DE1570352C - Process for the production of high molecular weight amorphous copolymers from 1 olefins, alone or in a mixture with multiple olefins - Google Patents

Description

R-SO ₂ -X, R-SO-X, RS
or S _n X ₂

-X

where R is an optionally chlorinated alkyl, cycloalkyl or aryl radical or a halogen atom, X is a halogen atom and η - 1 or 2 is used.

2. The method according to claim 1, characterized in that before the respective addition of the Activators intercool the polymerization solution.

It is known that 1-olefins or mixtures thereof and mixtures of 1-olefins and multiple olefins using the low-pressure process with mixed catalysts made from organometallic compounds of the elements the I. to III. Main group of the periodic table on the one hand and compounds of the elements of IV. To VI. or VIII. Subgroup of the periodic table on the other hand to polymerize to high molecular weight substances.

Vanadium compounds are used as mixed catalyst components for the production of amorphous copolymers and alkyl aluminum halides are particularly suitable, taking into account the solubility of the vanadium compound in the inert solvent in which the polymerization is carried out is advantageous.

The known processes have the disadvantage that the catalysts are used in relatively high concentrations must use, since the amount of polymer formed per contact unit is not particularly large. 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. One is therefore compelled use the monomers in very high concentrations in order to maximize the catalytic effect to take advantage of. As a result, however, high heats of polymerization occur within a short time one can only master it to a very limited extent, especially since the dissipation of heat in such solution polymerizations experience has shown that this is already considerable due to polymer deposits on the reaction vessel walls, which reduce the heat transfer through the reaction vessel wall is impaired. All these disadvantages limit the economics of these polymerization processes. So you already have Modified mixed catalysts proposed as the modifying component one or more contain compounds which improve the effectiveness of the catalysts. Such substances are for example Esters of chlorinated organic acids or halides of organic or inorganic sulfonic acids or sulfur-containing acids. With such additions one probably achieves a better utilization however, the effectiveness of these relatively short-lived catalyst systems does not solve the problem the heat dissipation is still necessary for the economic utilization of the catalyst life very rapid polymerization.

A process for the production of high molecular weight amorphous copolymers has now been made 1-olefins, alone or in a mixture with multiple olefins, with the aid of mixed catalysts composed of organometallic Compounds or metal hydrides of the elements from I. to HI. Main group of the periodic table on the one hand and connections of elements of the IV. to VI. or the VIII. subgroup of the periodic table on the other hand in the presence of activators, the activators of the polymerization solution only after at least partial consumption of the Adding catalysts in one or more proportions, found, which is then extremely advantageous Both an excellent catalyst utilization and a completely sufficient heat dissipation achieved when compounds of the general formula are used as activators

r> C / ~ VVDC i ^ i V Ό QV

Ix OW ₂ Λ, tv oW Λ, rs. ο Λ.

or S _n X ₂

where R is an optionally chlorinated alkyl, cycloalkyl or aryl radical or a halogen atom, X is a halogen atom and η = 1 or 2 is used.

So you work according to a multi-stage process, with the polymerization in the first stage the previously usual way to the extent that the heat dissipation allows, and then one the polymerization solution with its then largely ineffective catalysts in one or more subsequent process steps after entering only the activating additives further polymerized.

In French patent 1,370,358, a process for the copolymerization of α-olefins, optionally together with diolefins, in the presence of a mixed catalyst composed of a vanadium compound and an organoaluminum compound and a halogenated cycloolefin as an activator described. The polymerization can be started without an activator and then the activating agent can be added. In addition, from the designed Documentation of the Belgian patent 652 314 the copolymerization of olefins, optionally together with diolefins, in the presence of catalysts made from certain organometallic compounds and Vanadium compounds and an activating agent, e.g. B. a nitrose or azoxy compound is known.

The activator can only be fed in in the 2nd polymerization zone. However, these activators are less effective than the sulfur compounds used in the process of the invention.
From the laid out documents of the Belgian patent 653 010 a process for the polymerization of ethylene, also together with other monoolefins and with multiple olefins, in the presence of mixed catalysts from an alumi-

Organonium compound and a vanadium compound and in the presence of an ester of a halogenated one Known carboxylic acid. The polymerization can be started and then without activating agents be continued with the addition of an activating agent.

Esters of halogenated carboxylic acids are in their activating effect in the process of Invention used sulfur-containing compounds equivalent. However, those with the sulphurous Compounds obtained polymers have considerable advantages that those in the presence of halogenated carboxylic acid esters obtained polymers do not have, as shown in Table VIII below in Example 5 is shown.

It is also known that in the polymerization of u-olefins using catalysts made from organometallic compounds of metals from I. to III. Group of the Periodic Table and compounds of metals from IV. To VI. Subgroup or VIII. Group of the Periodic _{Table of compounds of the formula RSO 2} X or RSOX or thionyl chloride (R is hydrocarbon radical, X is halogen) (cf. laid out documents of Belgian patent 635 903 and French patent specification 1 180 416). The thionyl chloride can be added in the course of the polymerization.

French patent specification 1 180 416 and the laid-out documents of Belgian patent 635 903 however, only describe homopolymerizations. In contrast, the subject of the invention is an improved one Copolymerization process in which an amorphous product is obtained. The catalysts that deliver the best products are made from soluble vanadium compounds. But this one have the serious disadvantage of causing a considerable loss of activity after a short time show: 90% of the initial activity can be lost after just 2 minutes. According to the invention The right to use additives is reserved to revive the catalysts in this special case or to prevent the loss of activity.

In the homopolymerizations that lead to crystalline products, the catalysts used are on the other hand, practically unchanged in their activity over the entire duration of the polymerization. This applies both to the combinations of French patent specification 1 180416, preferably titanium and aluminum compounds, as well as those in the laid out documents of Belgian patent 635 903 mentioned combinations, since it is always a question of homopolymerizations. In the inventive The method thus solves a problem which is not even posed in the cited publications has.

Finally, the effect achieved is also surprising. According to the documents laid out by the The additives used in Belgian patent 635 903 increase the isotaxy of the polymers, i. h., they increase the crystallinity. However, such an effect was with the copolymers of the process of the invention absolutely undesirable, and it was not to be expected that she would not be here. From the French Patent specification 1 180 416, however, it follows that the main effect of the additives is the To reduce yields quite strongly, d. i.e. to lower the activity of the catalysts. The task with the present Copolymerizations, however, consisted in reducing the catalyst activity by orders of magnitude to raise or to maintain. Thus not only was there no incentive whatsoever in the specified publications The mentioned additives should also be tested here, but the attempt alone was prohibited out of two serious ones Establish. At least the success that has now been achieved could not be foreseen. It also shows that the additives must develop a completely different mechanism of action here.

1-olefins suitable for copolymerization are next to Ethylene especially propylene, butene (l), pentene (l), hexene (l), decene (l). Also branched 1-olefins, e.g. B. 4-methyl-pentene- (l) can be used. The process succeeds in the copolymerization

two or more of these olefins, these being used in any molar ratio be able. Mixtures which contain ethylene, for example those of ethylene and propylene, are preferred or from ethylene and butene- (l), especially in a molar ratio between 1:10 and 10: 1, since these too Copolymers with optimal properties lead and are therefore of the greatest importance.

However, the copolymerization process of the invention can also advantageously be applied to such mixtures that still contain a multiple olefin.

Polyolefins suitable for copolymerization are, for. B.

Hexadiene (1,4), hexadiene (1,5), pentadiene (1,4), 2-methylpentadiene (1,4), 3-methylhexadiene- (1,4), 4-methylhexadiene- (1,4), decadiene- (1,9), decatriene- (1,4,9), Trivinylcyclohexane, dicyclopentadiene, alkenylnorbornenes, such as 5- (methylene) -norbornen-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-yl) -norbornen-2, 5- (cyclohexen-3-yl) -norbornen-2, Norbornenedienes, such as 2-alkyl-norbornenediene-2,5 and cyclodienes or cyclotrienes, like cyclooctadiene-1,5,

mono- and disubstituted alkyl-cyclooctadiene-1,5 and

Cyclododecatrienes.

The molar ratio of the monomers used depends on the desired composition of the copolymer and depends, among other things, on the type of monomers.

Suitable mixed catalysts for the process according to the invention consist of compounds of Elements of the I. to III. Main group of the periodic table that contains at least one hydrogen atom or contain an alkyl or aryl group bonded to the metal atom, and compounds of the metals of IV. To VI. or the VIII. subgroup of the periodic table.

As compounds of I. to III. Group of the periodic table containing at least one hydrogen atom or contain an alkyl or aryl group bonded to the metal atom, for example amyl sodium, Butyllithium, diethyl zinc, but especially aluminum compounds, for example trialkyl, Triaryl and triaralkyl compounds such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, Triphenylaluminum, tri- (ethylphenyl) aluminum and mixtures thereof, and also dialkylaluminum monohalides like diethylalu-

minium monochloride and diethylaluminum monobromide, finally also monoalkylaluminum dihalides, z. B. Monoäthylaluminiumdichlorid, Monoäthylaluminiumdibromid and Monomethylaluminiumdichlorid. The alkyl aluminum sesquihalides can also be used with particular advantage designated mixtures of equimolar amounts of dialkyl aluminum monohalides and alkyl aluminum dihalides, z. B. ethyl aluminum sesquichloride or methyl aluminum sesquichloride. In addition, alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride are also suitable.

Suitable compounds of metals from IV. To VI. Subgroups of the periodic table are titanium tetrachloride and chlorotitanic acid esters such as dichlorotitanic acid diethyl ester (Ti (OC ₂ H ₅ ) ₂ Cl ₂ ), but especially vanadium compounds, for example vanadium trichloride, vanadium tetrachloride, vanadium oxytrichloride, vanadium esters such as vanadium triacetate

(V (C ₂ H ₃ O ₂ J ₃ )
and vanadium triacetylacetonate

(V (C ₅ H ₇ O ₂ J ₃ ) ■ Ζ ⁵

The copolymerization in the liquefied monomers can optionally take place under pressure, however, it is advantageous to work in the presence of inert diluents, e.g. B. in hydrocarbons or hydrocarbon mixtures that are liquid under the polymerization conditions, such as butane, pentane, hexane, cyclohexane, isopropylcyclohexane, gasoline fractions such as petroleum ether, also benzene, toluene and xylene or also chlorinated hydrocarbons such as chlorobenzene, tetrachlorethylene or carbon tetrachloride and their mixtures. Mixtures of aliphatic and cycloaliphatic compounds have proven particularly suitable Proven hydrocarbons.

The reaction proceeds particularly smoothly if mixed catalysts are used that are used in the Diluents are soluble or colloidally distributed. The reaction products are particularly suitable which one by bringing together vanadium compounds, such as vanadium tetrachloride or oxytrichloride and vanadium esters with organometallic compounds of aluminum, such as triethylaluminum, Trimethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diethyl aluminum chloride, Dimethyl aluminum chloride or ethyl aluminum sesquichloride as well as methyl aluminum sesquichloride in an inert diluent.

The copolymerization takes place within a very wide temperature range. Particularly advantageous temperatures between -30 and + 7O ⁰ C. The reaction is achieved without the application of pressure at a sufficient rate, but can also be carried out under pressure or slightly reduced pressure.

The polymerization, which is preferably carried out continuously, is activated by adding hydrogen Substances such as water, alcohols, carboxylic acids or ketones, canceled.

The polymer can be worked up in a manner known per se, for example by Precipitation with alcohols or evaporation of the diluent by steam distillation.

The specified sulfur compounds are sufficient as activators, called promoters in the examples of the general formulas

R-SO ₂ -X, R-SO-X, R-S-X
or S _n X ₂

in a small amount.

Examples of compounds of this type are: sulfonic acid halides, such as benzenesulfochloride, benzenesulfobromide, p-toluenesulfochloride, p-toluenesulfobromide, Tetrapropylenebenzenesulphochloride and _ other alkylbenzenesulphohalides, higher sulfochlorinated hydrocarbons, sulfinic acid halides, such as benzosulfinic acid chloride, p-toluenesulfinic acid chloride, sulfenic acid chlorides, such as benzenesulfenyl chloride, p-toluenesulfenyl chloride, trichloromethanesulfenyl chloride, sulfuryl 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 of the first polymerization stage is so high It has long since subsided that the addition of the activating agent does not lead to too large a temperature that is difficult from a thermal point of view leads to dominant further polymerization.

The activating additives are expediently 0.1 to 99, preferably 5 to 85 mol percent, based on the metal-carbon or metal-hydride bonds of the organometallic compounds used Compounds or the metal hydrides of the I. to III. Main group of the periodic table of the elements, used.

These substances are preferably introduced in solution. The above are already suitable as solvents named solvents in which the polymerization takes place.

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

The use of the catalyst is based on the step-by-step reactivation of the polymerization solution that has already become inactive by adding the reactivating agents in several series-connected Reaction vessels are better than if the entire activator was only added to the first reaction vessel would be.

This effect, by adding the activating additives alone, is already largely or even To make completely polymerization-inactive catalysts again effective is surprising, in particular also because the substances used for the modification, applied in larger quantities, known to destroy the catalyst.

The process of the invention has the additional advantage that between the individual process steps before the respective reactivation With the addition of the reactivating component, intermediate cooling of the polymerization solution is carried out can, so that the heat dissipation is particularly efficient and can be controlled very well.

In contrast to the claimed process, the previously known processes involved intermediate cooling Although possible, the polymerization could then only be achieved by adding more catalyst or by adding at least one of the catalyst components essential for catalyst formation (Organometallic compounds of the elements

the I. to III. Main group of the periodic table or compounds of the elements of IV. To VI. or the VIII. Subgroup of the periodic table) reintroduce. By such measures, however, the Economic efficiency of the process as a result of the ver? increased expense for the catalysts worsened. In addition, it is unfavorable that the resulting amount of polymer obtained is not proportional is the amount of catalyst added. The quality of the product also decreases as a result of an increase in the Ash components are essential.

example 1

The terpolymerization of ethylene, propylene and dicyclopentadiene is carried out continuously in a laboratory apparatus with three 2-1 glass reactors connected in series. First of all, all three reaction vessels are used without the addition of promoters, then the promoters are only added in the second and third reaction vessel. The catalyst components ethyl-Al-sesquichloride and VOCl ₃ are only added in the first reaction vessel, the monomer supply is kept in excess. A further increase in the supply of monomers no longer results in an increase in solids. The comparative experiment without the addition of a promoter (experiment 1) shows that the catalyst in the second and third reaction vessel is already completely inactivated. Only when the promoter is added in the second and third reaction vessel is the catalyst reactivated, as experiments 2 to 4 according to the process of the invention show. ,,. . ,.

Test conditions

0.5mmol VOCI3 / I hexane.
6 mmol ethyl-Al-sesquichloride / 1 hexane
Molar ratio of ethylene to propylene to dicyclo

pentadiene in entry = 1: 2: 0.075.

Ethylene supply 60 l / hour

Pressure 1 ata

Temperature 35 ° C

Mean residence time in each of the

three reaction vessels 1 hour

Table I.

attempt
No. Reaction
vessel no. Solids content
the solution g polymer /
g VOCl ₃ g polymer /
gAlhyl-Al-sesqui-
chloride Type of promoter mmol promoter /
1 hexane 1*) 1 2.2 173 20th 2 2.2 173 20th - - 3 2.2 173 . 20th - - 2 1 2.2 173 20th - - 2 4.5 353 41 Thionyl chloride 1 3 6.3 495 58 Thionyl chloride 1 3 1 2.2 173 20th - - 2 4.3 338 39 p-Toluene sulfochloride 1 3 6.1 480 56 p-toluenesulfonyl chloride 1

*) Comparison test.

The terpolymerisals produced in this way contain 4 to 5 double bonds per 1000 carbon atoms and between 47 and 58 percent by weight propylene and are vulcanizable with sulfur.

In a further comparative experiment, the entire amount of promoter is only poured into the first reaction vessel added, the solids contents are lower (4.8 to 5 percent by weight) than when the additional dosage takes place in reaction vessels 2 and 3, and are the same in all three reaction vessels.

Example 2

The experimental set-up is as in Example 1, but four reaction vessels connected in series are used. The experimental conditions are the same as indicated in Example 1, with the exception of those indicated in Table II.

Table!!

attempt
No. Reaction
vessel
No. Type of promoter mmol promoter /
1 hexane Solids content
the solution g polymer /
g VOCl ₃ g polymer /
gäthyl-Al-sesqui
chloride 1*) 1 - - 2.3 181 21 2 - - 2.3 181 21 3 - - 2.3 181 21 4th - - 2.3 181 21 2 1 - - 2.3 181 21 2 Thionyl chloride 0.75 4.2 330 39 3 Thionyl chloride 0.75 6.1 478 56 4th Thionyl chloride 0.75 7.3 573 67 3 1 - - 2.2 173 20th 2 p-toluenesulfonyl chloride 0.8 4.0 314 37 3 p-toluenesulfonyl chloride 0.8 6.0 472 55 4th p-toluenesulfonyl chloride 0.8 7.1 558 65

*) Comparison.

309621/193

If the entire amount of the promoter is only added to the first reaction vessel, the solids contents are lower in this reaction vessel between 4.5 and 5 percent by weight and no longer rise in reaction vessels 2 and 3. The terpolymers contain 4 to 5 double bonds per 1000 carbon atoms and between 45 and 50 percent by weight Propylene. They can be vulcanized with sulfur.

10

If butene-1 is used instead of propylene, the ratios are similar.

Example 3

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

Table III

attempt
No. Reaction
vessel no. Type of promoter mmol promoter /
1 hexane Solids content
the solution g polymer /
g VOCl ₃ g polymer /
g methyl
Al-sesquichlond 1*) 1 - 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 Thionyl chloride 0.75 7.0 549 77 4th Thionyl chloride 0.75 8.2 644 91 3 1 - - 3.6 283 40 2 p-toluenesulfonyl chloride 0.8 5.3 417 59 3 p-toluenesulfonyl chloride 0.8 6.9 542 76 4th p-toluenesulfonyl chloride 0.8 8.0 628 88

*) Comparison test.

If the entire amount of the promoter is only added to reaction vessel 1, the solids contents are lower in this reaction vessel between 6 and 6.3 percent by weight and rise in reaction vessels 2 and 3 only weak to 6.5 percent by weight. The double bond content of the terpolymers is between two 3.5 and 4.5 percent by weight, the propylene content between 45 and 60 percent by weight. you are vulcanizable with sulfur.

Example 4

The terpolymerization of ethylene, propylene and dicyclopentadiene is carried out continuously in three reaction vessels connected in series with a volume of 5,100 and 2001. Initially, all three reaction vessels are used without the addition of promoters. The catalyst components ethyl-Al-sesquichloride and VoCl ₃ are only added in the first reaction vessel, whereas the monomers are added in all three reaction vessels. The polymerization heat is removed by cooling the Eingangshexans to 0 ⁰ C by jacket cooling and with an adjustable, up to - 10 ⁰ C discharged cold cooling medium.

Again, the experiment without the addition of a promoter shows that the catalyst in the second and third reaction vessel is already completely inactivated. Only by promoter addition in the second and third reaction vessel of ¹ catalyst is reactivated. Test conditions

0.5 mmol VOCI3 / I hexane

6 mmol ethyl-Al-sesquichloride / l hexane

Pressure 5 ata

Temperature 50 ° C

Molar feed ratio of ethylene to propylene too

Dicyclopentadiene see Table IV

Ethylene supply see table IV

Average residence time in the

For reactors see Table IV

Table IV

Reaction
vessel no. Molar insert
ratio ¹ )
A: P: DCP Ethylene supply ² )
kg / hour Through
average
Dwell time 1
2
3 1: 2: 0 # 2
1: 1: 0.02
1: 1: 0.02 2.0
1.5
1.5 20th
40
80

') Be used for calculating the molar usage ratio only the amounts of monomers freshly introduced into the reaction vessels are taken into account.

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

i 570 352
11 12

The clear effect on the solids content of the polymer solutions is shown in Table V.

Table V

Reaction
f- O "KTf Type of promoter mMoI
Promoter / Solid g Polymerisaf g polymer
gäthyl-Al- RSV) ML-4 ² ) Weight Double
ties Ver
search getuLS INr. 1 hexane content of
solution g VUUl ₃ sesquichloride percent
Propylene 1000 ° C No. Weight in poly 1 - - percent 314 37 1.6 70 merisat 4.1 1*) 2 - - 4.0 314 37 72 48 4.1 3 - - 4.0 314 37 73 47 4.1 1 - - 4.0 314 37 69 49 4.0 2 2 Thionyl chloride 1 4.0 573 67 55 46 4.1 3 Thionyl chloride 1 7.3 738 86 46 46 3.9 1 - - 9.4 ■ 314 37 71 48 4.1 3 2 p-toluenesulfonyl chloride 1 4.0 549 64 58 49 4.0 3 p-toluenesulfonyl chloride 1 7.0 723 84 48 48 4.2 9.2 1.6 50 , 6 , 6 1.3 , 2 , 6 , 4 , 3

') Reduced specific viscosity, measured in toluene at 20 ^° C. ² ) Mooney viscosity according to DIN 53 523.
*) Comparison test.

If the entire amount of the promoter is only added to the first reaction vessel, the solids contents are lower in all three reaction vessels at around 7 percent by weight, if at the same time the one entered there Monomer amount is increased to double. A further increase in the addition of monomers does not bring about any result Increase in the solids content of the polymer solutions.

Example 5

It is polymerized in the same apparatus as in Example 4. The catalyst components VOCl ₃ and ethyl-Al-sesquichloride are only added to the first reaction vessel. The promoters are fed in in all three reaction vessels, namely in the first vessel after at least some of the catalyst has been consumed. As a result, and by increasing the use of catalyst and the supply of monomers, the solids content of the polymer solution in the first reaction vessel can be increased to up to 8 percent by weight, the limit for the dissipation of the heat of polymerization being reached at the same time.

An attempt in which the feed of the promoter after at least partial consumption of the catalyst occurred only in the first reaction vessel shows that the catalyst in reaction vessels 2 and 3 has already become ineffective. The catalyst is only reactivated again by further reactivation Addition of the promoter in the reaction vessels 2 and 3, whereby there by, further external cooling the additional heat of polymerization can be removed.

35

40

45 test conditions

0.6 mmol VOCI3 / I hexane

7.2 mmol ethyl-Al-sesquichloride / 1 hexane

Pressure 5 ata

Temperature 5O ⁰ C

Molar feed ratio of ethylene to propylene too

Dicyclopentadiene see Table VI

Ethylene supply see table VI

Average residence time in the reactor see Table VI

Offer of promoters see Table VII

Table VI

Reaction vessel no.

Molar usage ratio ¹ )
A: P: DCP

2
3

1: 2: 0.02
1: 1: 0.02
1: 1: 0.02

Ethylene supply ² kg / hour

) Average residence time

1.5

1.5

20 40 80

') Be used for calculating the molar usage ratio only the amounts of monomers that are freshly added to the reaction vessels are taken into account.

² ) The amount of ethylene freshly added to the individual reaction vessels is given.

The reactivating effect of the promoter states on the polymer solution which has become inactive without these additives is shown in Table VII.

Table VII

Reaction Type of promoter mmol Feststorf g polymer
g VOCl ₃ g polymer RSV ML-4 Weight Double Ver vessel Promoter / content of g ethyl-Al- percent ties search No. I hexane solution 294 sesquichloride Propylene 100 ° C No. - Weight 294 1.8 81 in poly 1 - - percent 294 34 1.8 79 merisat 4.3 1*) 2 - . - 4.5 34 1.8 79 '49 4.0 3 - 4.5 34 46 4.1 4.5 48

*) Comparative tests.

continuation

Reaction Type of promoter mmol - 1 - Solid 17 Ρ / λ] vmiirri'ίf α polymer ' RSV M L.-4 Weight Double Ver let promoter - 0.75 content of £ ι uiynicriSdL
ei vnn "gAlhyl-Al- percent ties search No. I hexane 0.80 solution g V ULI ₃ sesquichloride Propylene 1000 ¹ C No. Thionyl chloride 1 Weight 1.5 57 in poly 1 - 1 percent 523 61 1.5 56 merisat 4.0 2 2 - 8.0 523 61 1.6 58 47 4.2 3 Thionyl chloride 8.0 523 61 1.6 55 45 4.3 1 Thionyl chloride 8.0 523 61 1.4 46 46 4.1 3 2 Thionyl chloride 8.0 840 98 1.3 42 48 4.4 3 Trichloroacetic 10.7 1083 126 1.6 58 48 4.1 1 acid methyl ester 13.8 511 59 51 4.3 4 *) - 7.8 1.6 56 50 2 511 59 1.6 58 4.0 3 7.8 511 59 48 4.2 7.8 49

*) Comparison test.

If the entire amount of the promoter is only added to the first reaction vessel, the solids contents are lower between 8.5 and 8.9 percent by weight, although the heat of polymerization is no longer in can be discharged to a sufficient extent, which results in an increase in the temperature in the polymerization batch above the desired value has.

In Table VIII below, the aging resistance of polymers according to Table VII, tests 3 and 4 is compared. Aging was carried out in a circulating air drying cabinet (gel aging) at 120 ⁰ C for 100 hours.

Table VIII

Activating additive

Polymer properties

Strength, kp / cm ²

Strain, %

Module (at 300%)

Permanent elongation,%

Hardness, "Shore

Elasticity (at 2O ⁰ C),%
Elasticity (at 75 ° C),%

*) Comparison test.

Thionyl chloride

before I after aging

230

390

140

200

260

160

68 50 56

Table VIII shows the typical range of values for aged vulcanizates. The aging resistance of the Product made with thionyl chloride is significant, recognizable by its strength and elongation cheaper.

This means that you can vulcanize at a high temperature if you use thionyl chloride processed products without adding a lot of stabilizer. This is why it is important because unsaturated rubber made from 1-olefin polymers, in contrast z. B. to isoprene rubber, has a relatively low vulcanization rate, which can only be compensated by a higher temperature.

Trichloroacetic acid methyl ester *)

before I after aging

235

415 145 12 67 49 53

185

142

167

70 52 57

Example 6

The polymerization is carried out as in Example 2, but different catalyst combinations are used used.

Test conditions

0.6 mmol vanadium compound / l hexane

6 mmol of organic aluminum compound / l hexane

Ethylene supply 60 l / hour

Pressure 1 ata

Temperature 95 ° C

Mean residence time in each of the
three reaction vessels 1 hour

Table IX

Reaction Type of L * Type of promoter mmol Solid g Polym./ g Polym./ Ver vessel Vanadium Kind of Al-organic Promoter / content of g vanadium g Al- search No. connection ver dinoung 1 hexane solution connection organic No. Ver 1 Vanadium Triac- ■ Ethyl-al-sesqui- 2.6 103 binding 1*) tylacetonate chloride - 24 2 the same the same - - 2.6 103 3 the same the same - - 2.6 103 24 4th the same the same - 2.6 103 24 24

*) Comparison test.

continuation

Ver
search
No. Reaction
gera ß
No. Type of
Vanadium
connection Kind of Al-organic
connection 2 1
2
3
4th Vanadium Triac
tylacetonate
the same
the same
the same Ethyl-al-sesqui-
chloride
the same
the same
the same

Type of promoter

Thionyl chloride
the same
the same

mmol

Promoter

1 hexane

0.75
0.75
0.75

Solids

the

solution

g poly / g vanadium compound

2.7

4.3
6.2

7.5

107

171 246 298

g Polym./

g inorganic

connection

25th

39 57 69

If the entire amount of the promoter is only introduced into the first reaction vessel, the Solids contents below 6 percent by weight. They no longer rise in reaction vessels 2, 3 and 4. The double bond content of the terpolymers is

between three and four double bonds per 1000 carbon atoms, the propylene content between 40 and 60 percent by weight. The terpolymers can be vulcanized with sulfur.

Example 7

The polymerization is carried out as in Example 2, but there are other polyunsaturated Hydrocarbons as a tertiary component in the ter-

time is 1 hour in each of the reaction vessels. The ethylene supply is 70 liters per hour. The monomers are therefore kept in excess and only

polymerization with ethylene and propylene used. 25 added in the first reaction vessel. The remaining Polymerization is carried out without pressure; the mean residence reaction conditions are shown in Table X.

Table X

Reak
functional
just 13
No. Vanadium
connection mmol /
1
Hexane Al-organic
connection mmol /
I.
Hexane Poly
merisat
Temp.
° C Dien or Trien Molars Per
engine,
mmol /
I hexane Solid g poly
merisat,
g Vana
dinver
binding g poly
merisat,
g Al-
organi
cal ver
binding Ver
search
No. I. Vanadin oxi- 0.5 Ethyl- 6th 35 Hexadiene-1,4 mission
ratio
Ethylene too
Propylene
at service
or Trien salary
the
solution
Ge
weight
percent 432 50 1*) trichloride Al-sesqui- 1: 2: 0.1 5.5 chloride 2 - 432 50 3 - 5.5 432 50 1 Vanadin oxi- 0.5 Ethyl- 6th 35 Hexadiene-1,4 5.5 432 50 2 trichloride Al-sesqui- 1: 2: 0.1 5.5 chloride 2 0.7 526 61 3 0.7 6.7 605 71 • 1 Vanadin oxi- 0.5 Ethyl- 6th 40 5- (Methy! En) - - 7.7 314 37 3 *) trichloride Al-sesqui-
plilnriH norbornene-2 1: 2: 0.04 4.0 2 Willis 1 IU 322 38 3 - 4.1 322 38 1 Vanadin oxi- 0.5 Ethyl- 6th 40 5- (methylene) - - 4.1 322 38 4th trichloride AI-sesqui- norbornene-2 1: 2: 0.04 4.1 2 LlIiUI IU 0.75 4.87 57 3 0.75 6.2 565 66 1 Vanadin oxi- 0.5 Ethyl- 6th 35 5- (cyclohexene - 7.2 345 40 5 *) trichloride Al-sesqui- 3-yl) -nor- 1: 2: 0.05 4.4 chloride bornen-2 2 - 345 40. 3 - 4.4 345 40 1 Vanadin oxi- 0.5 Ethyl- 6th 35 5- (cyclohexene __ 4.4 345 40 6th trichloride Al-scsqui- 3-yI) -nor- 1: 2: 0.05 4.4 chloride ' bornen-2 2 0.7 416 49 3 0.7 5.5 503 59 1 Vanadin oxi- 0.5 Ethyl- 6th 35 5- (buten-2-yl) - 6.4 314 37 7 *) . trichloride Al-sesqui- norbornene-2 1: 2: 0.05 4.0 2 cmoriu - 314 37 3 - 4.0 314 37 *) Comp request. 4.0 309 621/193

continuation

Reak
functional
gera ß
No. Vanadium
connection mmol.
1
Hexane Al-organic
connection mmol
1
Hexane Poly
merisat
Temp.
"C Dien or Trien Molars Per
engine.
mmol /
1 hexane Solid g poly
merisat,
g Vana-
dinver-
Oinding g poly
merisat,
g Al-
organi
cal ver
binding Ver
search
No. 1 Vanadin oxi- 0.5 Ethyl- 6th 35 5- (buten-2-yl) - Mission-
ratio
Ethylene too
Propylene
at service
or Trien salary
the
solution
Ge
weight
percent 314 37 8th trichloride Al-sesqui-
chloride norbornene-2 1: 2: 0.05 4.0 2 0.75 479 56 3 Ethyl- 0.75 6.1 588 69 1 Vanadin oxi- 0.5 Al-sesqui- 6th 35 5- (2-methyi- 7.5 ■ 306 36 9 *) trichloride chloride buten-2-yl) - 1: 2: 0.05 3.9 norbornene-2 2 - 306 36 3 Ethyl- - 3.9 306 36 1 Vanadin oxi- 0.5 Al-sesqui- 6th 35 5- (2-methyl- - 3.9 314 37 10 trichloride chloride buten-2-yl) - 1: 2: 0.05 4.0 norbornene-2 2 0.75 487 57 3 Ethyl- 0.75 6.2 620 72 1 Vanadin oxi- 0.5 Al-sesqui- 6th 40 5- (3.5-Di- - 7.9 306 36 11 *) trichloride chloride methylhexene 1: 2: 0.05 3.9 4-yl) -nor- " bornen-2 2 - 306 36 3 Ethyl- - 35 306 36 1 Vanadin oxi- 0.5 AI-sesqui- 6th 40 5- (3.5-Di- 35 306 36 12th trichloride chloride methylhexene 1: 2: 0.05 35 4-yl) -nor- bornen-2 2 0.7 479 56 3 Diethyl 0.7 6.1 597 70 1 Vanadium 0.75 Al chloride 7.5 15th Cycloocta- - 7.6 165 26th 13 *) tetra diene-1.5 1: 3: 1 • 3.5 chloride 2 - 169 27 3 Diethyl - 3.6 169 27 1 Vanadium 0.75 Al chloride 7.5 15th Cycloocta- 3.6 169 27 14th tetra diene-1.5 1: 3: 1 3.6 chloride 2 0.75 226 36 3 Ethyl- 0.75 4.8 273 44 1 Vanadin oxi- 0.5 Al-sesqui- 6th 40 n-decane __ 5.8 299 35 15 *) trichloride chloride triene-1,4,9 1: 2: 0.04 3.8 2 - 299 35 ■■ 3 Ethyl- 3.8 299 35 ■ ' 1 Vanadin oxi- 0.5 Al-sesqui-
chloride 6th 40 n-deca- 3.8 299 35 16 trichloride triene-1,4,9 1: 2: 0.04 3.8 2 Ethyl- 0.7 440 51 3 AI-sesqui- 0.7 5.6 542 63 1 Vanadin oxi- 0.5 chloride 6th 35 3-methylhexa- - 65 416 49 17 *) trichloride diene-1,4 1: 2: 0.1 5.3 2 Ethyl- - 416 49 3 Al-sesqui- - 5.3 416 49 1 Vanadin oxi- 0.5 chloride 6th 35 3-methylhexa- 5.3 416 49 18th trichloride diene-1,4 1: 2: 0.1 53 2 0.7. 542 63 3 0.7 6.9 620 72 75

*) Comparative tests.

With methyleyclooctadiene and dimethylcycloocta- 65 entire amount of the promoter only in the first reaction

diene and 4-methylhexadiene-1,4 are added in a similar vessel in the first reaction vessel

Get results. ■ deeper than in the case of the above-mentioned inventive

Again, if the correct implementation of the reactivation of the catalyst, the solids contents

tors in a multistage reaction. The solids in reaction vessels 2, 3 and 4 also do not rise more if the entire promoter is only added in reaction vessel 1.

5 Example 8

The polymerization is carried out as in Example 2 with the difference that copolymers from Ethylene and propylene as well as from ethylene and butylene-2 are produced.

Table XI

Test conditions

0.3 mmol VOCI ₃ /! Hexane 3.6 mmol ethyl-Al-sesquichloride / 1 hexane Molar ratio of ethylene to propylene (butylene-2) = 1: 2

Ethylene supply 80 l / hour

Pressure 1 ata

Temperature 40 ⁰ C

Average residence time in the

Reaction vessels for 1 hour each

Ver
search Reaction
vessel Type of olefin Type of promoter mmol promoter / Solids content
the solution g polymer / g polymer /
gäthyl-Al- No. No. 1 flexan Weight percent g VUCl ₃ sesquichloride 1*) 1 Propylene - - 5.6 732 85 2 - - 5.7 745 87 3 - - 5.7 745 87 4th - - 5.7 745 ■ 87 2 1 Propylene Thionyl chloride - 5.6 732 85 2 0.5 7.6 995 116 3 0.5 8.9 1163 136 4th 0.5 10.3 1347 157 3 *) 1 Butylene-1 - - 4.7 615 72 2 - - 4.7 615 72 3 - - 4.7 615 72 4th - - 4.7 615 72 4th 1 Butylene-1 Thionyl chloride - 4.7 615 72 2 0.5 5.9 772 90 3 0.5 6.7 876 102 4th 0.5 7.8 1020 119

*) Comparative tests.

If the entire amount of the promoter is only added to the reaction vessel, the solids contents are lower in the case of 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 solids from reaction vessel 1 to reaction vessel 4.

Claims (1)

Patent claims: 1. Process for the production of high molecular weight amorphous copolymers from 1-olefins, alone or in a mixture with multiple olefins, with the help of mixed catalysts made of organometallic Compounds or metal hydrides of the elements of the I. to III. Main group of the periodic table on the one hand and compounds of elements from IV. to VI. or the VIII. subgroup of the periodic table on the other hand in the presence of activators, whereby the activators the polymerization solution only after at least partial consumption of the catalysts in one or several parts are added, characterized in that compounds are used as activators of the general formulas