DE1251533B - Process for the production of olefin polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

C08f

Int. Cl .:

German class: 39cr-25/01

Number: 1 251 533

File number: H 42697 IV d / 39 c

Filing date: May 25, 1961

Open date: October 5, 1967

C03F 10-00 &

It is known in the process for the production of polyolefins according to Ziegler, in the organometallic Compounds of I. to III. Group and compounds of the IV. To VIII. Subgroup of the periodic System are used as catalyst components, the molecular weights of the products obtained thereby to regulate that one works with changing ratios of the catalyst components. An increase the organometallic component, in particular the aluminum alkyl, causes an increase in the medium molecular weight, and vice versa. The general procedure is to use the two Components react with each other in a certain ratio and then immediately so resulting mixture is used for the polymerization. Depending on the set ratio of the two catalyst components can be z. B. Ethylene polymers with molecular weights of less than 20,000 to over Set 3000000. The amount of catalyst used has an influence on the course of the Polymerization in such a way that, in the case of relatively small amounts, the polymerization occurs with an increase in the molecular weight The course of the polymerization is slower, while higher amounts of catalyst result in a faster course of the polymerization with the formation of lower molecular weights. In the fractionation of such polymers provides it turns out that there are several maxima in the polymer distribution, two particularly pronounced and thus a wide range of molecular weights is obtained.

The amounts of transition metal compound used in the technical implementation of such processes are generally quite high and experience has shown that they are usually several grams per liter, but at least about 1 g / l of the solvent used for the polymerization. Processes are also known which work with less than 1 g of solvent per liter. However, all these processes have a low yield of polymer, based on the transition metal compound used, and it is generally necessary to subject the polymer to special work-up measures in order to remove the catalyst residues. For example, this can be done by treatment with methane hydrochloric acid or generally by treatment with inorganic or organic acids or alkalis. A process in which the polymer is washed with alcohols, such as propanol, for example, which can optionally also be used in solution in hydrocarbons, is of particular industrial importance. It is also possible to process alcohol washes of this type with water washes
Olefin polymers

Applicant:

Hibernia chemistry

Company with limited liability,

Gelsenkirchen-Buer

Named as inventor:

Dr. Fritz Gude,

Dr. Dietrich Schlüter, Wanne-Eickel

combine. All of these processes have the disadvantage that they completely reduce the production of the polymer burden considerable costs, and often the achievable effects are not great enough.

It is also known to use mixtures of TiCl ₄ and VOCl ₃ as the transition metal compound component. However, they are used in considerably larger amounts, so that a special work-up of the polymer cannot be dispensed with. In addition, the space-time catalyst yields achieved are significantly poorer than those of the process according to the invention.

The invention therefore relates to a process for the preparation of olefin polymers by polymerization or copolymerization of olefins in the presence of solvents, a catalyst system composed of titanium tetrachloride, vanadium oxychloride and an organometallic compound of a metal from I. to III. Group of the periodic system and optionally hydrogen, characterized in that the polymerization is carried out in the presence of a catalyst system which is obtained from a reduction of a mixture of TiCl ₄ and VOCl ₃ with an aluminum trialkyl, optionally in a manner known _{per se in a BF 3} atmosphere , obtained insoluble precipitate in amounts of 600 to 5 mg / 1 and an organometallic compound of a metal of I. to III. Group of the Periodic Table in amounts of at least 100 mg / 1 of the solvent used for the polymerization.

The method according to the invention achieves very good, for a large-scale industrial process,

709 650/402

3 4

bare space-time yields. The polymers can be made of the solvent, or one can after a narrow molecular weight spectrum, which is what polymerizes the solvent with water vapor In contrast to the known polymers in particular drive off. In such a way of working then more in a higher tear strength, elongation and the organometallic compound in an insoluble Noticeable impact strength. Furthermore, the compound is converted in the case of 5, the aluminum alkyl in the case of waiver on special work-up measures, for example in aluminum hydroxide, which then as Low halide content. Filler can remain in the polymer. In one

It is expedient to work in the absence of such a case, it is advisable to use substances which can disrupt the course of the polymerization, such as trialkyls of aluminum, such as oxygen and water, as catalyst. To avoid any io components, since no traces of these impurities can be reliably formed during hydrolysis with water.
component in amounts of at least 0.1 g / l of the solvent used as the polymerization in the process according to the invention. _{A mixture of TiCl 4 is used as the transition metal component.} In the procedure according to the invention and VOCl ₃ in different proportions, the molecular weights of the polymers are used relative to one another, which is relatively high before use. One can, by known means, polymerize a separate reduction, e.g. B. such as B. addition of hydrogen in the polymer with aluminum triethyl in the molar ratio transition station or by thermal treatment of the poly metal compound to aluminum alkyl of 1: 4, undermerisats the molecular weight is thrown to the desired level at 20. Only the constant yield will then lead to the polymerization. insoluble fraction accrued here is used.

The invention has made it possible, and activation of the catalyst is also advantageous

the very small amounts of TiCl ₄ and VOCl ₃ , which are obtained by using it in a manner known per se

come to use, treated by cumbersome boron trifluoride.

foreseen work measures for the polymer. 25 Otherwise, the conditions for the

In particular, washing with alcohol can be dispensed with entirely, while the method according to the invention can be carried out

if not for extremely high purity of the product, otherwise usual methods for the Ziegler process.
Value is placed. Then only remain in the polymer
very small amounts of transition metal compound,

the chlorine content is also very low. Then 30 examples
A very simplified work-up can be done, for example, in such a way that the aluminum alkyl compound is evaporated off together with the solvent experiments can be seen from the table below, and then subsequently, if necessary after addition of the amounts for TiCl _{4 and VOCl 3} refer to fresh aluminum alkyl, according to the relation to the amounts which, before use for polymerisation in the reaction, immediately a further tion of a separate reduction with the use of aluminum, z. B. the polymerization reaction, would be subjected to triethyl. The reduction is carried out leads. The separation of the polymer from was carried out at -30 ⁰ C. Upon addition of BF _3, the reductive-solvent may be in insoluble plastics, such as BF tion under ₃ atmosphere, in other cases, polyethylene, polypropylene, poly - «- butylene, initially 40 under nitrogen.

by suction filtration, centrifugation or another After completion of the polymerization, this can suitable known method happen. This applies polymer to be worked up as follows: At the especially when at temperatures above experiments 1 to 6, the solvent was from Room temperature is filtered. The solvent polymer separated by suction filtration. The gasoline woman The aluminum alkyl compound can then solution of this 45 in a thin film evaporator The polymer proportions are given with the aid of thin-film or a vacuum chamber. There it was steam, by injecting gasoline into a vacuum chamber, which at the same time acts as an entrainer for the aluminum or another suitable operation, such as, for example, the nium alkyl compound, was removed and a thermal treatment was carried out in a cycle to evaporate the run for polymerization after the addition of the consumed the solution with a large surface. Soluble 50 amounts of aluminum alkyl recycled. The ab polymer z. B. ethylene-propylene copolymers, separated polymer was immediately after drying after polymerization, usable after draining. If necessary, there could be another one the overpressure, by heating in the solvent, additional cleaning with alcohols or the like about 100 to 2C0 ° C on a sufficiently movable throw.

Brought gel. In experiments 7 and 8, the gasoline solution was carried out under the autogenous pressure of the boiling solvent, if necessary under pressure, to a temperature. Filtration can then be carried out through between 110 and 200 ^° C. A filter candle can be used during production, or the separation is carried out with a low ^ r ^ value in the lower part by injecting it into a vacuum chamber. This temperature range remains, while the transition metal 60 products with a higher? _Re , 2 value in the upper temperature component have already been treated for the most part in the filter candle area. As a result, the polymerization vessel was flushed back from where it is possibly flushed back with the solvent to form a solution or a mobile gel. Further treatment was as for the above

If you want to use the solvent before recycling, the experiments described in the thin-film evaporator

for polymerization or before another use 65 or in a vacuum chamber. In the lower part was

The polymer is then deducted from the organometallic contained in it, which is then used in

Compounds, especially aluminum alkyls, are treated further with special requirements

gen, so this can be done by a simple water wash.

Art Dilution
middle lot
(D VOCl ₃ + TiCl ₄
before the reduction lot
(g / l
Solution
middle) Organometallic
link
I. to III. group
(2nd catalyst
component) lot
(g / l
Solution
middle) Olefin yield
to poly pressure Space-time
catalyst
yield (g)
Time (h)
Room (1) Art 2 amounts
relationship 0.50 1.8 merisat
(kg) (atü) Transition
metallver
binding (g / l) 1 petrol 2 VOCl ₃ , TiCl ₄
60:40 mole percent 0.15 Al diethyl
monochloride 0.55 Ethylene 0.312 - 104 2 petrol 2 VOCl ₃ , TiCl ₄
80:20 mole percent 0.15 Al-triethyl 0.55 Ethylene 0.105 - 108 3 petrol 2 VOCl ₃ , TiCl ₄
40:60 mole percent 0.05 Al-triethyl 0.55 Ethylene 0.123 - 86 4th petrol 3 VOCl ₃ , TiCl ₄
60:40 mole percent 0.03 Al-triethyl 1.1 Ethylene 0.185 - 435 5 petrol 3 VOCl ₃ , TiCl ₄
50:50 mole percent
BF ₃ 0.01 Al-triethyl 1.1 Ethylene 0.445 3 824 6th petrol 150 VOCl ₃ , TiCl ₄
50:50 mole percent
BF ₃ 0.15 Al-triethyl 1.6 Ethylene 0.214 3 1189 7th petrol VOCl ₃ , TiCl ₄
50:50 mole percent
BF ₃ Al-triethyl Ethylene—
Propylene
50:50 volume 19.8 7th 196 150 0.025 1.6 percent 8th petrol VOCl ₃ , TiCl ₄
50:50 mole percent
BF ₃ Al-triethyl Ethylene—
Propylene
50:50 volume 11.0 8th 326 percent

Claims (3)

Patent claims: 1. Process for the preparation of olefin polymers by polymerization or copolymerization of olefins in the presence of solvents, a catalyst system composed of titanium tetrachloride, vanadium oxychloride and an organometallic compound of a metal from I. to III. Group of the periodic system and optionally hydrogen, characterized in that the polymerization is carried out in the presence of a catalyst system which is obtained from a reduction of a mixture of TiCl ₄ and VOCl ₃ with an aluminum trialkyl, optionally in a manner known _{per se in a BF 3} atmosphere , obtained insoluble precipitate in amounts of 600 to 5 mg / 1 and an organometallic compound of a metal of I. to III. Group of the Periodic Table in amounts of at least 100 mg / 1 of the solvent used for the polymerization. 2. The method according to claim 1, characterized in that predominantly in the manufacture insoluble polymers these from the solvent are separated, after which the filtrate obtained in this way from the soluble fraction dissolved in it separated and then, if necessary after replenishing the consumed proportions of organometallic Compound, is returned to the polymerization stage. 3. The method according to claim 1, characterized in that in the production of predominantly soluble polymers, the solvent is brought to temperatures between 110 and 200 ⁰ C after the polymerization and separated from the polymer, after which the solvent, optionally after supplementing the consumed proportions of organometallic compound , is returned to the polymerization stage. Considered publications:
German Auslegeschriften Nos. 1 017 791, 1 049 584, 616, 1097 137; Austrian Patent No. 207 562;
French Patent Nos. 1,158,804, 203,779, 1204167; Belgian Patent Nos. 543 082, 554 271, 350;
British Patent Nos. 799 850, 846 731. 709 650/402 9. 67 © Bundesdruckerei Berlin