DE2256533A1 - MIXED POLYIMINE HYDRIDES, CONTAINING ALUMINUM AND METALS OF THE SECOND GROUP - Google Patents

Description

Dr. F. Zumsteln sen. - Dr. E. Ar.smann Dr. R. Koenlgsberger - Dipl.-Phys. R. Holzbauer - Dr. F. Zumstein Jun.

PATENT LAWYERS

TELEPHONE: SAMMEU-NO. 22S341

TELEX 529979

TELEGRAMS: ZUMPAT CHECK ACCOUNT: MUNICH 91139

BANK ACCOUNT: BANK H. HOUSES

8 MUNICH 2.

BRÄUHAUSSTRASSE 4 / III

12 / me

SNAM PROGETTI S.p.A., Milan / Italy

Mixed, aluminum and metals of the second group

containing polyimine hydrides

The present invention relates to aluminum and metals containing the second group of the periodic table of the elements mixed polyimine hydrides, which are characterized by the presence of sequences of the species

H -

ι- ι

R E

are characterized in which M is the metal of the second group of the periodic table and R is a substituted or unsubstituted one Can be alkyl, aryl, alkaryl or cycloalkyl radical.

In particular, the invention relates to compounds of the formula

U) - (-Al-N) r-X « y ι ζ

MR

309821/1089

(2)

where χ, y and ζ represent the number of repeating units. Here, x, y and ζ can be identical or different and range from 1 to 100. The terminal groups X and X ¹ can be identical or different and form groups such as -H, -AlH ₂ , -NHR, -MH.

It is clear that the atomic ratio M / Al need not be 1, since in the same polyimine chain sequences of the type (1) along with polyimine sequences of various lengths that only aluminum atoms or the other metal atoms may be present.

Viewed from another specific point of view, the invention also encompasses complexes of the above compounds: Complexes include the addition products of the compounds mentioned with other molecules that act as Lewis bases, like aliphatic ^, aromatic, cyclic ethers, tertiary amines, thioethers, alkali metal hydrides, and some ethers, as well to understand the intrinsic complexes of the compounds themselves created by the mutual action of the nitrogen atom of the imine group formed with one or both metals, or the intrinsic complexes formed by the interaction of atoms belonging to the same chain or to different polymer chains.

The compounds of the invention are generally by direct reaction of the alanate of the metal of the second group with a primary amine or an organic nitrile prepared according to the following reaction schemes:

; ■; ζ 3 8 21/1 ο 8 9

a) x

+ 3x R-

H
I. H Al-N-M-N- -Al-N- 1 I. I. R R R.

R - CN

Al

N /

M - N /

HI

Al

The reactions can take place in aromatic and aliphatic hydrocarbon solvents or in solvents of the polar. · Type, such as ethers, tetrahydrofuran, tertiary amines, etc. carried out will.

They are preferably carried out in tetrahydrofuran which contains the Conversions are favored because of the good solubility of the end products as well as because of the solubility of some of the starting alanates.

The reaction proceeds via a simple and slow addition of a certain amount of the amine or organic nitrile "dissolved" in a suitable solvent, to a solution or suspension of the alanate of the metal of the second group in the same or another solvent. Preferably the same solvent is used to dilute the amine and alariate.

Both the starting and the end products are generally decomposed by air and moisture. It is therefore necessary manufacture and maintain the products under an inert gas atmosphere. ·. ■.

The reaction is generally carried out at room temperature, however, it can also be carried out at a lower or higher temperature. The limits depend on the highest Temperature of the stability of the reaction products and with respect to

'- ^:; ■ ■ '1/1 0 β fi

the lowest temperature depends on the reactivity of the alanate with amine.

According to the above reactions, products with an M / Al atomic ratio close to 1: 2 are generally obtained. Products with a value different from this ratio, by treating the raw reaction products with suitable solvents, which have different dissolving power with respect to the fractions of different composition will.

The value for χ is in the range from 1 to 100, preferably from 5 to 10. Alternatively, the products according to the invention can be obtained by reacting polyalkyl (aryl) imino derivatives of the metals second group and polyalkyl (phenyl) iminoalanes are obtained. The reaction is carried out under those for the above synthetic methods specified conditions carried out.

The nature of the products according to the invention was, apart from the chemical elemental analysis, also by IR spectrometry and Precision tests carried out by the column extraction method which are usually used to characterize compounds of a polymeric nature have been highlighted.

It is known from the literature that polyimine compounds that only Containing aluminum, an IR band (V Al - H) in the area from 1830 - 1905 cm ", with the correct position being a such a band depends on the nature of the hydrocarbon residue, which is bound to the nitrogen atom [Makromol. Chemie 122, 168 (1969)].

The same imine radicals and the partial replacement of aluminum atoms by metal atoms from the second group cause the products according to the invention a splitting of the \ 7 Al - H absorption band, generally to a lower frequency because of the lower electronegativity of the metal of the second Group regarding aluminum. The splitting amount depends on

3098? 1/1 (\ n <\

the difference in electronegativity of the two metals in the chain.

Fractionation by the column extraction method allows the crude reaction product to be subdivided into several fractions, which contain both metals;

With regard to the nature of the metal of the second group and / or the reaction conditions for the preparation of the product, show The resulting fractions have a very similar composition or very different compositions, but contain both Metals.

Examination of the raw products by X-ray diffraction Powders showed that these are generally amorphous Connections.

The compounds obtained are readily soluble in polar solvents and especially in tetrahydrofuran, but it is correspondingly the nature of the imine residue, the nature and amount of the metal of the second group and the degree of polymerization possible, also solutions in non-polar hydrocarbon solvents to obtain.

The products according to the invention can be used as catalysts as such can be used in the polymerization of monomers of the vinyl, acrylic, epoxy, aldehyde, etc. type. In particular makes the presence of

H I «. # · -M-N-Al-. ··

I.
R.

the products are active, e.g. for the homopolymerization of methacrylonitrile to crystalline polymers.

The polymerization of the above-mentioned monomers can be carried out in aliphatic, aromatic or cycloaliphatic hydrocarbons

309821/1089

solvent solvents, in polar solvents, preferably Ethyl ether or tetrahydrofuran, or in the absence of any Diluents can be carried out.

In addition, the compounds obtained are very effective reducing agents for both organic and inorganic ones Links. This property and the ability to react with the transition metal derivatives make such products useful components of catalyst systems suitable for the polymerization of olefin and diolefin monomers.

Therefore, the compounds with some derivatives of the transition metals and preferably titanium and vanadium are combined.

The aluminum / transition metal atomic ratio can be used as an index for the molar ratio used according to which the invention Compounds and the transition metal derivative can be reacted in the catalyst system.

Such a ratio can range from 0.2 to 100.

The polymerization is usually carried out in a hydrocarbon solvent
carried out.

solvent at a temperature in the range from -30 to 100 ^° C

The following examples serve to better illustrate the invention Products and their use.

All operations were carried out under a nitrogen atmosphere, the nitrogen being completely anhydrous and free of oxygen and COp.

All reagents and solvents were made anhydrous prior to use.

309821/1089

Example Γ

A solution of 110 mmol of Ca (AlH ₂ ^) ₂ in 4θΟ ml of tetrahydrofuran was introduced into a three-necked flask equipped with a mechanical stirrer and a funnel. A solution of 330 mmol of n-butylamine dissolved in 70 ml of tetrahydrofuran was added dropwise to the above-mentioned stirred solution at room temperature.

Hydrogen evolution was observed during the addition. The mixture was stirred at room temperature for 18 hours. At the end traces of insoluble material were filtered off and the solution evaporated under reduced pressure. The residue was dried again for 6 hours at 10 "^ mm Hg white plague with the following chemical analysis was obtained:

C # = 47.20 H % = .9.90 N # = 10.14 Al % = 13.17 Ca % = 12.32 H active / Al = 1.37.

The analytical data agree well with the average composition

5EHF

^ Ca - H - Al-

TKF

-N- Al-- U -r Ca ~ K - Al- *

I f

- H-Al-Ii -CaH

C..H

9 ^ 9

with a molecular weight of 1258.6, from which the following theoretical values are calculated:

C % = 49.57 H % = 9.69 N ^ = 10.01 Al fa = 12.86 Ca % = 12.73 H active / Al = 1.32.

3CPSV 1/1

- 8 The IR examination of the product suspended in Nujol showed a broad absorption band V _a -i_h with a maximum at 1720-1750 cm "; in solution in tetrahydrofuran a less broad band resulted with a maximum at 1730 cm".

13 »g of a 5 by a similar preparation obtained product was dissolved in 80 cc of tetrahydrofuran and the obtained solution were successively added with different amounts of n-heptane to obtain a slightly cloudy haze was formed. Then in each case the solution was cooled to -78 ⁰ C and after one night at this temperature for the precipitation of the supernatant solution was removed by decantation, and analyzed dried in vacuo. In this way, four different fractions were separated off which showed a composition which was quite similar to the crude product and corresponded to a very homogeneous distribution of two different metals in the polyimine chain (cf. Table 1).

The IR analyzes of the fractions showed a V ^- Al - H absorption of the same frequency as the crude product.

Example 2

A solution of 25 mmoles of Ca (AlH ^) ₂ in 150 ecm of tetrahydrofuran was placed in a three-necked flask equipped with a stirrer and a filling funnel. A solution of 75 mmol of aniline in 40 ecm of tetrahydrofuran was then dripped into the above stirred solution.

It was stirred overnight at room temperature and a fine white precipitate formed.

It was filtered through a porous glass septum, the precipitate

was washed several times with tetrahydrofuran and in vacuo

-2
(3 hours at 10 mm Hg at room temperature) to give 10.5 g of a powdery white compound.

'*. C * - "HV 1/1 0 8 9

Analysis: = 62 , 10 • 50 , 65. N C % t = 8 , 21 H % 7, ■ 6 Al 5 Ca % =

The analytical data agree well with an average composition

THF

-H-- Ca - K - AO. -

. t / *
THF C 'BL THF
6 5

-H- Al - K - Ca - Κ '- Al. *.

ί f I t I • C ^ H, - THF CH- THF C ^ H-

Ο? ΙΪΡ

THF

J Ψ

/. t

from the molecular weight of 4132.9, from which the following theoretical Calculate values:

C % '= 61, βθ
Al '% = 7.83

H % = 7.60 Ca % = 6.78.

= 6.10

IR analysis of the product suspended in Nujol showed a Absorption band that corresponds to the V Al-H band with a maximum at

-1
1750 cm could be assigned.

The solution obtained from the reaction became the solvent removed by evaporation in vacuo. The white powdery The residue showed, dried in vacuo, a composition which was very similar to that of the insoluble part:

Al % = 8.26

% = 6.96.

In this case too, the IR analysis showed that suspended in Nujol Product a band that could be assigned to the Al-H bond, with a maximum at 1750 cm "",

30982 1/1089

- ίο -

The above aniline derivatives darken with time.

Example 3

A solution of 27.25 mmol of Ca (AlH ₁ ^) ₂ in 200 ml of tetrahydrofuran was placed in a three-necked flask equipped with a stirrer and a filling funnel. A solution of 81.75 mmol of pivalonitrile in 25 ml of tetrahydrofuran was added dropwise to the above stirred solution.

It was stirred for 18 hours at room temperature. At the end the solution was evaporated under reduced pressure and the residue

—Ρ
dried again for 5 hours at 10 mm Hg. A yellow solid was obtained with the following chemical analysis:

C # = 52.50 Al % = 11.42

H # = 10.39 Ca % = 9.63.

N ^ = 9, ^ 0

The analytical data agree well with an average composition of

THF

HI

H - Ca - N - Al I R

H.
Γ

THP.

-N-Al-N-Ca - N - Al -

I. R.

I Al

N 1 R

THP

Φ CaH

with molecular weight 3079.2, wherein

R = - CH ₂ - C

tIi-; 821/1089

- li -

The following theoretical values are calculated:

C # = 53.43 H # = 10.18 * N % = 9.55 Al $> = 12.26 Ca Jg = 10.41.

Upon IR examination in Nujol, the product showed a V Al-H band at 1760 cm " ¹ .

Example 4

6.75 mmol of Mg (AlHJi) ₂ and 100 ml of tetrahydrofuran were placed in a three-necked flask equipped with a stirrer and a hopper. A solution of 20.25 mmol of n-butylamine dissolved in 50 ml of tetrahydrofuran was added dropwise to the stirred suspension. At the end a solution was obtained which was stirred at room temperature for 15 hours. The solution was then filtered off from traces of insoluble material and evaporated under reduced pressure. The remaining white solid became

_ ρ

dried again for 5 hours at 10 mm Hg and showed the following

Analysis: = 50.72 H Jl f = 9.50 N % = 11.22 1 , 09. C% £ = 13.79 Mg % = 7.08 H active / Al = Al J

The analytical data agrees well with an average Composition of

IT - Al - H - Mg -

E Mg - H - Al

° / °. H - Al - It - MgH

V ₉ V ₉

with molecular weight 4121.8. The following theoretical values are calculated from this:

309821/1089

C % = 52.44 H # = 10.19 N % = 11.22 Al Jg = 14.39 Mg % = 7.08 H active / Al = 1.09.

The IR examination showed the product both in suspension in NuJoI as well as dissolved in tetrahydrofuran a \ 7 Al-H band with a maximum at 17βθ - 1770 cm ".

The product obtained by a similar procedure underwent fractional precipitation following that given in Example 1 Working method, subjected. The results are shown in Table 2.

All fractions obtained contain aluminum and magnesium, which leads to the formation of polyimine chains, which contain both metals, is equivalent to.

Example 5

a) 7.77 mmol of Mg (AlH ^) ₂ and 100 ml of THF were placed in a three-necked flask equipped with a stirrer and a filling funnel. A solution of 2.5.31 mmol of aniline in βθ ml of THF was then added to the stirred suspension. A solution formed. After stirring for about 2 hours, a white precipitate formed which was stirred for 18 hours. The white precipitate was filtered off, washed and dried for 6 hours at 10 mm Hg and analyzed:

C % = 62.15 H % = 8.40 N % = 7.70 Al % = 10.25 Mg % = 5.0 H active / Al = 0.96.

With reference to a polymeric compound having the formula

H THF. H

Al-N-Mg-N-Al-N-

CvH_ TIIF CUI_ Ο-Η_

6 5 6 5 6 5

309821/1089

corresponds to where χ is very large, the following are calculated theoretical values:

Mg % = 4.98 Al % = 10.82 N $ = 8.44 C % = 62.70 H % = 6.70.

The IR spectrum in Nujol showed a V Al-H band at 1800 cm
about 70

p
1800 cm ". The yield of insoluble product was

b) Magnesium polyphenylimide was prepared as follows:

A solution of 70 mmol of aniline in diethyl ether was stirred to a fresh solution of 70 mmol of MgA'tp in ether, Dioxane obtained according to that described in the literature Procedure, joined. The total volume of the solution was 200 ml (50 + 150). Formed upon addition of aniline a precipitate which then dissolved again. At the same time, evolution of gas was observed. At the end it was stirred for one night, under reflux for two hours heated and the white precipitate formed was separated by filtration. The latter was washed with water and dried. When decomposed with acidic water, it did not develop any gas, the decomposition products showed chromatographic analysis the presence of dioxane "

= 7 * 38

Analysis s = 61,
: ■ = 12 45
, 24. H 5 D.
i
Mg 6.8o C %
Mg % for . (- - ■ M -) Calculated ^C 6 ^H 5

D = dioxane

C ^ = 59 * 20 H fa = 6.40 N $ = 6.90

Mg % = 12.05.

309821/1 © i9 '

-u-

The yield was about 70 %. The compound was soluble in tetrahydrofuran and spontaneously decomposed on contact with air.

Part of magnesium polyphenylimide (32.5 gram atoms of magnesium), dissolved in 150 ml of tetrahydrofuran, was with polyphenylimino-alane (65 gram atoms of aluminum) in the form of a powder. The mixture was stirred for one night, and in the end, the resultant became Suspension filtered.

The insoluble portion was washed with THF, dried and analyzed (2 g of product were obtained).

C $ = 59.00 H # = 8.30 N % = 8, O ^

Al % = 11.53 Mg % = 5.30 H active / Al = 0.75

When examined by IR, the above product showed a

V Al-H absorption with a maximum at 1800 cm "*.

The solvent was removed from the solution by evaporation under reduced pressure and the residue was dried

and analyzed:

C % = 57.30 H % = 6.0 N $ = 8.63

Al % = 10.44 Mg % = 4.90 H active / Al = 0.90.

The IR examination showed a V Al-H absorption with a maximum at 1780-1800 cm " ¹ .

Both the insoluble fraction and the soluble fraction had a chemical composition and an IR spectrum that those of the aluminum and magnesium polyphenylimino derivative, obtained by method a), was similar.

Part of the product obtained by evaporating THF was fractionated by the column extraction method and the Results are in table; 3 listed.

J fj HH? 1/10 8 9

Example 6

In a beverage bottle with a capacity of 200 ml, which was free of air and moisture, βθ ml of toluene, 2.6 mmol [Mg AIg (NR) ^ Hp- ^ x ^un ^ "* "° ^{ml 3} ^ ⁰ Pyl ^enox iä introduced; with

[Mg Al ₂ (NR) -Z Hp] is meant the product obtained from the reaction between Mg (AlHn) ₂ and n-butylamine in a molar ratio of 1: 3t according to Example k .

The bottle was then closed with a neoprene stopper, sealed with a crown cork with a metallic shell and stirred in a thermostatic bath at + 80 ° C for 24 hours.

At the end, the polymerization was interrupted by adding methyl alcohol, which destroys an antioxidant. The reaction mixture was diluted with toluene and the solution was then distilled with acidic water, alkaline water and Washed water to remove the remains of the catalyst. The polymer was found as a residue after steam removal recovered the excess monomer and the solvent. 0.9 g of an elastic polymer was obtained, the basal molar Viscosity, determined in toluene at 30 ° C, the fourth of Was 5.07.

Example 7

According to the method given in Example 6, propylene oxide was polymerized according to the following recipe: 60 ml of toluene, 3.5 mmol. [Ca Al ₃ (NR) ₅ Η ₂ ] _χ and 10 ml of propylene oxide is with [Ca Al ₂ (NR) ^ H ₂ ^ _x ^the reaction product of Ca (AlH ^) ₂ and n-butylamine in a molar ratio of 1 : ■ 3, according to Example 1, meant. .

0.8 g of an elastic polymer were obtained, was dessen'Wert (77) at 30 ⁰ C in toluene 2.82.

30 ^ 82

Examples 8-11

The polymerization tests of methacrylonitrile were as follows carried out.

Under a nitrogen atmosphere, 90 ml of solvent was added and 1 mmol aluminum and magnesium (or calcium) in a 250 ml three-necked flask equipped with a mechanical stirrer, Cooler and funnel, introduced. When the certain temperature was reached, the monomer was quickly through the Filling funnel introduced.

At the end, the polymerization was stopped by adding methyl alcohol, which contained an antioxidant. The polymer was obtained from the reaction mixture after adding an excess of methyl alcohol and dried ^{at 50 ° C. in vacuo.}

Table 4 shows some of the results obtained.

In general, the methacrylonitrile polymers, which have been found with the help of aluminum and magnesium (or calcium) polyimine derivatives as catalysts were produced, in the X-ray examination as crystalline.

Examples 12-17

The polymerization tests of ethylene were generally carried out according to the following procedure.

In a one liter stainless steel autoclave equipped with a stirrer and a rotating magnetic connector with an armature impeller, the solution (or suspension) of the transition metal compound in 90 % of the solvent used for the test was placed. The solution (suspension) was saturated with ethylene at a certain pressure and temperature.

309871/1089

Then the aluminum and magnesium coders were added while stirring Calcium) poly! Minor derivative, dissolved (or suspended) in the remaining amount of the solvent added. Stirring and the temperature were kept constant during the test; even the pressure of the monomer was kept constant by connecting the autoclave to the cylinder containing ethylene. At the end the polymerization was stopped by adding methyl alcohol containing an antioxidant.

The excess monomer was removed and the polymer was removed from the reaction mixture after a further addition of an excess from methyl alcohol, mixed with HCl, obtained. The polymer was then dried at 50 ° C. in vacuo.

Alternatively, a stainless steel autoclave with a fit of 0.25 1 is used. In this case it was shaken and after the introduction of the monomer it became no longer fed in during the test.

The polymers obtained in each case were crystalline and showed a high molecular weight. The intrinsic viscosity, determined at 135 ° C in decalin, was -10 or above.

Some of the results obtained are shown in Table 5.

Example 18

50 ml of toluene, 0.75 mmol of Ti- (0-n C ₂₁ H ₉ ) ^ and 2.6 mmol [Al ₃ Ca (NR) ₅ H ₂ were in a vessel with a capacity of 200 ml, which was free from air and moisture was introduced. It was worked under a nitrogen atmosphere and with stirring.

The [Al ₂ Ca (NR) -, H ₂ ] was the reaction product of Ca (AlHh) ₂ and n-butylamine in a molar ratio of 1: 3> according to Example 1.

The vessel was then closed with a neoprene stopper and a metal stopper with a crown stopcock.

3Ü9821 / 1089

The metallic plug was pierced to expose a portion of the neoprene plug, allowing 11.5 grams Introduce butadiene from the butadiene-containing cylinder by connecting it to a needle for subcutaneous use.

A few minutes after the reaction between the catalyst components butadiene was introduced; the vessel was stirred in a thermostatic bath at 50 ° C. for 9 hours. In the end the Polymerization stopped by adding methyl alcohol, which contained an antioxidant, and after adding an excess the polymer was recovered from methanol, mixed with HCl, and dried in vacuo at 50.degree.

1.4 g of a solid polymer were obtained, in which, according to the IR investigation, the monomer units were bound as follows:

1.4 trans- # = 15 1.4 cis- # = 0 1.2 % = 85-

Example 19

According to the procedure described in Example 18, butadiene was polymerized according to the following formulation:

Toluene 50 ml

Ti (NXt ₂ ) ^ 0.75 mmol

[Al ₂ Ca (NR) ₅ H ₂ J _x 2.6 mmol

Butadiene 12.4 g.

1.6 g of a solid polymer in which the monomer units were obtained were obtained predominantly in the 1,4 bond; in particular, the following bonds were present according to the IR investigation:

1.4 trans- # = 60 1.4 cis- # = 20 1.2 % = 20.

3 09821/1089

'Table 1

Results of fractionation of Ca- and Al-polyimine derivative obtained by reaction

of Ca (AlHj ^) ₂ and n-

molar ratio 1: 3

(Starting solution: 13.5 g polyimine derivative in 80 ml tetrahydrofuran)

Precipitated solid

309821 raw connection fraction after another
added to
parts of Hept
(ml) ο 1. fraction OO
co 2. fraction 120 3. fraction 25th 4th 30th 45

composition

•Rest

Ca % N % H act./Al

13.90 13.17 10.20 1.17

3.3 13.60 14.70 10.10 1.38 4.7 13.25 13.77 10.85 1.37

1.4 12.97 13.00 10.31 1.25 1.0 10.72 11.00 8, βθ n.d.

2.5 14.50 8.9 12.01 1.13

IR analysis VAl-H (cm " ¹ )

in NuJoI - in THF • 1720 1720-1750 * 1720 1720-1750 1720 1720-1750 1705 1740 n.d. n.d. 1720 n.d. '

CD Ol CO

Table 2 Results of fractionation of a Mg- and Al-polyamine derivative obtained by the reaction

of Mg (AlH ^) ₂ and nC ^ HgNH _o in the molar ratio 1:

(Starting solution: 12.5 g polyimine derivative in 80 ml tetrahydrofuran)

successively added proportions of heptane (ml)

raw connection

1st parliamentary group 70

2nd parliamentary group 20

3rd fraction 75 remainder

Precipitated solid

composition

IR analysis V Al-H (cm)

G Al % Mg % N % in THF $ rsj
'cn
¹ cn
cn
co
co - 15.12 7.46 11.81 1780 3.0 15.02 9.74 11.56 1770-1790 1.3 n.d. n.d. n.d. 1800 0.7 13.36 16.55 9.75 1770-1780 7.1 16.39 4.02 13.18 I78O

Tabel

Results of the fractionation of an Al and Mg polyphenylimine derivative obtained by reacting [-Al-HN-CgH ₁ -] and [-Mg-N-CgH ₁ -] in a molar ratio

Al / Mg = 2/1

(Starting solution 10.5 g

successively added proportions of heptane (ml)

raw connection

1st parliamentary group 20

2nd parliamentary group 25

3rd political group 25

4th parliamentary group 30

5th Group 45

6th fraction 60 remainder

^M S mixed polyiminoalane in 150 ecm tetrahydrofuran)

composition

G N % Al % Mg % - 8.63 10.44 4.95 3.095 8.3 10.7 3.9 2.549 7.96 10.3 4.0 2.822 6.85 9.6 4.62 0.725 10.3 9.75 5.04 0.374 9.35 10.3 5.73 0.553 8.5 9.57 5.47

Precipitated solid

IR analysis

VAl-H (cm " ¹ )

in Nujol

I79O I79O 1785 I79O I8OO n.d. n.d.

0.210

CJl CD

Tabel Examples of the polymerization of methacrylonitrile using catalysts

made of Al- and Mg- (Ca-) - poly! less! vat en

Example catalyst (#)

solvent

Art

mmol Art

[Al ₂ Mg (NR) ₃ H ₂ ]

1
1

Toluene toluene

Tetrahydro furan

ml

90 90 90

90 temperature - _lt
Methacrylic rature cm- ",
nitrile ml ⁰ C ^Stä '

10 10 10

10

2
2

at you- 2
dunk
d.solvent

G
3

5.3
2

4.0

solid polymer

5.46
1.77
10.6

n.d.

solubility
in acetone %
(***)
14.5

■ 5.3

7.2

(*) [Al ₂ Mg (NR) ₃ H ₂ J _x (or [Al ₂ Ca (NR) ₃ H ₂ J _x ) represents the reaction product of Mg (or Ca (AlH ^) ₂ ] and n-butylamine in the molar Ratio 1: 3

(# *) at 25 ⁰ C in dichloroacetic acid (■ ***) 24-hour extraction with boiling solvent

ro cn <T> cn co co

Table 5

Examples of the polymerization of ethylene with catalysts based on transition metals, mixed with Al and Mg (Ca) - Po Iy iminderi vat en

At- autoclave catalyst
game type (*) type mole

Cocatalyst Al / Me solution - Ethy type («*) (***) medium len,

Type ml kg / cm ^Ä

Temp. Time of solid polymer Oq hours. From RX % Kribeute stallini · tat

12th A. βο 13th B. 14th A. »Λ
ο 15th B. OO
co 16 A. 17th A.

TiCl ₅ AA 1.1

[Al ₂ Mg (NR) ₃ Hg] _x [A IgCa (NR) ₃ Hg] _x TiCl ₄ 3.45 [Al ₂ Mg (NR) ₃ Hg] TiCl ₄ 1.56 [AlgCa (NR) ₃ Hg] 1 , 2 [Al ₂ Mg (NR) ₃ Hg] 1.2 [Al ₂ Ca (NR) ₃ Hg] _x

VCl ₂
VCl ₁

X X

2.3 toluene 250 20

"100 25

0.75 "200 25

0.75 "100 25

2 1 "200 25
25th

70
50
50
50
6o
6o

18th

1.9
1

134

'5.5
5.2

13th

(*) A-I 1 autoclave

B - 0.25 l autoclave

(* ■ *) [Al ₂ Mg (NR) ₃ Hg] _x (or [AIgCa (NR) ₃ Hg] _x ) represent the reaction product of Mg (AlH ₄ ) ₂ (or Ca (AlH ₄ ) g) and n- Butylamine in a molar ratio of 1: 3

(***) Me = transition metal '■

+) AA "means that the titanium compound contains traces of aluminum.

Claims (13)

Claims Iv) Mixed polyimine hydrides, the aluminum and a metal of the second group of the periodic table contain the sequences of the type -M- N I Al -N- have, wherein M is the atom of the metal of the second group of Periodic table represents and R is a substituted or unsubstituted Can be alkyl, aryl, alkylaryl or cycloalkyl radical. 2.) Polyimine hydrides according to claim 1 with the formula - N
I. -> _y - H I. ■ R. I. R. ~ · (- M (- Al wherein x, y and ζ represent the number of repeating units, can be the same or different and are in the range from 1 to 100; X and X ^{1 are} terminal groups which can be identical or different and are selected from -H, -AlH ₂ , -NHR, -MHj and M and R have the meanings given above. 3 ·) Mixed polyimine hydrides, which are aluminum and a metal of the second group of the periodic table, according to one of the preceding claims, characterized in that the Metal of the second group is preferably selected from Ca and Mg. ' 309821/1089 4.) Complex compounds of the polyimine hydrides according to a of the preceding claims, characterized in that they. with molecules that act as Lewis bases are added, where- / with the latter among the aliphatic, aromatic or cyclic ethers, tertiary amines, alkali metal hydrides and in particular Tetrahydrofuran are chosen » 5.) Mixed polyimine hydrides according to one of the preceding Claims, characterized in that they have an IR absorption band (V Al-H) in the range from 1700 to 1800 cm "own * 6.) Process for the preparation of the mixed polyimine hydrides according to one of claims 1 to 4, characterized in that the alanate of the metal of the second group with a primary AmIn is implemented « 7.) Process for the preparation of the mixed polyimine hydrides according to one of claims 1 to 4, characterized in that the alanate of the metal of the second group with an organic Nitrile is implemented. 8.) Process for the preparation of the mixed polyimiji hydrides according to one of claims 1 to 4, characterized * that polyalkyl (aryl) imine derivatives of the metal of the second group be reacted with polyalkyl (phenyl) iminoalanes. 9.} Process according to one of claims 6 to 8, characterized in that the reaction is carried out in the presence of a solvent, selected from aromatic or aliphatic hydrocarbons, Ethers, tetrahydrofuran and tertiary amines. 10.) Method according to claim 8, characterized in that tetrahydrofuran is used as the solvent. 11.) Method according to one of the claims 6 to 9, characterized in that that the reaction takes place in a temperature range is performed, the top and bottom limits of which after the 3 09821/108 9 22S6533 Stability of the reaction product or according to the reactivity of the starting product are selected. 12.) The method according to claim 11, characterized * that the reaction is carried out at room temperature. 13.) Catalyst, suitable for the polymerization of vinyl, Acrylic, epoxy, aldehyde, olefin and diolefin compounds, consisting of mixed polyimine hydrides, the aluminum and contain a metal of the second group of the periodic table, with the formula X - H ί wherein M represents the metal atom of the second group of the periodic table, preferably selected from Ca and Mg] R can be a substituted or unsubstituted alkyl, aryl, alkaryl or cyoloalkyl radical; x, y and ζ represent numbers, which are the same or different, indicating the number of repeating units and are in the range of 1 to 100 j and X and X ^{1 are} terminal groups, which are the same or different, and are selected from -H, -AlH, -NHR, -HH. 309821/1089