DE2329058A1 - PROCESS FOR MANUFACTURING COPOLYMERISATES AND THEIR USE - Google Patents

Description

DR.-ING. TH. MEYER DR. FUES D I P L-CH EM. ALE K VO N K R E IS LE R DIPL.-CHEM. CAROLA KELLER DR.-ING. KLDPSCH DIPL.-ING. SELTING

5KOLNLDEICHMANNHAUs 2329058

Cologne, June 6, 1973 Ke / Ax

MONTECATINI EDISON S.p.A., J) I, Foro Buonaparte, Malland (Italy).

Process for the production of copolymers and their use

The invention relates to a process for the copolymerization of ethylene with α-olefins of the formula GHp = CHR, in which R is an alkyl radical having 1 to 6 carbon atoms, in the presence of or Absence of unsaturated compounds containing two or more double bonds and those obtained thereby elastomer compounds with very good mechanical properties.

The copolymerization of ethylene with α-olefins in the presence or absence of diolefins or polyenes has heretofore been carried out with different types of catalysts. One of the most commonly used catalysts is the product of the reaction between a vanadium compound and an organometallic derivative of metals from the first, second and third groups of the periodic table. The use of these catalysts enables the production of essentially amorphous copolymers which are characterized by valuable elastomeric properties in the vulcanized state. The ones used on the However, catalyst-related polymer yields are not very high. From some older patent applications of the

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The applicant is aware of ethylene polymerization catalysts which have a very high catalytic activity and from the product of the reaction between a hydride or an organometallic compound of Metals of the first, second and third groups of the periodic table and the product obtained by bringing together Titanium compounds with a carrier consisting of an anhydrous halide of magnesium, manganese, zinc or calcium exists under or using the conditions under which the anhydrous halide is activated Halide has been obtained in already activated form.

Compared to the customary Ziegler catalysts, the supported catalysts of the invention have the advantage one related to the titanium compound used significantly higher polymer yield. Above all, enable it is, because of the particularly high yields, any treatment to purify the polymer from catalyst residues to be avoided after the polymerization has ended.

When these catalysts are used for the copolymerization of ethylene with α-olefins, they draw are also characterized by very high activity, but they result in elastomeric products that are vulcanized in the Condition have the disadvantage of an excessively large deformation residue at break.

It is also known from U.S. Patent 3,642 7 ^ 6, that the copolymerization of ethylene with propylene or other α-01efinen in the presence of Ziegler supported catalysts can be carried out, the component applied to the carrier is produced by first formed a complex of a magnesium or manganese dihalide with a Lewis base and the complex then with a liquid halogenated titanium compound

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under conditions under which the Lewis base is removed from the magnesium or manganese dihalide, reacted and then isolating the magnesium or manganese dihalide essentially free of the base from the reaction mixture. The essential feature of this process is thus that the Lewis base is first with the magnesium dihalide converted into a complex and then before combining with the organoaluminum compound from the Complex must be removed. Furthermore, the order in which the reactants are added is critically important for the formation of active catalysts. For example, when the titanium compound, the magnesium dihalide and the Lewis base are added at the same time or the Lewis base is added to the 'organoaluminum compound, Catalysts are obtained which have a much lower activity than those according to the U.S.A. patent produced catalysts. The copolymers produced in the known process form vulcanizates with a large deformation residue after breakage. The yield of copolymer per gram of titanium is generally low. A representative type of this class of catalysts is that described in Comparative Example 3 Attempt used.

It has now surprisingly been found that it is possible is, saturated elastomeric copolymers of ethylene with cc-olefins and unsaturated copolymers of ethylene with cc-olefins and with dienes or polyenes with excellent mechanical properties and in particular with a relatively low deformation set in high yields and consequently with those mentioned above Benefits obtained when polymerizing the mixtures of ethylene and cc-olefins is carried out in the presence of appropriately modified catalysts.

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This is achieved by the invention, according to which a mixture of ethylene with one or more higher α-olefins or a mixture of ethylene with one or more higher α-olefins and one or more polyenes, ie hydrocarbon monomers which contain two or more double bonds, using a catalyst is copolymerized, which is prepared by mixing

a) a hydride or an organometallic compound especially of aluminum with

b) another catalyst-forming component consisting of the product obtained by

■ Binding of a halogenated titanium compound on a carrier made of an anhydrous magnesium or Manganese halide, which by partial or complete complex formation with a to form complexes with the halide capable Lewis base has been modified., exists or contains this halide.

According to another embodiment of the invention the copolymerization is carried out in the presence of a catalyst which has been prepared by mixing the component (a) in which the organoaluminum compound is partially complexed with the Lewis base, with the component (b) obtained by bringing the halogenated titanium compound together with a carrier composed of an anhydrous, previously activated magnesium or manganese halide consists or contains this, or by Merging the halogenated titanium compound with the anhydrous magnesium or manganese halide under conditions among which the activated magnesium or manganese halide is formed.

In each case, the molar ratio of the anhydrous magnesium or manganese halide to the Lewis base is, with the

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the halide is partially or fully complexed, 1: 2 to 20: 1.

By "anhydrous activated magnesium or manganese halide" is meant an anhydrous magnesium or manganese halide to understand that up to a state in which there is a surface of regardless of the particle size

.more than 5 m / g has been activated.

The preactivated magnesium or manganese halides can be produced by various processes. Suitable a method which comprises dissolving the anhydrous halide in alcohols, ethers or other anhydrous organic solvents, the major part of the solvent is removed, for example by rapid evaporation and then the removal of the solvent under reduced pressure at a temperature above 100 ⁰ C, especially completed at a temperature of 150 ° to 400 ° C.

Another method is used to grind the anhydrous magnesium or manganese halide intensively until its Surface is larger than 5 m / g. However, it is preferred a process in which the halogenated titanium compound and the magnesium or manganese dihalide under conditions below which a surface area of more than 5m / g is obtained will be ground together.

The component (b) of the catalyst can be prepared by a preformed complex of the anhydrous Magnesium or manganese halide with the Lewis base, which is able to form a complex with the halide, with the halogenated titanium compound under conditions under which the titanium compound is bound to the support, is treated. For example, the treatment can be

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be taken by a solution of the titanium compound in a hydrocarbon in the presence of the carrier on The reflux condenser is heated. The pre-formed complex can be prepared by various methods, e.g. by dissolving the magnesium or manganese halide in the Lewis base with heating and subsequent precipitation the complex by cooling and separating the complex from the reaction mixture.

Instead of using a pre-formed complex, the catalyst component (b) can be prepared by Bringing together the halogenated titanium compound with the support, which consists of the preactivated magnesium or manganese halide consists or contains this halide, in the presence of the Lewis base used in such an amount is that the molar ratio of the active anhydrous magnesium or manganese halide (consisting of that with the base complexed part and any non-complexed part of the halide) to the Lewis base 1: 2 to 20: 1.

In the preferred method, the catalyst-forming component (b) is prepared by adding the Lewis base with an anhydrous magnesium or manganese halide or a mixture of a pre-formed complex of the Lewis base ground with the magnesium or manganese halide, the halogenated titanium compound with the ground product added and milling continued. It is also possible to use the catalyst component (b) by common Milling the titanium compound with a pre-formed complex of the magnesium or manganese halide with the base to manufacture.

Milling is carried out under conditions under which, in the absence of the base or its complex, the ground magnesium or manganese halide a surface

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of more than 5 m / g. It has been found that by milling together in the presence of the Lewis base or the preformed complex thereof, a product is generally obtained which has a significantly smaller surface area than the product obtained in the absence of the base.

The milling of the anhydrous magnesium or manganese halide, which may or may not be complexed, or one Mixture of the halide with a Lewis base or with a Lewis base and the halogenated titanium compound is preferably carried out in a ball mill under dry conditions, i.e. in the absence of inert liquids Diluents carried out.

The anhydrous magnesium or manganese halides, which can be in activated or non-activated form, can also be mixed with inert solid extenders, which consist of the anhydrous compounds of the metals of the first, second, third and fourth group of the periodic table, can be used without the high activity the catalysts obtained in this way is significantly deteriorated. Particularly good results are achieved with Use of aluminum oxide obtained as an inert extender.

The Lewis bases used for the preparation of the catalyst component (b) have to form complexes be capable with magnesium or manganese halides. Electron donor compounds are generally used as the bases used in which oxygen, phosphorus or nitrogen is present as an electron donor atom.

As examples of particularly suitable Lewis bases, the production of copolymers with good mechanical Allow properties in high yields include: benzonitrile, p-anisonitrile, POCl ^, tri-

ethylamine, pyridine, ethyl benzoate, / ethyl ether, ethyl acetate, 30985 1/0950

Diethyl aniline, ethyl p-anisate, diethyl carbonate, trimethyl phosphite and diethyl- ^ N-diethylcarbainate.

As already mentioned, the molar ratio of the magnesium or manganese halide to the Lewis base is in the Component (b) of the catalyst between 1: 2 and 20: 1. The best results were with ratios of 2: 1 to 5 * 1 received. In general, it should be noted that the copolymer yield with increasing content of the base in of component (b) falls, while the elastomeric properties improve as this ratio falls wont to be.

Suitable titanium compounds for the purposes of the invention are the halides, oxychlorides, halogen alcoholates and halogen titanates and halogen titanites. Titanium compounds which can be obtained from the aforementioned titanium compounds and from the alcoholates and amides of the alkali metals, for example LiTi (OC ₅ H ₇ ) Cl _5, are also suitable.

Examples of titanium compounds that are suitable for the purposes of the invention include: TiCl ₄ , TiCl ,, 3TiCl _5, AlCl ₅ , Ti (OC ₅ H ₇ ) Cl ₅ , Ti (OC ₄ Hg) ₂ Cl, Ti / O-C (CH ₅ ) = CH-CO-CH ₅ Z ₂ Cl ₂ , TiZR (C ₂ H ₅ ) ^ Cl Z () ^

(TiCl _{5 -OSO 2} -C ₆ H ₅ ), Ti (C ₆ H ₅ COO) Cl ZN (CH ₅ ) ^ Ti ₂ Cl ₉ , TiBr ₄ .0 (C ₂ H ₅ ) ₂

LiTi (OC ₅ H ₁ O ₂ Cl, TiCl ₅ CH ₅ , TiCl ₅ C ₅ H ₅ , TiCl ₅ C ₆ H ₅ S,

₅ ,

The amount of titanium compound used to make the supported catalyst component is within wide limits of less than 0.1% by weight; <6 up to 30% by weight or more, based on the carrier. Particularly good results with regard to the yield of copolymer based on the titanium compound are achieved obtained when the amount of titanium-

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compound is 0.5 to 5 wt%, expressed as Ti metal.

Of the soluble hydrides and organometallic compounds of the metals of the first, second and third groups are Al (C ₂ H) AlCiC ₄ H ₉ ), Al (C ₂ H ^) ₂ H,. Al (iC ₄ H _q ) _o H and A1CC ₂ H ₅ ) ₂ C1 are particularly well suited for the production of the catalyst.

The molar ratio of organometallic compound or hydride to titanium compound is not critically important. However, it is preferably between 50 and 1000.

The process according to the invention is carried out in the liquid phase in the presence or absence of inert diluents carried out. The copolymerization is preferably carried out in a mixture of the liquid monomers carried out without inert diluents. If inert diluents are used, their narrow range is preferred less than 50% by weight, based on the monomers. as inert diluent used as the reaction medium liquid aliphatic, aromatic and cycloaliphatic halogenated are suitable, for example and non-halogenated hydrocarbons such as η-hexane, n-heptane, benzene, toluene, xylene and cyclohexane.

The copolymerization temperature is preferably between -20 ° and + 8O ⁰ C. It is however also possible to use both below -20 ⁰ C, z. B. at temperatures down to -50 C, as well as at temperatures above 80 ⁰ C, for example up to 150 C to work. In carrying out the copolymerization without inert diluents v ird worked / preferably at temperatures between 0 ° and +40 ⁰ C.

The elastomeric ethylene-propylene copolymers are produced by keeping the ethylene-propylene molar ratio in the liquid phase below 1 · or at 1: 4. The ethylene content in the binary copolymers varies

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generally from JO to 70 wt. The diene content or polyene content in the unsaturated copolymer seeds is 0.1 to 2 mol%. As dienes or polyenes. cyclic or acyclic non-conjugated dienes and polyenes can be used, for example cyclooctadiene-1,5 * dicyclopentadiene, norbornadiene, ethylidene norbornene, 5-methyltetrahydroindene, hexadiene-1,4, 4,8-dimethyl-1, 4,9-decatriene and Dienes containing endomethylene groups. The molecular weight of the copolymers prepared in this way can be adjusted during the copolymerization by working in the presence of chain transfer agents, for example alkyl halides, organometallic compounds of zinc or cadmium, or in the presence of hydrogen. It is known that the activity of Ziegler catalysts, which are obtained from transition metal compounds and from organometallic compounds of metals of the first, second and third groups of the periodic table, is considerably reduced if hydrogen or other chain transfer agents used to adjust the molecular weight of the polymer are present in the polymerization system serve, are present. The process according to the invention, on the other hand, has the great advantage that it is possible to keep the molecular weight of the copolymers within the limits of practical usefulness (corresponding to an intrinsic viscosity of 1.5 to 4 dl / g, measured in tetralin at 150.degree ), and still keep the yield of copolymer, based on the amount of catalyst used, high.

The following comparative examples 1 to 4 are intended to illustrate that the presence of the Lewis base in the catalysts used in the process according to the invention is crucially important. The experiments described in Comparative Examples 1 and 4, in which no Lewis base was used, and the experiments described in Comparative Examples 2 and 3, in which the Lewis base

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was removed from the catalyst, show that the copolymers obtained are substantially poorer elastomers Have properties than the copolymers obtained by the process according to the invention. Compare for example, the deformation rest of the vulcanizates obtained according to Comparative Examples 2 and 3 the deformation rest of the vulcanizates of Examples 2 to

Comparative example 1

9.1 g of anhydrous WgCIp, which has ^{been calcined for 48 hours "at 45O 0} C in gaseous flowing HCl, and 0.39 g of TiCl ^ are 62 hours at 20 ° C in a glass mill (length 100 mm, diameter 50 mm), the 550 contains 6 steel balls of 9.5 in diameter, ground under nitrogen, 530 g of propylene are introduced into a 3-1 steel autoclave which is equipped with a manometer, stirrer and thermometer and is kept at + 5 ° C. Then ethylene is added up to 8.5 kg / cm and hydrogen up to 9.5 kg / cm. The obtained by mixing 2 ml of Hq) ₅ with 0.07 g of the mixture of MgCl ₂ and TiCl ^

Catalyst prepared in 8 ml of n-heptane is pressed into the autoclave with nitrogen. During the trial the pressure is kept constant by pushing in ethylene. The polymerization is terminated after one hour. 202 g of dry product are obtained.

The infrared spectrum of the copolymer shows that it contains 44% by weight of propylene. Based on the X-ray analysis the copolymer has a typical polyethylene crystallinity of 4.5%. The intrinsic viscosity (inherent viscosity) in tetralin at 135 C (25 g copolymer in 100 ml) is 2.1 dl / g.

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100 parts by weight of copolymer v / ground on a two-roll mixer with 50 parts of HAF carbon black, 6.75 parts of 4O; 6igem dicumyl peroxide (Perkadox BC 40) and 0.32 parts of sulfur mixed. The mixture is in a press for 40 minutes vulcanized at 165 ° C. A vulcanized plate with the following properties is obtained here:

Tensile strength 202 kg / cm ²

Elongation at break 440 %

Modulus at 300 % elongation. 122 kg / cm ²

Deformation rest at break 24 %

Comparative example 2

In the mill described in Comparative Example 1, 7 g of anhydrous MgClp and 3 _? 8 g of benzonitrile were ^{ground at 20 °} C. for 48 hours. 6.9 S MgCl ₂ -O ^ C ₆ H ₅ CN are suspended in TiCl ^, whereupon the mixture is mixed under nitrogen at 125 ° C. for 1.5 hours. The suspension is filtered hot, washed several times with excess TiCl ^ at 125 ° C. until the benzonitrile is removed and finally washed with n-heptane until the chlorine ions in the washing medium disappear. After drying under reduced pressure, the product contains 1.58% by weight of titanium.

In the autoclaves described in Comparative Example 1 and kept at +5 ° C., in the order given the following respondents introduced:

510 g propylene, ethylene up to a pressure of 8.5 kg /

2?

cm, hydrogen up to a pressure of 9.5 kg / cm and the catalyst obtained by mixing 2 ml Α1 (ίσ ^ Η ~) -, with 0.05 g of the mixture of MgClp and TiCl ^ in 8 ml of n-heptane has been prepared. During the experiment, the pressure is kept constant by forcing in ethylene. The attempt is terminated after one hour. as

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Product v / ground obtain 184 g of copolymer having a propylene content of 45.5 percent - has / o and typical for polyethylene and polypropylene crystallinity of 9.5%.. The inherent viscosity is 2.2 dl / g.

The copolymer obtained in the mixture described in Comparative Example 1 under the conditions mentioned there has been vulcanized has the following properties:

Tensile strength 214 kg / cm ²

Elongation at break 420 %

Modulus at 300 % elongation 133 kg / cm residual shape change at break 20 #

Comparative example 5

19.4 g of anhydrous MgClp, which is suspended in 100 ml of hexane, are mixed with 10.1 g of benzonitrile while stirring and under nitrogen. The mixture is refluxed for 6 hours, filtered and dried under reduced pressure. This gives 22.6 g of a solid product, the composition of which corresponds to _{the formula MgGIp.0.5CgH 1 -CN.} 9.4 g of this product are treated with TiCl ^ used in excess under the conditions mentioned in Comparative Example 2. After drying under reduced pressure, the product contains 0.24% by weight of titanium.

A copolymerization test using 0.126 g of the mixture of MgClp and TiCl prepared in the above-described manner is carried out under the conditions mentioned in Comparative Example 2. carried out. This gives 53.5 g of a product with a propylene content of 47.6% by weight and a crystallinity of 6.7 % typical for polyethylene. The product has an inherent viscosity of 2.1 dl / g.

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The vulcanized in the mixture mentioned in Comparative Example 1 under the conditions mentioned there Copolymer has the following properties:

Tensile strength 200 kg / cm ²

Elongation at break 420 %

Module at 300 % elongation 115 kg / cm ²

Deformation rest at break 20 %

Comparative example 4

A copolymerization attempt is carried out at $ ° C in one 5 1 autoclave carried out in the following Reactants are introduced in the order listed: 515 S propylene, ethylene up to a pressure

from 7 »7 kg / cm, hydrogen up to a pressure of ρ

8 »7 kg / cm and a catalyst which was prepared by in 8 ml of n-heptane 2 ml of AlCiC ₄ Hg) with 0.071 g of a TiCl ^ / MnClp mixture obtained by grinding 6> 72 g of anhydrous MnClp and 0.29 g of TiCl ^ was prepared, were mixed. The attempt is canceled after one hour. 67 g of a copolymer are obtained with the following properties:

Propylene content 53.2% by weight

Intrinsic viscosity (inherent viscosity) 2.3 dl / g

According to the X-ray diagram, the copolymer has a crystallinity of 7.6 #.

That vulcanized in the mixture described in Comparative Example 1 and under the conditions mentioned there Copolymer has the following properties:

tensile strenght

Elongation at break 420 / o

Module at 300 % elongation 117 kg / cm

Deformation rest at break 14 ^J / o

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A comparison of the deformation rest of this vulcanizate with the deformation rest of that produced according to Example 33 Vulcanizate shows that the deformation rest of the last-mentioned vulcanizate is significantly lower.

example 1

In those described in Comparative Example 1 and in 5 C held autoclave, 525 g of propylene are

2 leads, whereupon ethylene to 7.7 kg / cm and hydrogen to

8.7 kg / cm can be applied. A catalyst is then pressed into the autoclave with nitrogen, which was prepared by adding 0.036 g of the MgClp / TiCl ^ mixture prepared according to Comparative Example 1 and 2 ml of Al (IC ₄ Hq); ,, that 1 minute in 5 ml of n-heptane had reacted with 0.02 ml of benzonitrile, were mixed in 4 ml of n-heptane. The pressure is kept constant during the experiment by forcing in ethylene. The attempt is canceled after one hour. There are 50.5 g of a copolymer obtained, which contains 52.4 wt.% Propylene, and typical for polyethylene and polypropylene crystallinity of 7.8% and an intrinsic viscosity (inherent viscosity) of 1.9 dl / g has.

100 parts by weight of the copolymer are mixed with 50 parts of HAP carbon black and 6.75 parts on a two-roll mixer 40 # dicumyl peroxide (Perkadox BC40) and 0.32 parts Mixed sulfur. The mixture is vulcanized in a press at 165 ° C. for 40 minutes. The vulcanized copolymer has the following characteristics:

Tensile strength 217 kg / cm ²

Elongation at break 420 %

Module at 300% elongation 126 kg / cm ²

Deformation rest at break 16 %

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Example 2

Under nitrogen, 6.16 g of anhydrous MgGIp and 3,54- g of benzonitrile are milled at 20 ⁰ C in the manner described in Comparative Example 1 mill. After 24 hours, 0.41 g of TiCl2 are mixed in, followed by grinding for a further 62 hours.

In the autoclave described in comparative example 1, which is kept at 5 ° C., the following are introduced in this order: 550 g propylene, ethylene up to a pressure of 7.7 kg / cm, hydrogen up to a pressure of 8.7 kg / cm and a catalyst which was prepared by adding 2 ml of 'AlCiC ^ Hg), with 0.028 g of the _{mixture obtained by grinding the TiCl 4} / MgCl ₂ .0.5C ₆ H ₅ CN mixture (Ti content 1 wt .- ^ ) were mixed in 8 ml of n-heptane. The pressure is kept constant during the experiment by pushing in ethylene. The attempt is canceled after one hour. 130 g of copolymer are obtained with a propylene content of 4.5% by weight , a crystallinity typical of polyethylene of 2.3 % and an intrinsic viscosity of 1.8 dl / g. The copolymers prepared according to this example and the following examples were vulcanized in the mixture described in example 1 and under the conditions mentioned there. The vulcanized copolymer has the following properties:

2 tensile strength 212 kg / cm

Elongation at break 400 %

Module at 300 % elongation 133 kg / cm

Deformation rest at break 10 ^r / o

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Examples 3 to 20

Copolymerization experiments are based on the in Example 2 described '.Veise using complexes of MgGIp with various Lewis bases as carriers of TiCl ^ carried out. The complexes and the bond of the TiCl ^ were among those described in Example 2 Conditions made. The results obtained are given in the table below. The vulcanization was carried out in the mixture described in Example 1 and under the conditions specified there.

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example

No.

carrier

link

5 6

10 11 12

14 15 16 17 18 19 20

Table 1

Bound to Aldenes

Ti, wt .-? O

ml

Ethylene Hp Requirement Over Loan Time, pressure pressure Atm. Atm. Hours.

MgCl ₂ (J-CN

MgCl ₂ -O.5CH ₅ O (^ -COOC ₂ H MgCl ₂ .O.25 OC (OC ₂ H ₅ ) ₂ MgCl ₂ .0.5 £ Λ -COOC ₂ H ₅

, .0.5 coumarin

^. 0.2 CH ₃ COCH ₅

• COCH,

, .0.25 ^ ⁷

i.0.5 K McCIp.0.2 (j> _Ii

, .0.5 CII ₅ CN ', .0.5 GIl ₅ O; .0.5 POCl ₅

> -CN

• 2 · ¹

0.057

0.03

0.045

0.045

0.031

0.053

0.068

0.05
0.04

0.05

0.042

0.122

0.037
0.044

0.052
0.033
0.045

0.05

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

0.9

2 2 2.3

1.7 1.8

1.6

3.3

1.3

1.2

1.5

2.5

1.8

1.9 1.9 1.9 1.9 1.9 1.9 1.5 1.9 1.9 1.9 2.2

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

2 1 1 1 1 1 2 1 1 1 1 2 1 1 2 1

0.5 2

example Copoly- ° 3 Crystal Tabel 1 (cont. fracture
strain of the vulcanizates shape
change-
rest at
Fraction, % No. merisat, 42.4 line,
(Roentgen-
Ό diagram 'Border 390 300> -
, Module,
ρ
kg / cm 10 5 50 49 . 3.9 visco
sity
dl / R properties 360 150 10 4- 137 44 2.6 2.1 train
firm
ability ^
kg / cm 390 151 10 5 93 41 3 1.8 220 390 170 10 6th 72 48 1.8 2.1 196 440 137 12th CJ 7th 135 44.6 track 2.2 227 400 122 10 CD
CD 8th 34.5 49.4 track 1.9 210 450 139 12th CX)
cn 9 67.5 54.8 3.6 2.3 221 440 113 12th 10 85 47.2 track 2.4 220 420 124 16 CD 11 14th 43.2 5.8 2 214 290 130 10 CD
cn 12th 9.5 46.2 3.9 2.7 213 380 - 8th O 13th 48.5 52.6 track 2.5 211 500 166 12th 14th 115 43.2 2.6 248 400 87 16 15th 1.7 43.4 3.3 219 400 125 12th Ιό 42 46 4.6 2.7 190 370 158 10 17th 49.5 42.4 1.3 2.6 196 390 172 8th 18th 112 45.8 2.1 2 232 400 160 10 19th 155 42.8 track 2 239 400 130 10 20th 38 2.5 2 218 156 2.5 205 225

Example 21

In the Liühle described in Comparative Example 1, 4.8 g of anhydrous MgCl ₂ , 4.78 g of MgCl and 0.41 g of TiCl. Ground for 60 hours. The following reactants are placed in a 3 liter autoclave kept at 5 ° C. in the order given: 510 g propylene, ethylene up to a pressure of 8.6 atm., Hydrogen up to a pressure of 9> 6 atm. and a catalyst prepared by adding 2 ml

with 0.037 g of the mixture of TiCl ^ and ₂₅ COOC ₂ H, - were mixed in 8 ml of heptane. During the experiment, the pressure is kept constant by forcing in ethylene. The duration of the experiment is 1 hour. 47 g of a copolymer with a propylene content of 40% by weight are obtained. The X-ray diagram of the copolymer shows a crystallinity of 5i? # · The intrinsic viscosity is 2.2 dl / g. The vulcanizate has the following properties:

Tensile strength 262 kg / cm ²

Elongation at break 340 / o

Module at 300 % elongation 210 kg / cm ²

Deformation rest at break 12 70

Example 22

4.79 g of anhydrous MgCl ₂ , 4.8 g of MgCl ₂ .0 (C ₂ H ^) ₂ and 0.41 g of TiCl ^ are ground for 60 hours under the usual conditions. The copolymerization is carried out in the manner described in Example 21 at an ethylene pressure of 2.8 atm. carried out. The catalyst is prepared by mixing 2 ml of AlCiC ₄ Hg) ₅ with 0.046 g of the mixture of TiCl ^ and MgCl ₃ .1 / 3-0 (C ₂ Hr) ₂ in 8 ml of n-heptane. The attempt is canceled after one hour.

Weight of the copolymer 33 g

Propylene content 46

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_ ₂₁ _

Intrinsic viscosity
Crystallinity

Properties of the vulcanizate: tensile strength
Elongation at break
Modulus at 300 % elongation. Deformation rest at break

Example 23

Under the usual conditions, 3 »97 g of anhydrous MgCl ₀ and 0.60 g

3, 2 dl / g 1, 8 ^c / o 248 kg / cm 340 % 196 kg / cm 8th %

Ground for 24 hours. After adding 0.2 g of TiCl ^, is Milled for another 62 hours. The copolymerization is carried out under the conditions described in Example 21 an ethylene overpressure of 1.9 atm. and a hydrogen overpressure of 1 atm. carried out. The catalyst is prepared by adding 0.94 ml of Al (IC ^ Hq), with 0.062 g

H ₂ - CH ₂ \

the mixture of TiCl. and MgCl ₀ .1 / 10 0

XH ₂ -

be mixed in 8 ml of n-heptane. The experiment is terminated after 2 hours.

Yield of copolymer, propylene content
Intrinsic viscosity
Crystallinity

Properties of the vulcanizate: tensile strength
Elongation at break
Modulus at 300 ^: / o elongation, deformation rest at break

20 g 47.8 2.2 dl / g %

3.1 %

217 kg / cm ^fc> 440 % 122 kg / cm ² 16 / o

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_ 22 _

Example 24

4.48 g of anhydrous MgCl ₂ and 2.42 g of C ₆ H ₁ -CN are ground for 24 hours under the usual conditions. After adding 0.3 g of 3TiCl, .AlCl ^, grinding is carried out for a further 62 hours. The copolymerization is ^{carried out at 30 °} C. by adding 480 g of propylene into the autoclave and ethylene up to 16.7 atm. is pressed. The catalyst is prepared by mixing 2.5 ml of AlCiC ₄ H ₁ O ₅ with 0.038 g of the mixture of 3TiCl, .AlCl, and MgCl ₂ .0.5C ₆ Ht-CN in 8 ml of heptane. The experiment is terminated after one hour, and 189 S copolymers with a propylene content of 51.4% by weight and an intrinsic viscosity of 1.8 dl / g are obtained. The X-ray diagram shows traces of crystallinity. The vulcanizate has the following properties:

Tensile strength 190 kg / cm ²

Elongation at break 400 ^C / O

Module at 300 ^: / o elongation 121 kg / cm ²

Deformation rest at break 12 %

Example 25

The copolymerization is carried out under the conditions described in Example 24. The catalyst is prepared by adding 4.24 ml of AlCiC ^ HgK with 0.065 g of a mixture of TiCl ₅ (OC ₆ Hc) and MgCl ₂ -0.5C ₆ H ^ CiJ, which is obtained by grinding 4.04 g of MgCl ₂ , 2 , 19 g of C ₆ H ₅ CN and 0.35 6 TiCl ₅ (OC ₆ Hc) has been prepared under the conditions described in Example 24, are mixed in 8 ml of heptane. 262 g of copolymer with a propylene content of 53> 2% by weight, an intrinsic viscosity of 1.8 dl / g and traces of crystallinity are obtained. The vulcanizate has the following properties:

Tensile strength 173 kg / cm ²

Elongation at break 440 %

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Module at 300 # elongation 101 kg / cm

Deformation rest at break 13%

Example 26

The experiment described in Example 2 is carried out at a temperature of -10 C, an ethylene pressure of 1.3 atm. and a hydrogen pressure of 1 atm. repeated. The catalyst is prepared by mixing 8.5 ml of Al (IC ₄ Hq) with 0.119 g of a TiGl ₄ ZMgCl ₂ -0.5C ₆ H ₅ CN gel. The attempt is canceled after one hour. There are 152 g of a copolymer having a propylene content of 50.8 wt -.% To obtain an intrinsic viscosity of 2 dl / g. The X-ray diagram of the copolymer shows traces of crystallinity. The vulcanizate has the following properties:

tensile strenght 200 ρ
kg / cm Elongation at break 390 Module at 300 % 139 kg / cm 10 % " Strain Deformation rest at break Example 27

The experiment described in Example 26 is in a

Temperature of 40 ⁰ C and an ethylene pressure of

3.7 atm. carried out in the absence of hydrogen.

The catalyst is prepared by mixing 2 ml of AKiC ₄ H ₉ ) with 0.029 g of a TiCl _{4 AIgCl 2} .0.5C ₆ H CN-

Mixture in 8 ml of heptane. The attempt is made after a

Hour canceled.

Yield of copolymer 88 g

Propylene content 46.2% by weight

Intrinsic viscosity 2.2 dl / g

The X-ray diagram of the copolymer shows traces of crystallinity. The vulcanizate has the following Characteristics:

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Tensile strength 203 kg / cm ²

Elongation at break 420 #

Module at 300 % elongation 114 kg / cm ²

Deformation rest at break 8 %

Example 28

2.52 g of anhydrous MgCl ₂ and 1.37 g of C ^ H ^ CN are ground under nitrogen for 24 hours. Then 3.89 g of Al ₂ O (calcined at 1200 ° C. for 6 hours) are added and the mixture is ground for a further 4 hours. After adding 0.695 g of TiCl ^, milling is continued for a further 62 hours. The copolymerization is carried out under the conditions described in Example 21 under an ethylene overpressure of 1.9 atm. and a hydrogen pressure of 1 atm. carried out. The catalyst is prepared by mixing 1.3 ml of Al (IC ^ Hq) with 0.042 g of a TiCl ^ / Al ₂ O ₅ ZMgCl ₂ .0.5C ₆ H, -CN mixture (titanium content 2 wt .- #) . The attempt takes 0.5 hours.

Yield of copolyraerisate 191 g

Propylene content 4-4.5 wt .- ^ 6

Intrinsic viscosity 2 dl / g

Crystallinity traces

Properties of the vulcanizate:

tensile strenght 219 ρ
kg / cm Elongation at break 440 % Modulus at 300 % elongation 123 kg / cm Deformation rest at break 8th * Example 29

The copolymerization is carried out under the conditions mentioned in Example 21 at an ethylene overpressure of 1.9 atm. and a hydrogen pressure of 1 atm. carried out. The catalyst is prepared by adding 2 ml of Al (IC _{4 Hq) 7} with 0.065 U of a TiCl ^ / AlO ^ / MgCl ₂ .0.25 (C ₂ H ₅ ) ₂ NC00C ₂ H ₅ gel mixture based on the in Example 28 by grinding 5.6 g MgCl ₂ , 1.73 g (C ₂ H ^) ₂ NGOOC ₂ H ₅ , 1.5 _{U Al 2} O ₃ and 0.38 g 309851/0950

has been prepared, mixed in 8 ml of n-heptane will. The attempt is canceled after one hour. Yield of copolymer 115 g

Propylene content 46.8% by weight

Intrinsic viscosity 2.1 dl / g

The X-ray diagram of the copolymer shows traces of crystallinity. The vulcanizate has the following Characteristics:

Tensile strength 210 kg / cm

Elongation at break 420 OK

Module at 300 % elongation 123 kg / cm ²

Deformation rest at break 10 %

Example 30

6 g of anhydrous JgCl ₂ and 3.26 g of C ^ Hj-CN are ground for 24 hours. After adding 0.73 g of TiCl ₄ .2 (C ₂ Hc) ₂ O, milling is continued for a further 62 hours. The copolymerization is carried out under the conditions mentioned in Example 21 at an ethylene overpressure of 1.9 atm. and a hydrogen pressure of 1 atm. carried out. The catalyst is obtained by mixing 1.23 ml of Al (i0,, H _n ) -. with 0.017 g

^ " 7 0

of the titanium-containing mixture described above in 8 ml of n-heptane. The attempt will take place after an hour

canceled.

Yield of copolymer 63.5 g

Propylene content 43 wt .- #

Intrinsic viscosity 2.1 dl / g

Crystallinity ₍ 2.6 %

The vulcanizate has the following properties:

Tensile strength 223 kg / cm ²

Elongation at break 400 %

Module at 300 / _o extension 146 kg / cm ²

Shape change remainder at break 8 ^c / o

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Example 31

760 g propylene, ethylene up to a pressure of 7.7 atm. and hydrogen to a pressure of 8.7 atm. are placed in a 3 liter autoclave kept at 5 ° C. A catalyst is introduced into the autoclave under nitrogen pressure, which is produced by mixing 0.06 g of a TiCl ^ / MgClp.0.5C ₍ ~ H _C -CN mixture (prepared in the manner described in Example 2) with 4, 25 ml of Al (IC ^ Hg), which has been reacted for 3 minutes with 0.02 ml of benzonitrile, has been prepared in 8 ml of n-heptane The experiment is terminated after one hour.

Polymer yield 85 g

Propylene content 40.4 wt .- / o

Intrinsic viscosity 2.3 dl / g

Crystallinity 4.3%

The vulcanizate has the following properties:

2 tensile strength 211 kg / cm

Elongation at break 380 / o

Module at 300 fo elongation 151 kg / cm ²

Deformation rest at break 12 ^J / o

Example 32

The experiment is carried out in the manner described in Example 2 using 0.032 g of the TiCl ^ / MgCl ₂ -0.5C ₆ H, -CN mixture and 2.6 ml of Al (C ₆ H ₁ ^) ₃ and after canceled an hour.

Yield of copolymer 55 g

Propylene content 41.2 wt .- ^

Intrinsic viscosity 2.2 dl / g

Crystallinity 1.9 / o

The vulcanizate has the following properties:

Tensile strength 245 k _G / cm ²

Elongation at break 380 '/ o

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Modulus at 3OO % elongation 16 ¹ J kg / cm ²

Deformation rest at break 10 %

Example 33

_{The experiment described in comparative example 4 is} repeated using 1.7 ml of Al (iC ^ Hq) -, and 0.058 g of a TiCl 4 / MnClp.0.5C ₆ H ₍ -CN mixture. This mixture was prepared as follows : 6.61 g of anhydrous LinCIp and 2.7 "! G of 0, -Hj-CN v / ground for 24 hours. After adding 0.33 g of TiGl ^ it is ground for a further 62 hours. The copolymerization is after 1, discontinued 5 hours. this gives 39 g of copolymer! sat having a propylene content of 43.5 wt .-% and obtain an intrinsic viscosity of 2.2 dl / g. the X-ray pattern shows that the copolymer comprises 2 jo crystallinity. the vulcanizate has the following properties:

Tensile strength 211 kg / cm ²

Elongation at break '400 %

Module at 300 % elongation 135 kg / cm

Deformation rest at break 8 %

Example 34

4.8 g of anhydrous MgCl ₂ and 5j25 g of benzonitrile diluted with 50 ml of anhydrous n-heptane are introduced into a 100 ml flask under nitrogen. The mixture is refluxed with stirring for 100 hours. It is then cooled to room temperature, washed several times with n-heptane and dried under reduced pressure at room temperature. The analysis shows that the product obtained has the formula MgCl ^ · Ο, -Η, -CN. 6.3 g of the complex thus obtained are suspended in 50 ml of n-heptane under nitrogen in a 100 ml flask. After adding 0.56 g of TiCl ^, the mixture is heated under a reflux condenser with stirring for 3 hours. It is then filtered at room temperature and twice with a total of

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Washed 200 ml of n-heptane. No benzonitrile was found in the wasoh liquid. The analysis shows that the TiCl ^ / MgCl ₂ «C ₆ H, _CN mixture contains 1 wt .- ^ titanium metal.

In those described in Example 1 and kept at 5 ° C Autoclaves are used in this order 550 g propylene, Ethylene up to a pressure of 7.7 atm., Hydrogen up to a pressure of 8.5 atm. and introduced a catalyst, by mixing 3 ml of AICiC ^ Hq), with 0.062 g of the TiCl./MgClp.CVH.-CN mixture in 8 ml of n-heptane has been. The attempt is terminated after 2 hours. There are 23 g of copolymer with a propylene content of 37.5 wt .-> & and an intrinsic viscosity of 2.4 dl / g. The vulcanizate has the following Characteristics:

Tensile strength 241 kg / cm ²

Elongation at break 410 %

Module at 300 ^ elongation 1 ^ 9 kg / cm

Pormander residue at break 10 %

309851/0 950

Claims (12)

Claims a) a hydride or an organometallic compound of aluminum with b) one of the following catalyst-forming components: A) the product obtained by bonding a halogenated titanium compound to a support, of an at least partially complexed with a Lewis base anhydrous magnesium or Manganese dihalide consists B) the product obtained by adding the halogenated titanium compound to a carrier consisting of a anhydrous magnesium or manganese dihalide with a surface area of more than 5 m / g consists in The presence of a Lewis base is combined; C) the product obtained by adding the halogenated titanium compound to a carrier consisting of a Anhydrous magnesium or manganese dihalide and a Lewis base consists, under conditions, under which the carrier has a surface area of more than 5 m / g in the absence of the base will; D) the product obtained by adding the halogenated titanium compound to a carrier consisting of a at least partially complexed with a Lewis base 30985 1/0950 bur.denen anhydrous magnesium or manganese dihalide exists, under conditions under which the non-complexed magnesium or manganese dihalide a surface of more than 5 m / g is obtained, is brought together, being the molar ratio between the magnesium or manganese dihalide and the Lewis base in the catalyst is 1: 2 to 20: 1. 2.) Process for the production of saturated, elastomeric and vulcanizable copolymers of ethylene with higher cc-01efinen of the general formula CHp = CHR, in which R is an alkyl radical with 1 to 6 carbon atoms, or of weakly unsaturated copolymers of ethylene, higher oc-olefins and polyenes, characterized in polymerizing the monomer mixture in the presence of a catalyst which has been prepared by mixing a) one of the partially complexed with a Lewis base Hydrides and organometallic aluminum compounds catalyst-forming component with b) a catalyst-forming component, which consists of the product obtained by treating the halogenated Titanium compound with a carrier consisting of a magnesium or manganese dihalide and has a surface area of more than 5 m / g, the molar ratio of the magnesium or manganese dihalide to the Lewis base in the catalyst is 1: 2 to 20: 1. 3.) The method according to claim 1, characterized in that are used as Lewis bases electron donor compounds in which the electron donor atoms O, P and / or N are. 30985 1/0950 4.) Process according to claim 1 to J>, characterized in that the Lewis bases are triethylamine, pyridine, diethylaniline, ethyl ether, ethyl benzoate, ethyl acetate, POCl ,, trimethyl phosphite, diethyl carbonate, ethyl N, N-diethyl carbamate, acetonitrile, benzonitrile , Ethyl p-anisate and / or p-anisonitrile are used. 5.) The method according to claim 1, characterized in that a catalyst component (b) is used, which by joint kahlening of the halogenated titanium compound with a support consisting of an anhydrous magnesium or manganese dihalide in the presence of the Lewis base under conditions under which the Carrier in the absence of the base a surface
has been received. 2 the base has a surface area of more than 5 m / g, 6.) The method according to claim 5i, characterized in that a catalyst component (b) is used, which is obtained by co-grinding one of an anhydrous magnesium or Manganese dihalide existing carrier with the Lewis base and then merging the common Milling obtained product with the halogenated titanium compound has been obtained. 7.) The method according to claim 6, characterized in that the co-grinding is continued after the halogenated Titanium compound with the product of the joint grinding of the magnesium or manganese dihalide and the Lewis base has been merged. 8.) The method according to claim 7, characterized in that a catalyst-forming component (b) is used, which by grinding together the halogenated titanium compound with a support made of at least partially complexed with a Lewis base magnesium or 309851/0950 Manganese dihalide exists under conditions under which the non-complex-bound carrier has a surface area of more than 5 m 2 / g has been obtained. 9.) The method according to claim 1, characterized in that as a catalyst-forming component (a) partially Aluminum trialkyls or aluminum trialkyls complexed with a Lewis base are used. 10.) The method according to claim 1 to 9 »characterized in that the monomer ^{mixture at a temperature in the range of -50 0} C to +150 ⁰ C, vorzui
+ 80 ° C is copolymerized. from -50 ⁰ C to +150 ⁰ C, preferably in the range from -20 ° to 11.) Process according to claim 1 to 10, characterized in that the monomer mixture in the absence of inert liquid diluents is copolymerized. 12.) The method according to claim 1 to 11, characterized in that that ethylene and propylene are copolymerized and a molar ratio of ethylene to propylene of less than 1: 4 or 1: 4 in the liquid phase of the copolymerization mixture maintains. 309851/0950