DE1545028A1 - Process for the production of olefin copolymers - Google Patents

Description

D *. E. WIEGAND MONKS

DIFL-INO. W. NIEMANN

HAMBURG 'ATINTANWXlTt

W. 11 846/64 13 / Ko

Mönchen is, ^{June 12} , 1964 NUSSBAUMSTRASSE10

Toyo Rayon Kabushiki Kaisha Tokyo (Japan)

Process for the production of olefin copolymers

The invention affirmed to a process _Z for H-steUung of new Ki _B chpol _ym erisaten and particularly to a PROCEDURES _"for Her ₈ tel _lu n _g of Mischp _0lym eri ₈ a _t s of a" onoolefin _{nit a} terminal _B oppe _1Wnd un _g a "Vinyiather. I _{n reference to al} . _Iat8aohe> ^ ..,. _Eolyethylene ^ _ftlyprowl

and this year _ale the others knew

and _Elastlzitat are ervorrasend, _{OIOS 8LE ale} s * the He _r8t e _{Settin g clay Sa8} he _s now or

_80Wl e ve of _rs0 h _led ene _{n g} e _forBt other en _d e _g ene "rtvon. _{The polyolefins belong to} ^^^ ^

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in terms of their chemical structure to the hydrocarbons of high molecular weight and since they do not have polar atomic groups themselves, they have many defects. Such defects or deficiencies that their dyeability is poor, that they have poor hygroscopicity, if any and that the surfaces of molded articles made therefrom have a waxy feel have, are the disadvantages that they have when processing into piping or threads. In addition, there is certain types of polyolefins, for example polypropylene, a disadvantage or deficiency in the fact that due to their high brittleness or brittleness temperature the resulting manufactured molded articles often cannot be used at low temperatures «

Numerous attempts have been made to overcome these disadvantages of olefin polymers. A possibility to overcome this deficiency of the olefin polymer consists in a copolymerization of these with Monomers having polar atomic groups in their molecules to carry out · However, although homopolymerization of polar vinyl compounds in some cases with a catalyst made from a mixture of transition metal compounds and organometallic compounds ei) which

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previously "used in the polymerization of olefins The interpolymerization of polar vinyl compounds and olefins is particularly possible difficult.

In an extensive investigation of this type of copolymerization reaction, it was surprisingly found that that vinyl ethers copolymerized with olefins in the presence of the catalyst described below can be and, moreover, the products thus obtained consist of new copolymers, in which the from the deficiencies and disadvantages exhibited by common olefin polymers and copolymers have been overcome

The invention relates to a process for the production of copolymers from a monoolefin with a terminal double bond and a vinyl ether, in which a monoolefin with a terminal double bond with a vinyl ether using a coordination _{catalyst, ie 0 of} a catalyst from. (1) at least one Halide, alkoxyhalide or alkoxide of the transition metals of groups IV to VIa of the periodic table and (2) at least one hydride of the metals of groups I to III of the periodic table, an organometallic compound of the metals mentioned, a metal

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of groups II - III of the periodic table or the alloys thereof.

Although the ratio in which the olefin material and the vinyl ether are used varies widely can be used to determine the vinyl ether content in the entire copolymer, for example with regard to the brittleness or brittleness temperature and impact strength, to change a vinyl ether content in the copolymer in the range from 1 to 15 ^, and in particular from 2 to 10 ^, preferred

Monoolefins with a terminal double bond, which are used in the process according to the invention can be obtained by the general formula

R ₁ - CH = CH ₂

shown, in which R- Waseastoff, an alkyl radical with 1-8 carbon atoms, a phenyl or cycloalkyl radical, for example ethylene, propylene, butene-1, pentene-1, 3-methylbutene-1, 4-methylpentene-1, 5 -Methylhexene-1, 4,4 ~ dimethylpentene-1, vinylcyclohexane and styrene · These monoolefins can also be used as a mixture of two or more of them. In addition, they can also be used in admixture with β-olefins and other olefins. _90ββ86 / ₁₃₉ Β BATHROOM

On the other hand, the vinyl ethers consist of compounds which by the general formula

OH ₂ -CH-OR ₂

in which R _{2 is} an alkyl radical having 2 to 10 carbon atoms. Examples of these vinyl ethers are vinyl ethyl ether, vinyl propyl ether, vinyl isopropyl ether, vinyl n-butyl ether and vinyl butyl ether. These vinyl ethers can also be used in the form of a mixture of 2 or more

As the first constituent of the catalyst to be used according to the invention, the compounds of Titanium, zirconium, chromium, vanadium, molybdenum or tungsten are suitable. Examples of such compounds are titanium trichloride, Titanium tetrachloride, zirconium tetrachloride, chromium trichloride, Vanadium dichloride, vanadium trichloride, vanadium tetrachloride, Vanadyl trichloride, molybdenum trichloride, tungsten hexachloride and the corresponding halides in which the chlorine is replaced with bromine or iodine, and the Alkoxyhalogerd.de and Alkoxides, e.g. dibutoxytitanium dichloride, tetrabutoxytitanium, titanium tetra- (2-ethylhexyl), trinethoxy-vanadyl, triethoxyvanadyl and vanadyl ethoxy dichloride.

The second component can e.g. consist of the free metals, like metallic zinc and metallic magnesium,

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Hydrides such as sodium hydride and lithium aluminum hydride and the organometallic compounds such as lithium aluminum tetraethyl, Sodium aluminum tetrahexyl, triethyl aluminum, diethyl aluminum chloride, Siisftlttaittmhydri ^, diisobutyl aluminum hydride, Diisobutyl aluminum bromide, triisobutyl aluminum, trihexyl aluminum, diethyl zinc, sodium zinc triethyl and calcium zinc tetraethyl. It is also permissible, besides the two components given above a third component to increase the activity of the catalyst or to increase the crystallinity to incorporate the polyolefins.

According to a generally practicable procedure for carrying out the method according to the invention the olefin and the vinyl ether are simultaneously with the

Bred mixture of the catalyst components in contact. Although it is possible in this case, the polymerization carry out in such a way that the catalyst with the monomer mixture which had been liquefied, or with brings into contact with a monomer mixture in the vapor phase without using a diluent su, it is generally advantageous to carry out the polymerization process in an inert solvent. Suitable inert solvents are the hydrocarbons and the chlorinated ones

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Hydrocarbons, for example the saturated aliphatic hydrocarbons, such as pentane, hexane, heptane, Octane and decane, the alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene, the aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and tetrahydronaphthalene and the chlorinated ones Hydrocarbons such as chlorobenzene and ethylene dichloride, The hydrocarbon mixtures, such as test kerosene (white kerosene), petroleum spirit, ligroin and petroleum ether, are also used in a suitable manner. In all cases, dewatering or drying and Heini The preparation of these solvents is carried out before they are used.

In addition, it is also possible to determine the presence of zd3 in the polymerization system. To effect hydrogen, dialkyl zinc, dialkyl cadmin and of alkyl halides, which are known as molecular weight modifiers, when carrying out the polymerization of the olefins. The polymerization conditions are generally the same as those used in carrying out the homopolymerization of olefins. So is applied in eggs order of -50 ° to 200 ° C a olymerisationstenperatur 1, with a range of 30 to 100 ⁰ C is particularly suitable. Although the polymerization pressure of

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depends on the class of vinyl ether and olefin used, is for lower olefins, e.g. ethylene and propylene,

a pressure from about atmospheric pressure to 100 kg / cm,

and preferably 30 kg / cm is suitable. The polymerization time is about 20 minutes to 60 hours. The procedure according to the invention can be carried out continuously or batchwise. Furthermore, the following can also be used Polymerization process used, namely that when initiating the polymerization reaction only either the vinyl ether or the olefin of the two components can be present in the reaction system, or both can be present, in which case in the former case either that in the course of the polymerization process Olefin or the vinyl ether is added. In general, in the continuous polymerization process the catalyst components and the two classes of lionomers are partially fed to the polymerization vessel.

According to one of the features of the invention, it is also possible to initially use the aforementioned monoolefin alone to polymerize, the coordination catalyst described above applied and then at least one of the above-mentioned vinyl ethers to the reaction product without adding decomposition of the catalyst obtained in the polymerization of the monoolefin

is, and the polymerization reaction to bind a

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Block the vinyl ether polymer at the end of the polyolefin to continue. The general operating procedure of the process for making this copolymer is described below.

The first stage of the polymerization is based on the polymerization of the monoolefin having a terminal double bond. This can be achieved by means of known olefin polymerisation procedures. The usual molecular weight modifiers, for example hydrogen, alkyl halides and dialkyl zinc, can be used here. A Polymerisationsteöiperatur τοπ ° generally 0 - 20O ⁰ G _1, and preferably 30 ° - 120 ⁰ O, is used. Although there is no particular limitation on the pressure, an appropriate and suitable pressure is used depending on the conomer class, and a pressure of atmospheric pressure "to

2 ** 2

100 kg / cm, and preferably up to 30 kg / cm for ethylene and Propylene is suitable. The polymerization time is usually 20 minutes to 50 hours. In this process, after the clefin has polymerized, the vinyl ethers ~ information on the reaction product without decomposition of the polymerization catalyst made and then carried out the second stage of the polymerization reaction. Although unreacted olefin preferably from the poly

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meriKationsgefäß is removed before the second reaction stage, this is not absolutely necessary. As a method for removing unreacted olefin from the polymerisation vessel, the one described below can be used. If the first stage of the polymerisation reaction has been carried out under pressure, unreacted monomer is drained or removed and the polymerisation system is brought back to atmospheric pressure and, if necessary, this is done The converted olefin is either replaced by an inert gas 3 such as nitrogen or! r-gon _s , or it is removed from the pressure of the vessel.

The PöIj "iySri3sm &iASt3Lips>iS" 6iip & he second stage lies

iß ± ϊλ Bz ^ Qieh -ton -SO "

«Is SO ¹¹ O, with a relatively

2i ± s - '.' R-Lz $ ΰο ^ ν3ί-; ^; : ΐ ^ υ you tißtferliElb 6C ⁰ O especially

Sas Torgtslisnfi beso'hrie'bsns Yerfahrsn can knntcontinuliel'i oö32? aaeat-wise uu ^ üh% s £ ows. In the one way of working ζητ pralrtiscliss, Atiafühinaig of the process

o wsrdsn continuously swel ia Esilie arranged reactors co

^ applied; ₃ The olefin is used in the first polymerization

- ^ vessel polymerizes νύΐΊ the leaktioas product is then dem

^ second PolymeriastionsgefäS sugefükrt, in which after additions of the vinyl ether the polymerization is carried out. A flash still can between the first and second polymerization vessel

arranged to remove unreacted olefins.

The copolymers produced according to the invention have particularly good mechanical properties and are therefore very valuable as starting materials for the manufacture of fibers, threads, films and other shaped articles. There is an improvement in comparison with the conventional polyolefins, especially in the case of properties such as colorability and brittleness temperature. In addition, since the interpolymerization with a polar monomers took place, not only their hygroscopicity improved, but also the copolymers according to the invention are also formed with a concern for electrical properties and light permeability or transparency Substances obtained by interpolymerization between olefins are superior.

The polymer obtained in the process according to the invention can in addition to its use by itself solely in admixture with polyolefins or the Kqndensationspolymerieaten, z "B. Polyamides, polyesters, polyurethanes and polyureas, as well as the vinyl polymers and copolymers, e.g. polymethacrylates, polyvinylpyridines and the other vinyl polymers and copolymers, are used.

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The invention is explained in more detail below with the aid of examples, the brittleness temperature mentioned represents a value determined according to the ASTM D746-57T test method and the impact strength according to the test method ASTM D 256-56 was determined.

example 1

A 1000 cm glass reactor was placed under a sticker
substance atmosphere with 50 cm of purified test kerosene (bp =

180 ° -220 ° C), 15 cm ⁵ vinyl isobutyl ether and charged as a catalyst 11 millimoles of titanium trichloride (which was obtained by reducing titanium tetrachloride with aluminum with subsequent activation treatment) and 22 millimoles of diethylaluminum chloride. After replacing the nitrogen gas within the reactor with propylene gas, propylene gas was introduced up to 800 mm Hg. The polymerization reaction was carried out for 200 Minuaften at 30 ⁰ C while supplying propylene gas to maintain this pressure.

After completion of the polymerization, 100 om Methanol is added to the reaction product to decompose the catalyst and then the solid polymer is added by filtration separated The solid polymer was then suspended in 200 cm of methanol and after heating during

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Filtered under reflux for 3 hours, several times with methanol washed and then dried at $ 0 ° C under vacuum. 1.4 g of a polymer tinted with a very light purple color were obtained. If from this polymer Films were cast and an infrared spectrum thereof was examined, there was pronounced absorption in the vicinity of the wavenumber 1100, which are susceptible to the presence of ether bonds is, established

Example 2

A 100 car autoclave equipped with a magnetic stirrer was operated under a nitrogen atmosphere of 40 cm purified n-heptane 3.0? Millimoles of titanium trichloride (manufactured by reducing titanium tetrachloride with aluminum) and 6, TO'Millimol Mäthylaluminiumchlorid charged « After adding 7.6 g of Yiiiylisobutyläther and replacing the Nitrogen within the autoclave with propylene

2 propylene up to a Druok of 5 - atm initiated and the polymerization carried out at 50 ⁰ G 5 Stuaden long.

Methanol was added to the polymerization product to decompose the catalyst, whereupon the solid polymer separated by filtration, refluxed together with methanol to achieve its purification, and

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-H-

was finally dried under vacuum at 5O ⁰ C. This gave 18.23 g of a solid from a white polymer. The softening point of this polymer was was at 13O ⁰ C and its intrinsic viscosity in tetralin at 135 ⁰ C 1.73. Its solubility in solvents is greater than that of polypropylene. If, for example, it was extracted for 24 hours with the following solvents at their respective boiling points, the following values of insolubles were obtained *

Solvent Insoluble & r part according to Ex-

traction _f V ''

I .II »■■■«! ■■■ Il !! ■■! »■! ■■ ■■ ■ ■ M I I ■ 1 I ■ I II III I

Acetone 34 j 4

3 & _s 9

If Pi? OpjI®Ki alone tiRtei? entspreelasnden conditions with the AbänclsriMg that no vinyl isobutyl ether was present, was polymerized, was anöererseits the ätherunlöslielie portion 97 "6 ^ _s during äthanolunlösliche portion 100 $ £ * _o Ss far infrared spectra were measured of the acetone soluble and -unlöslicfeeii / steep; with those in Pig. 1 of the zeiohnwiig represented Eu ^ ven were obtained. In both Iraqions the absorption is in NUie of the wave

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number 1100, which is attributable to the presence of ether bonds is pronounced. In Fig. 1, the results of the soluble fraction are shown by curve A while Curve B indicated the insoluble fraction

Example 3

The autoclave used in Example 2 was under

a nitrogen atmosphere with 40 cm of purified n-heptane, 3.0 millimoles of titanium trichloride and 600 millimoles of diethyl aluminum chloride loaded. After adding 3.8 g of vinyl isobutyl ether, the nitrogen within the autoclave became complete replaced with ethylene, whereupon ethylene up to one

Overpressure of 3 kg / cm was introduced and the polymerization was carried out for 5 hours at 50 ⁰ O. The reaction product was purified according to the same procedure as described in Example 2, using methanol. 7.84 g of a solid polymer were obtained. This polymer was white and was softer than polyethylene obtained with the same catalyst system. Furthermore, its inherent viscosity was in tetralin at 135 ⁰ C 1.82 "

Example 4

The copolymerization of 4-methylpentene-1 and vinyl isobutyl ether was made using the same autoclave

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and the same polymerization conditions as specified in Example 3 carried out. Instead of the ethylene in Example 3, 13.35 g of 4-methylpentene-1 were used and vinyl isobutyl ether was used in an amount of 7/6 g. By polymerization for 5 hours at 5O ⁰ C in a nitrogen atmosphere, 3 "63 g of a methanol-insoluble polymer obtained. This was a syrupy semi-solid mass.

Example 5

A 150 cm glass plunger was placed 50 cm Purified petroleum ether, 3.0 millimoles of vanadium trichloride, 6.0 millimoles of ethyl aluminum dichloride and 3.8 g of vinyl isobutyl ether introduced, then propylene up to a pressure of 3 kg / cE ^ introduced uno the polymerization reaction during

18 Stimlei at 40 ⁰ C with shaking the flask in a

had executed. The product was mixed with methanol, as! "And ee, 5 ₅ 3 g of solid polymer were obtained.

In a 15C cm pressure flask made of glass, 50 cm Petroleum benzine, ", 0 millimoles of titanium tetrachloride, 6.0 millimoles of iriethyaluminum and 3.8 g of vinyl n-butyl ether were introduced and then execution, the polymerization reaction during 4 hours at 60 ° C by introducing propylene up to

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an excess pressure of 2.4 kg / cm was the product with methanol treated, 6.22 g of a solid polymer were obtained. The amount of vinyl n-butyl ether in the copolymer was 9 | 2 # calculated from the oxygen analysis values

Example 7

When using 3.8 g of vinyl ethyl ether or 3.8 g Vinyl isopropyl ether instead of vinyl n-butyl ether in example 6, the polymerization yields were 4.73 g and 6.10 g, respectively.

Example 8

When using 3 »0 Milümol Tetrabutoxytltan instead of vanadium trichloride in Example 5 »where im the rest of the polymerization was carried out under appropriate conditions as indicated in this example 1 | 45 g of a solid polymer obtained

Example 9

In a 630 car pressure flask made of glass, 250 cnr purified n-heptane, 4.5 millimoles titanium trichloride (Stauffer Chemical Company AA Grade) and vinyl isobutyl ether and after replacing the internal gas volume of the flask with

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Propylene gas, were 9.0 millimoles of diethyl aluminum chloride

added and propylene gas further up to an overpressure of

2
3 kg / cm introduced. The flask was then placed in a hot,

immersed in a water bath held at 50 ° C. and the polymerization carried out for 24 hours while shaking the flask. After completion of the polymerization, about 100 cm of methanol were added to deactivate the catalyst, whereupon the product was left to stand overnight, then purified by heating under high pressure in le: hanol and removed under vacuum. The results, which: ei Zueat '.: of. vernch i -iclentr; Rengen of Vinylisobutyläthers ^ - "haiten vurd-r ^ _1.:.: -ι χπ c» r rachsteher ^ r ^r "ABLE I: ifgeführt.

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Table I.

Experiment Amount of 7 i η ν 1 ia ο - ·, butyl ether cm

Polymer yield g

Vinyl iso-

butyl ether in the polymer ⁺ , (Jew. i °

Brittleness Impact Strength <-Sp / C temperature ability

kg / cm / in

34

7.8

5.8

1
2

33 34

35 4.1
J, 5

0.8
1.6

4.8

20th
19th

5.5

10
20th

40 45 7.6
7.8

+ jiin; ert, calculated au «den; ; ■ the ether bond; "sV / ellenzahl 1 * absorption spectrum

++ In tetralin at 135 ° C; C ~ _; ■■: - dftfj errsde of the light absorptions between that and that of the propylene wavenumber 978 of the infrared

¹ OO cc

CD hü OO

Example 10

A 200 cm 'autoclave provided with a stirrer was charged with 80 cm of ⁵ n-heptane, 1 millimole of titanium trichloride, 1.5 millimoles of diethylaluminum chloride and 1 millimole of triethylaluminum. After addition of 5.0 g of vinyl n-butyl ether, the autoclave was closed, was replaced its inner gas volume with propylene and then through the further introduction of propylene bit to a gauge pressure of 5 kg / cm, the polymerization reaction for 2 hours running, the polymerization temperature was 42 ° -. 45 ⁰ O. by adding a methanol-isopropanol mixture (50 : 50) the polymerization was terminated, whereupon the solid polymer was separated off by filtration and heated under reflux with methanol. The polymer was obtained in an amount of 31.5 g after drying under vacuum. Analysis by means of an infrared spectrum showed that it was 8. 5-n-butyl ether, vinyl $ contained. This polymer had a viscosity '\ _B ^ / q (in tetralin at 135 ⁰ C, C = 0.208 / 100 cm ^) of 6.85 and a Sprödigkeitst emperatur of -2.0 ⁰ C. On the other hand, the polymer, which was obtained by polymerization for 1.5 hours under appropriate conditions, but without the presence of vinyl n-butyl ether, had a viscosity of I.gp/Q = 5 » 43 and a Sprödigke its tempera door of 5.6 ⁰ C.

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Example 11

An autoclave, as used in Example 10, was charged with 1 millimole of titanium trichloride (aluminum-reduced, Stauffer Chemical Co-AA Grade), 1O ⁰ C cm ^{5 of} toluene and 1 millimole of triethylaluminum and, after blowing propylene into the solvent and adding 2.8 g of vinyl isobutyl ether was further fed propylene and the polymerization carried out for 1.5 hours at 60 ⁰ C while maintaining a propylene pressure of 2.5 atm. The polymerization yield was 21.5 g "with its Vinylisobutyläthergehalt 9 | 8 i" and its brittleness point at 2.5 C was ^0.

Example 12

Corresponding to the same working method as in the example 11 described, but using 1 millimole of vanadium trichloride instead of the titanium trichloride, the Polymerization of propylene and vinyl ether carried out.

When the amounts of vinyl isobutyl ether were changed, the results shown in Table II below were obtained obtain. Here, however, isopropanol was used for post-treatment.

_Λ "bad

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- 22 Table II

Ver vinyl polymer vinyl ether brittleness search ether yield content temperature

a 0 17.5 0 0.6

b 1 19.2 3.2 -5.4

c 1.85 18.1 7.3 -4.8

d 4 16.5 17.4 0.8

⁺ IIaverage, obtained after polymerizing twice

Although when using this catalyst the brittleness temperature, even if there is no vinyl ether is low, these are lowered even further, when the polymerization reaction in the presence of vinyl ether is performed.

Example 13

In a 630 cm glass plunger were in a Nitrogen atmosphere 250 cm 'of heptane, 1.5 millimoles of titanium trichloride (as used in Example 9) and a vinyl ether, followed by 3.5 millimoles of diethyl aluminum chloride added and finally 30 grams of propylene containing 200 parts per million (ppm) hydrogen under pressure were introduced. The polymerization reaction was under

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carried out this condition by shaking the bottle immersed in a hot water bath kept at 50 ° C became. The reaction product was purified according to conventional procedures using methanol. There were those listed in Table III below Results obtained

Table III Polymeri
station
yield
G Vinyl-
ether im
Polymer Brittle
quality tempe-
rature
0 Sp / C Kind of kenge vinyl
Vinyl ether ether g 27.5 1.8 __ 5.8 Vinyl ether 2.5 28 7.5 also 5.0 25.5 2.1 7.4 Vinylisopropyl. 1.5 28.0 3.1 3.6 also 2.5 29.2 5.5 4.2 also 5.0 27.5 12.5 9.0 Vinyl-n-octyl 10.0

without

26.5

13.2

2.03

In sp iel 14

Sin 1000 oj? I glass reactor vaircle in one atmosphere Purified from nitrogen iriit 500 enr a test kerosene (white

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kerosene) (b.p. 18 ° C -. 220 ⁰ C) and 2.16 g of titanium trichloride (obtained by reduction of titanium tetrachloride with metallic aluminum) were charged, followed maintained by replacement of the Gasvolumcns in the reactor uit propylene ^ as, the temperature at 30 ° C and propylene was introduced to an absolute pressure of 1550 mm Hg. 10.9 cm (concentration 2 mol) of a solution in testkei'oein of diethyl aluminum chloride was then added to the reactor and the polymerization was initiated. The polymerization reaction was carried out while continuously stirring the contents by means of a magnetic stirrer and while maintaining the propylene pressure at 1550 mmHg. After a poly-merisationsdauer of 100 minutes, the polymerization system was to atmospheric pressure zurückg "introduced * r * m the

3 to remove unreacted propylene gas, whereupon 15 cm Vinyl isobutyl ether is added and the polymerization reaction was carried out for a further 100 minutes while maintaining the temperature at 50 c. After completion the polymerization was added to the reaction product 20 cm of methanol to decompose the catalyst, whereupon a solid polymer was separated off by filtration. This polymer was then in 200 cm of methanol suspended and refluxed, whereupon several times with

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Washed methanol and then dried at 60 ° C. under vacuum became. 12 g of a pink-colored polymer were obtained. If a small amount of this polymer u brought between glass plates and melted and pressing between the platens was converted into a film-like product upon examination a remarkable absorption by means of the infrared spectrum near the wave number IGO, which is the presence is attributable to ether bonds

Example 15

A 1000 cm glass reactor was under a nitrogen atmosphere with 500 cm of purified test kerosene (white kerosene) and 2.09 g of titanium trichloride (obtained by reducing Titanium tetrachloride with metallic aluminum), then after replacing the internal gas volume of the reactor with Propylene gas maintain the temperature at 30 ° C and propylene to an absolute pressure of 1550 mm Hg.

The polymerization was then started by adding 10.5 cm (Concentration 2 mol) of a solution in test kerosene of diethylaluminum chloride initiated. After the polymerization reaction for 20 minutes while maintaining the propylene

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pressure at 1550 mm Hg, propylene gas was removed as described in Example 9, then 15 cm Vinylisobutyläthfsr added and the polymerization reaction carried out for 100 minutes at 70 ° C. The cleaning and drying were similarly Post-treatment, as described in Example 14, carried out. The polymer obtained was light gray in color and was obtained in an amount of 10.5 g,

Example 16

A horizontally arranged shaking autoclave, the volume of which was 250 cm, was charged in a nitrogen atmosphere with 80 cm of ⁵ n-heptane, 4.5 Hillimol titanium trichloride (obtained by reducing titanium tetrachloride with metallic aluminum) and 8 Hillimol diethylaluminum chloride and after replacing the gas volume inside the autoclave with propylene the polymerization reaction was carried out for 40

Performed at 50 C for minutes. The propylene pressure during

2
this time was maintained at 5 kg / cm overpressure. The autoclave was then cooled to 20 ° C, whereupon the unreacted propylene gas was vented and removed.

After addition of 20 cm vinyl isobutyl ether, the reaction for 5 hours at 50 ⁰ O was performed. The Rea-

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tion product was then poured into Kothanoi, vigorously stirred and then the solid polymer isolated by filtration; then it was heated with more methanol and washed and ticcknet under vacuum at 50 ° C, \ * obei 32.3 g of a white polymer were obtained. After this polymer was subjected to extraction treatments for 10 After having been subjected to hours in both ether and acetone, the insoluble polymer was exposed to oxygen analyzed, where 1.31? ό were found.

A calculation of the vinyl isobutyl ether bonds in the polymer based on this value gave 4.2 mol $.

Example 17

3 A 100 cnr autoclave equipped with a magnetic stirrer

was in an atmosphere of nitrogen with 40 cm petroleum spirit (petroleum benzene), 3 millimoles of titanium trichloride (obtained by reducing titanium tetrachloride with hydrogen) and 6 millimoles of triethylaluminum charged, whereupon the polymerization was carried out after the introduction of propylene After polymerization for 1 hour at one temperature of 45 ° C and a propylene pressure of 1.5 atmospheres, the unreacted propylene was dry using Stripped off with nitrogen gas. 10 cnr vinyl n-butyl ether was then added added and the polymerization was during

24 hours at 40 ⁰ C to 45 ⁰ C,

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After the reaction product is purified by treatment with methanol and then dried under vacuum at 50 ° C 16.5 g of a solid polymer were obtained. This consisted of a somewhat sticky polymer. The oxygen analysis value was 5 »255 ° ·

Example 18

When 6 cm of vinyl isobutyl ether were used instead of the vinyl n-butyl ether in Example 17, when the polymerization was carried out under the same conditions as specified in Example 17, 13 * 1 g of a solid polymer were obtained. On the basis of an infrared spectral analysis, it was found that the content of external n-butyl ether in the polymer was 6.9%,

Example 19 .

The autoclave used in Example 17 was operated in an atmosphere of nitrogen with 40 cm of n-heptane, 1.9 millimoles

Titanium trichloride and 3 * 8 millimoles of triethylaluminum charged; then 13 »35 g of 4-methylpentene-1 were added and the polymerization carried out »After 6 hours of polymerization at a temperature of 5» 5 ° C, 5 »5 g of vinyl isopropyl ether were still added and the polymerization reaction continued for a further 6 hours at 50 ° C. After adding

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Isopropanol was added to the reaction product and the solid polymer was precipitated, the polymer was removed by ash Purified with methanol, 13.1 g of a solid polymer were obtained. The presence of the ether bonds could be clearly identified by an infrared spectral analysis to be confirmed

Example 20

When using 6.5 g vinyl isobutyl ether instead of the vinyl isopropyl ether in Example 19, the yield of polymer was 14.65 g.

Example 21

A horizontally arranged shaking autoclave with a capacity of 250 cm was in an atmosphere of Nitrogen with 80 cm 'n-heptane, 1.0 g titanium trichloride and 1.0 g of ethyl aluminum chloride charged and the Polymerization reaction was carried out for 40 minutes at 45 ° C and under a propylene pressure of 3.5 atmospheres.

Subsequently, 15 g of vinyl isobutyl ether were added and for 5 hours at 45 ⁰ C Removing the polymerization

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out, followed by washing with methanol. Eb were 20.6 g of a solid polymer were obtained. The infrared spectrum of this polymer is shown in FIG Curve B shown. This polymer was then extracted with toluene at 30 ° C. for 24 hours and then the Infrared spectrum measured, which is shown as curve C in Pig. 2 is shown.

A pronounced absorption, which can be ascribed to the presence of ether residues of polyvinyl isobutyl ether is found in the vicinity of the wave number 1100 and there is only a very slight attenuation in this Absorption takes place, even if the polymer with toluene, a solvent for the homopolymer of vinyl isobutyl ether, is extracted. It is therefore found that the vinyl isobutyl ether is chemically bound in the polypropylene is. Pur comparison is in Pig. Figure 2 shows curve A of the spectrum of polypropylene

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Claims (2)

Claims 1 »Process for the production of olefin copolymers characterized in that at the same time at least one monoolefin of the general formula R * - CH ⁼ CHp in which R _{1 is} an alkyl radical with 1 to 8 carbon atoms phenyl or cyclohexyl and at least one vinyl ether of the general formula CH ₂ = CH - 0 - R ₂ in welclar Rp an alkyl radical with 2 to 10 carbon atoms polymerized in the presence of a catalyst, which (1) at least one halide, alkoxy halide or alkoxide of the transition metals of groups IV to VIa of the periodic table and (2) at least one hydride of the metals of groups I to III of the periodic table, an organometallic Compound of these metals or a metal of the groups II and III of the periodic table or an alloy thereof ^EntMlt · BAD ORfCINAL 909886/139 5 2. The method according to claim I ₁ characterized »that one has at least one Honoolefin of the formula R ₁ -CH- OH ₂ in which R _{1 has} the meaning given above, polymerized in the presence of the catalyst and then without decomposition of the catalyst after adding at least one yinyl ether compound of the formula CH ₂ • OH - 0 - R ₂ in which R _{2 has} the meaning given above, carries out the polymerization reaction 909886/139