966 August ^{1, 1969}

Ver
search
No. Reak
gate
No. Art dos promoters mmol promoter /
1 hexane Feotstoff-
content of
. solution C Polym./
g VOCl ₅ g polymer /
g Kethyl-Al-
sesquiChlorid 1 1 _w 3.7 290 41 2 - - 3.8 298 42 3 - - 3.9 306 43 4th - 3.9 306 43 2 1 - - 3.7 290 41 2 Thionyl chloride 0.75 5.1 400 56 3 It 0.75 7.0 549 77 4th η 0.75 8.2 644 91 3 1 _ _ 3.6 283 40 2 p-toluenesulfonyl chloride 0.8 5.3 417 59 3 0.8 6.9 542 76 4th η 0.8 8.0 628 88

O CJ Ol IS)

> 4 t ti

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W: rd the entire amount of the Promotora only in the reactor 1 ί ;;. ,, Obon, the solids contents in this reactor are:

between 6 and 6.3 percent by weight and rise in the

Reactors 2 and 3 only slightly to 6.5 percent by weight.

The double bond content of the terpolymers is between 3.5 and 4.5 percent by weight, the propylene content between 45 and 60 percent by weight. They can be vulcanized with sulfur.

Example 4 . '_;

The terpolymerization of ethylene, propylene and dicyclopentadiene is in three reactors connected in series with a volume of 50 1, 100 1 and 200 1 continuously carried out. It is initially carried out in all three reactors without the addition of promoters. The catalyst components ethyl-Al-sesquichloride and VOCl.

are added only in the first reactor, eye performs the monomers, however, in all three reactors and DIT polymerization heat is removed by cooling the Eingangshexans to ⁰ ° C by jacket cooling with an adjustable down to -10 ^e C cold cooling medium.

Again, the experiment without the promoter addition shows that the catalyst in the second and third reactor is completely inactivated. Only through the addition of a promoter in the second and third reactor, the catalyst is reactivated, again. -.

009828/1662 BATH ORIGINAL

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Test conditions: 0.5 mmol VOClg / 1 hexane

6 ipmol ethyl-Al-sesquichloride / 1 hexane Pressure: 5 ata

Temperature: 50 ^e C Molar feed ratio of ethylene: Fropylen: Dicyölpentadien: see Table 4 Äthylenangebot '· see Table 4

Average residence time in the \ reactors

see table 4

Table 4 Molar in 1)
ratio «
A: P: DCP Ethylene supply 2)
kg / hour
I. Average
Dwell time T
reactor
No. 1: 2: 0.02
1: 1) 0.02
'I 11 i 0.02 : ^2. '°
. 1.5
Χ, δ 20th
40
80 1
2
8th

1) For the calculation of the molar ratio, only those monomers that were freshly fed into the reactors are taken into account «. * -

2) The amount of ethylene freshly fed into the individual reactors is given.

t The significant effect on the solids content of the polymer solutions

can be seen from table 5.
Table 5

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BATHROOM ORIGINAL.

Table 5

0.7 1966
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Ver
search
No. Reak
gate
No. Type of the projector rnMol
Promoter /
1 hexane - pest
material
salary
d . Lo'sg
Weight % g Polym./
g VOCl ₃
• g polym, /
g ethyl
Al-sesqui-
chloride RSV I
1) 70 Gcw.f!
Propy
len im
Poly
merisat bind
gene
1000 C 1 1 4.0 514 57 1.6 72 48 4.1 2 - Thionyl chloride 1 4.0 514. 57 1.6 75 47 4.1 5 1 4.0 514 57 1.6 69 49 4.1 2 1 _ ', » 4.0 514 57 1.6 55 46 4.0 2 p-Toluenesulfochlorld 1 7.5 575 67 1 * 5 46 46 4.1 5 " 1 9.4 758 86 1.2 71 48 5.9 5 1 4.0 314 57 1.6 58 49 4.1 2 7.0 549 64 1.4 48 48 4.0 5 9.2 725 84 1.5 50 4.2

1) Reduced specific viscosity measured in toluene at 20 ° C

2) Mooney viscosity according to DIN 5> 525

O OJ CJl KJ

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If the entire length of the promoter is only placed in the first tractor, the solids content in all three reactors is around 7 percent by weight if the ι., ΝΛ elr.j -; - ag <ηe Mcnorr-er quantity is doubled at the same time. "K; ne further increase of the λίοηο / nerone supply brings no fiei ^ orunj ^ oß solids content of the polymer solutions,

It is polymerized in the same apparatus as in Example 4. The K'xi lyser components Vf. ¹ Ci and ethyl-Al- esquichloride are aur irr. first. Reactor added. The promoters are fed into all three reactors. As a result and by increasing the number of catalyst and use of the mono-ner ^ nan ^ ebots, the solids content of the polymer y . · ;;; ■.; - ■ rm ^ n reactor can be reduced to 8 Increase weight percent, ■ ,, obei ;;. ■ ('· ..'. · -; tig the limit of the removal of the polymerizatiönev. Poor (7 · -. -'- ■ · \? D.

I.:r. ~ · '·: Ϊ́ -. - ... i <! ■ -.:, c ;; e delivery of the promoior only in the ereit.'i, 7 ^? ...- - .., - '-'. "'' oigt '-. shows that df? r' suita.vj ... o '· in the

^: cri v. ■ _.-: - .; jtorf; R.;. ;;; ',. ^ r. / ■ ■ :. h \ v>; i ": rre 'iüg3bu

f ^ ·· i "" ■ - ■ '■ -.'"'"'Ut'Tj ^ t ¹ U ₁ I ₁ -JrCTi '-' ■ u .'- s' ·. v-'O- ι μ ι ^; ·) Γί Gurch

ν, '. ". ''■ -.: -. Γι .. .. ^ -., -. Ug d', e additional Poh

ε. '. ; - j ■ ^: · - ^Γ ·: --- "prdtr'n lcann.

009828/1 B6? BATH ORIGINAL

ibelle 6

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0.6 mmol VOCl _0/1 hexane

7.2 mmol ethyl-Al-ses'quichloride / l hexane

Pressure:, 5 ata

Temperature: 50 ° C Molar loading ratio

ve- .. AthyleniPropylen ^ icyclopentadiene, aiehö Table 6

Ethylene supply: 'see Table 6

Average residence time in the reactor: see Table 6

Offer of the promoters:. see table 7

, Reactor
I No.
1 Molar insert -
relationship
A: P: DCP Ethylene supply
kg / hour " Average
Dwell time i 1 1: 2: 0.02 4th 20th ; 2 " 1: 1: 0.02 1.5 40 ί s
ί 1: 1 i 0.02 1.5 80

1) -To be the calculation of the molar usage ratio * .only the quantities of Ivlonomer freshly fed into the reactors \ -earth, taken into account. ·

- / 2s is the quantity of ethylene freshly added to the individual reactors specified. '

The reactivating effect of promoters additives on the diaae without additives inactive polymer solution become clear from the ■

',: ■ .bells 7 out.

.belle 7

008828/1662 SÄD ORIGINAL

Table ·: · Y

Ver
suchs -
No. React type of promoter
gate
No. mmol Pro-
engine /
1 hexane - Solid
content of
solution
Weight% g polym.
g ^ oci ₃ / g polym. /
g ethyl-Al-
se.squi-
chloride HSV M L-4 .low .; '
Propy
3 en π π:
Pc Iy ι:. jDop-
fur
lbindg.
Ίοοο c 1 1 . ■ - 4.5 294 34 1.8 81 49 4i3 O 2 1 4.5 294 34 1.8 79 4Π 4.0 to
00 3 - - 4.5 294 34 1.8 79 48 4.1 K)
OO 2 1 thionyl chloride - 8.0 523 61 , 1.5 57 47 4.0 2 1 8.0 523 '61 1.5 . 5C 45 4.2 ro
O)
KJ ·. . · 3 0.75 8.0 523 61 1.6 58 46 4.3 3 I thionyl chloride 0.80 8.0 523 61 1.0 "55 48 4.1 2 : 10.7 '840 98 1.4 46 48 4.4 . ·. . . 3 13.8 1083 126 1.3 42 51 4.1

cn -j ο co cn ro

OZ 1966 1.8.1969

If the entire amount of the promoter is only given in the first one, the solids contents are between S _p @ rad B _e 9 ',

Percentage by weight, although this is no longer discharged to a sufficient extent, which is an increase in the temperature in excess of the desired value! in % ητ sequence

The P-alymerieatiön wirö as · in the example 3 m but different KatB% s & t © rkoanfolnatt! »©! & € feg @ seteto

conditions a:
'iil Vanadiaver'.

'' H Äl- @ rgan * o @ lig 'WmwbMäm.gß Mgscm

■ mgm-istt §θ lfm t © ta

-stars'.

5? ÖFE I gfe

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Table 8

OZ 1966 1.8.1969

Ver
search
iir. Reak
gate
No. Type of
Vanadium compound Type of
A! Organs Type of
Promoters mmol Pro
engine/
1 hexane Solid
content of
solution g Polym./
g vanadium
verb indg. g Polym./
g Al-orga
niche ver
binding 1 1 Vanadium triacetyl
aoetonat Ethyl-Al-
aesqui-
ehlorid - - 2.6 103
r 24 2 η η - - 2.6 103 24 3 It η - - 2.6 103 24 4th it It 2.6. 103 24 2 1 Vanadium triacetyl
acetone Ethyl-Al-
sesqui-
chloride - - 2.7 107 25th 2 ι * η Thionyl
chloride 0.75 171 . 39 3 » It η 0.75 6.2 246 57 4th r 0 * 75 7.5 298 69

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If the entire amount of the promoter is only fed into the first reactor, the solids contents are below 6 percent by weight. You no longer rise in reactors 2, S and 4 ' at. The double bond content of the terpolymers is between 3 and 4 double bonds per 1000 C carbon atoms, '' the propylene content between 40 and 60 percent by weight, the terpolymers can be vulcanized in sulfur, . ·

Example 7.

The polymerization is carried out as in Example 2, however, other polyunsaturated hydrocarbons are used as a tertiary component in the terpolymerization Ethylene and propylene are used.

Polymerization is carried out without pressure, the average residence time in each of the reactors is one hour, the ethylene supply is 70 liters per hour. The monomers are therefore kept in excess and only added to the first reactor. The other reaction conditions are shown in Table 8 . .. · "-? ■: · · .. - .. <· ■.. ■ ■■ · .- _; - ^f - '· · - * ·· - /. ■ · ■'. ■ ·

Table θ

QQ9828 / 18S2 BAD OFUGlNAt

Table 9

OZ 1966 1.8.1969

O O

Ver Reak Vanadium mmol Al-orga mmol Poly Service • Molars Promo pest g poly g poly search gate ver /1 niche / 1 meri respectively. Hexa- Mission- gate, material merisat, merisat, No. No. binding Hexane Connect Hexane sat. Trien ditn- behaved mmol salary g Vana- g Al- manure Temp. 1.4 Ethylene: / 1 d.solution .dinver- organ. · ⁰ C Propylene: Hexane Weight % binding Connect Dien or manure Trien 1 1 Vanadium 0.5 Ethyl- 6th 35 Hexa- 1: 2: 0.1 5.5 432 50 oxitri- When it- serving chloride qui- 1.4 chloride 2 - 5.5 " 432 50 3 - 5.5 432 50 2 1 Vanadium 0.5 Ethyl- 6th 35 1i2 »0.1 _- 5.5 432 50. oxltri- Αΐ-βββ- ohlorid qui- ohlorid 2 0.7 6.7 §26 61 3 0.7 7.7 605 71 3 1 Vanadium 0.5 Ethyl- 6th 40 5- (Methy-1: 2: 0.04 4.0 314 37 oxitri- When it- len) - ehlorid qui- chloride norbor- 2 nen-2 4.1 322 38 3 4.1 322 38

cn: ro

Port setting Table 9

o.z. 1966

1.8.1969

4th 1 Vanadium O, 5 Kthyl " 6th • 40 5- (methyl-1; 2: 0.04 - 4 _# 1 322 38 oxitri- When it- len) - chloride qui- norbor- chloride nen-2 2 0.75 6, 2 487 57 3 0.75 7 » 2 565 66 O 5 1 Vanadium 0, 5 Ethyl 6th 35 5- (Cyclo-1! 2: 0.05 - 4th 345 40 O oxitrl- When it- witches-3 to chlorld qul- A. -yl) -nor- co chloride bornen-2 K)
CD 2 - 4, 4th 345 40 —Λ 3 • Ml 4th 345 40 CD NJ 6th 1 Vanadium O ₁ , 5 Ethyl 6th 35 5- (cyclo- 1 : 2: 0.05 - 4, 4th 345 40 oxitri- When it- witches-3 chlorld qui- -yl) -nor- chloride bornen-2 .2 0.7 5 5 416 49 3 0.7 6, »^ 503 59 7th 1 Vanadium 0 , 5 Xethyl 6th 35 5- (Bu- 1 : 2: 0.05 - H ►o 314 37 oxitri- Al- ^ ses- ten-2 chloride qui- -yi) - chloride norbor- ' nen-2 2 - 4th , 0 314 37 3 - 4th , 0 314 37

Port setting Table 9

o.z. 1966

1.8.1969

8th 1 Vanadium O, Ui I Kthyl-Al- 6th 55 5- (butene 1 : 2 : 0 4.0 514 57 oxitri- sesqui- 2-yl). chloride chloride -norbor- nen-2 2 6.1 479 56 5 7.5 588 69 σ 9 1 Vanadium O, 5 Ethyl- 6th 55 5- (2- 1 : 2 : 0 5.9 506 56 ο oxitri- When it- Methyl- CD chloride qui- butene-2- co chloride yl) -nor- bornen-2 00 2 5.9 506 56 _i 5 5.9 506 56 σο απ 10 1 Vanadium O, 5 Ethyl 6th 55 5- (2- 1 : 2 : 0 4.0 514 57 oxitri- When it- Methyl- chloride qui- butene-2- chloride yl) -nor- bornen-2 2 6.2 487 57 5 7.9 620 72 11 1 Vanadium 0, 5 Ethyl 6th 40 5- (5.5- 1 : 2 : 0 5.9 '506 56 oxitri- When it- Diraethyl chloride qui- witches-4- chloride yl) -nor- bornen-2 2 5.9 506 56 5 5.9 506 56 . 05 - 0.75 0.75 . 05 - - - . 05 - 0.75 0.75 . 05 - -

Port setting Table 9

OZ 1966 1.8.1969

12 1 Vanadium O, 5 Ethyl- 6th 40 5- (3.5- 1: 2: 0.05 0.7 3, 9 306 36 oxitri- When it- Dimethyl 0.7 chloride qui- witches-4- chloride yl) -nor- bornen-2 2 6, 1 479 56 3 em 7, 6th 597 70 O
O 13 1 Vanadium O, 75 Diethyl 7.5 15th Cycloocta- 1: 3: 1 3, 5 165 26th co tetra- Al- diene-1.5 00 ehlorid chloride KJ 2 0.75 3, 6th 169 27 co
. 3t 3 0.75 3, 6th 169 27 ED
05
KS 14 1 Vanadium O, 75 Diethyl 7.5 15th Cycloocta- 1: 3: 1 3, , 6 169 27 tetra- Al- diene-1.5 chlorld. chloride 2 4th ,8th 226 36 3 - _ 5. ,8th 273 44 · 15 1 Vanadium O, 5 Ethyl- 6th 40 n-decane 1: 2: 0.04 3 ,8th 299 35 oxitri- When it- trien- ciilorid qui- 1 4 9 chloride 2 3 ,8th 299 35 3 3 ,8th 299 35

Continuation of Table 9

oz 1966 1.8.1969

O CO CO ISi OO

16 1 Vanadium 0.5 ethyl 6th 40 n-deca- ■ 3-methyl- 1: 2: 0.04 - 1: 2: 0.1 MH 1: 2: 0.1 0.7 Previous year
to
ex" .. 299 35 oxitri- When it- trien- hexadiene 0.7 ■ " chloride qui- 1,4,9 5.3 chloride • 5.3 2 • 0.7 5.6 5.3 44o 51 3 0.7 6.9 542 • 63 17 1 Vanadium 0.5 ethyl * 6 35 3-methyl- 5.3 416 49 oxitri- When it- hexadiene ohlorid qui- 1.4 6.9 chlorld 7.9 2 416 49 3 416 49
* 18 1 Vanadium 0.5 ethyl 6th 35 416 49 oxitri- When it- chloride qui- chlorld . 2 542 63 3 620 72

- 31 - OZ 1966

1.8.1969

With methyl cyclooetadiene and dimethyl cyclooctadiene as well as with 4-methyl-hexadiene-1,4 are obtained.

Again, the solids are fetched when the total amount of the promoter was suggested only in the first reactor, deeper in the first reactor than in the above-mentioned erfindungegemäfien execution of the inactivation of the catalyst in one Multi-stage reaction. Also, the solids in reactors 2, S and 4 no longer rise if the entire promoter is only in the Reactor 1 is added.

Example 8

The polymerization is w £ @ performed as in Example 2 with the difference that copolymers m & s ethylene and propylene produced from ethylene and wide Butgrlen ^ Ü and »»

Trial conditions: ■

0.8 ΐπΜρΙ VOCl ₃ /! Hexane

3.6 ιϊιΜοΙ ethyl-Al-sesquichloride / l hexane

Molar ratio of ethylene: propylene (butylene-2) ■ 1: Ethylene supply: 80 l / hour.

Pressure: 1 ata '

Temperature: 40'C

Average residence time in the reactors: 1 hour each Table 10 ■

0 09828/1662 BAD ORlGfNAL

Table 10

oz 1966 1.8.1969

Ver Reak Type of promoter type - - mmol Pestilence g Polym./ g Polym./ search gate 1-olefins - Promoter / content of S VOCl, g ethyl-Al- No. No. - - 1 hexane solution j sesqulchloride Propylene thionyl chloride Butylene-1 thionyl chloride Gew.se 1 1 Propylene 5.6 732 §5 2 - 5.7 745 87 - ι - 5.7 745 87 Butylene-1 - · 5.7 745 87 2 2 .5.6 732 85 ι 0.5 X ' ⁶ 995 116 1 0.5 8.9 1163 136 2 0.5 10.3 1347 157 3 3 4.7 615 72 4th - 4.7 615 72 1 - 4.7 615 72 2 - 4.7 615 72 4th 3 4.7 615 72 4th 0.5 5.9 U3 90 0.5 6.7 876 102 0.5 7.8 1020 119

"- 33 - OZ 1966

1.8.1969

Is the entire amount of the promoter only in reactor 1 given, the 'pesticide contents are in the ethylene-propylene copolymer at 7 percent by weight, in the case of ethylene-butylene-2 copolymer at 6.5 percent by weight. In this case, there is no increase in pesticides from reactor 1 to reactor 4.

BAD ORIGlNAU

009828 / 1.6 62

Claims (2)

OZ 1966 1.8.1.969 Claims · A process for preparing hochaolelatlarer anorpher C ο polymeric or aliein In OewLsch old from 1-olefins Mehrfacholefinen using mixed catalysts of organometallic compounds or metal hydrides of the elements of groups I to III. Main group of the periodic table on the one hand and compounds of the IV. To VI or the VIII. Subgroup of the periodic table on the other hand in the presence of activating compounds of the general formula R - S0 _g - X, R - SO - X, R - S - X and 8 _β Χ ₂ , where R «optionally chlorinated alkyl» is cycloalkyl or aryl or halogen, X · halogen and η - 1 or 2, characterized in that the activating additives of the polymerization solution are only added after at least some of the catalysts have been consumed in one or more proportions clogs. 2. The method according to claim 1, characterized in that the polymerization solution is intercooled prior to the respective addition of the activating compounds. 009828/1662