DE1420573B - - Google Patents

Description

1 2

For the polymerization of aliphatic olefins masses used and on these initially in Abwurden already catalysts from compounds of essence of moisture and molecular acid metals the IV., V. and VI. Subgroup of Perio- the compounds mentioned of the metals of IV. dic system and organometallic compounds up to VI. Subgroup of the periodic system adder II. And III. Group of the periodic system presorbed 5 and only then mixed up with the metal alkyl. Particularly suitable compounds for binding converts, the weight ratio of Carrying out this process are the halides, carrier mass to compound the metals of IV. Bis especially the chlorides of metals from IV. to VI. Subgroup in the range between 1: 1 and 100: 1 VI. Subgroup. It is also possible to use alkoxy halides.

for example, use titanium dichlorodialkoxides. With io one preferably uses as an inorganic carrier

Flalognalkoxyd, such as titanium monochlorotrialkoxide, some silicic acid or alumina or their compounds

in which the majority of the metal valencies with alkoxy mixtures and as metal compounds of IV. to VI. Ne-

groups are saturated, polymers in lower group alkoxides, halogen alkoxides and acetyl

Yield and low molecular weight and acetonate of titanium or vanadium,

low crystallinity obtained. With halogen-free 15 With these catalysts according to the invention he

Alkoxides give products of low mole; in the polymerization of ethylene, linear products are obtained

Bulky weight and only small amounts of high- high polymers with regular structure, while

polymers. In the "polymerization of propylene, when using higher olefins, for example pro

the example bcii use of catalysts pylene, mixtures of amorphous, linear polymers

from titanium alkoxides predominantly polymers of low 20 are obtained with isotactic polymers, the

ecm molecular weight obtained that no low molecular weight products like in warm acetone

are soluble. The polymerization of ethylene will contain 2-methyl-1-pentene. The amorphous, solid ones

by catalysts made of aluminum triethyl and Aiko polymers of propylene result in the extraction

Holatcn of metals of the IV. to VI. Subgroup the fractions with hot solvents that are generally

DimeriEation to butene-1 causes (M a r t i n, Angcvv. 25 mean to have a much higher molecular weight than

Chemie, 68 [1956], p. 306). corresponding fractions of polymers that are under

According to a previous proposal, when using halide catalysts, the Polymerization of olefins catalysts used, transition metals were produced. The next one the production of which a previously produced firming table 3 shows these results as well as the inorganic ones Carrier first with reducible compounds - results of the fractionation of propylene polymers, fertilize transition metals from IV. to VIf. Ne- die with catalysts made from titanium tetrachloride and AIubengruppc or the VIII. Group of the periodic miniumtriethyl, and from the propylene system and then with organoaluminum compound polymers, those with catalysts made from titanium alkoxide fertilize, alkali or alkaline earth metals or their and aluminum triethyl obtained on a carrier Alloys, hydrides or their alkyl and / or 35 were. With the new catalysts you get Aryl compounds has been brought into contact. amorphous, linear polymers of «-olefins, the higher

It is also known from US Pat. No. 2,691,647 to have molecular weights as polymers obtained using a process for the polymerization of ethylene and known catalysts. This is known to propylene, in which oxides of chromium, Mo- are of particular importance, since amorphous polymers with lybdenum, tungsten or uranium together with an Al- 40 high molecular weight are important applications of potassium metal, and for example in metallic form as catalysts in the field of Have elastomers,
sator used. will. The process is used under moisture-free and heavy metal compounds in which, under conditions free from molecular oxygen, the metal is organic residues, carried out via an acid atom, and the conversion of the carrier material is bonded. There are still no 45 with the alkyl compound in the absence of alkyl compounds of metals of II. And III. Moisture and molecular oxygen. The verGruppe of the periodic system used, but used carrier material is supposed to have a large surface alkali metals in metallic form. With these catalysts and can be in the form of granules or fine lyzers, however, no high yields of ground powder will be available. Preferably, what is practically the same for the catalysts of the 50, the carrier material has acid character. In order to achieve good results in their manufacture, it must have a good adsorptive power instead of the alkali metals, alkaline earth carbides for the monomers to be polymerized. Be occupied. Preferred examples of suitable carrier materials are

It has now been found that significantly better silica, alumina or mixtures thereof, in particular yields in the · polymerization of aliphatic mixtures of the type such as those used as cracking catalyst olefins of the general formula CH ₂ = CHR, are used in the catalysts Application. In the reaction, R is a hydrogen atom or an alkyl radical, the alkoxides of metals from IV. To VI. In addition to using catalysts, the reaction group with a carrier material of this type is released from a certain amount of alcohol dissolved in organic solvents. It is therefore to fertilize metals of the IV., V. and VI. In addition to the assumption that there is a reaction between the alkoxide group of the periodic table, the organic residues and the carrier material,
Bound to the metal via an oxygen atom, the catalyst is expediently prepared in a polythene and alkyl compounds of metals in the II. merization vessel, with carriers and III. Group of the Periodic Table and a material and compound of the metal of IV. To carrier at temperatures between 20 and 100 ° C 65 VI. Subgroups have been reacted in the polymerization vessel prepared by a process which, and then a solution of the metal alkyl compounds, is characterized in that solid inorganic material is added. Optionally, the alkoxide niche, optionally calcined, porous support - first in a nitrogen atmosphere on the support -

adsorbed material and then the mass in the polymerization vessel with the metal alkyl in contact to be brought.

The quantitative ratio between the compound of the metals of IV. To VI. Subgroup and the Support material has a remarkable influence on the polymer yield per gram of the catalyst, since the percentage of amorphous polymer in the polymerization product to a certain extent of depends on this quantitative ratio. Titanium alkoxides have been found to have a given amount of alkoxide The amount of polymer obtained is increased by increasing the amount or the surface area of the support will.

An increase in the amount of the carrier leads to an increase, all other factors being the same Amorphous content in the polymerisation product. This allows the proportions of amorphous and isotactic To regulate polymers in the product within certain limits.

The catalysts according to the invention are particularly suitable for continuous polymerization Use of granulated carriers suitable. The polymerization can be carried out in the presence of a monomer solution carried out through a suitable reaction vessel containing a solid catalyst and the obtained Polymers are separated off by precipitation after each circulation of the solution. The received Polymers contains only small amounts of inorganic products, which is a great advantage. It contains In contrast to known polymers, since they can be produced chlorine-free, not chlorine-containing ones Products so that no hydrochloric acid and no corrosion of machines or nozzles due to hydrolysis can arise.

The catalytic activity of the catalysts according to the invention is considerably higher than that of known catalysts, in that, for example, yields of polyethylene per gram of catalyst per atmosphere of ethylene and per hour are achieved which are about ten times higher than the yields obtained with those from the USA. Patents 2,691,647 and 2,710,854 known catalysts can be achieved.
The following tables show:

Table 1

The course of the polymerization of propylene with catalysts made from titanium alkoxide and aluminum triethyl with and without carrier material.

Table 2

The course of the polymerization of propylene with a catalyst composed of vanadyl isopropylate and Aluminum triethyl with and without carrier material.

Table 3

The difference in the composition of the polymers made using titanium tetrachloride or titanium tetraisopropoxide on a support material in the preparation of the catalysts were obtained under otherwise identical conditions.

Table 4

The course of the implementation and the deviations in the composition of the polymers depending on the degree of dispersion of the catalysts on a particular type of Carrier material.

The tables relate to the following examples which illustrate the invention. The symbol η in the tables denotes the intrinsic viscosity measured in tetrahydronaphthalene at 135 ° C. The percentages given in the tables and examples are percentages by weight, unless otherwise specified. No protection is sought here for the polymerization process itself described in the examples.

table

Polymerization of propylene with catalysts made from titanium alkoxides and aluminum triethyl in the absence and presence of carrier material

A1 (C ₂ H ₆ ) ₃
Mole Catalyst r i Polymerization conditions Tempe
rature At first
pressure Received , Product example Ti (OR) ₄
Mole Weight
ratio
Al (C ₂ H ₅ ), Heptane ⁰ C atm total
product conversion 0.10 Ti (OR) ₁ ml 100 30th G % Without carrier 0.002 j 50 200 6th 3 With carrier 0.10 95 18.5 1 0.10 0.02 5 1000 95 30.0 44.0 19.8 2 0.05 0.02 5 500 95 12.0 45.0 29.5 13th 0.06 0.005 10 1000 95 16.5 26.0 15.5 6th 0.10 0.013 4.6 1000 90 21 86 50.2 5 0.10 - - 1000 90 14.0 : 85 54.0 12th 0.05 5 1000 ^ 28.0 • 18.0

Continuation to table 1

example

2-methylpentene-1

Acctone extract

0 /

/O

Fractionation of the product obtained

Ether extract

% j In) j Mw

Heptane extract | Residue

Vo j Μ j MW, j ° / uj W \ MW

Without carrier

With carrier
1

sense

Traces traces

without traces

without traces

without traces

without traces

59.6

14.0 9.15 5.6

12.1 7.5 9.8

32.7 0.37

44.5 43.9 55.3

53.1

63.0

83.2

1.47
1.10
1.40

0.71

0.69

1.42

7200 5.75 0.71 57600 12.5 3.60 37000 19.6 2.25 52500 18.0 3.80 18800 25.5 2.33 18100 23.2 2.01 55000 6.7 3.50

table

Polymerization of propylene with a catalyst composed of vanadyl isopropoxide and aluminum triethyl under the same conditions, with and without carrier material

18800

226000
112000
257000

118000

94000

218000 - -

400000 251000 395000

220000

190000

catalyst
and example

Acetone extract

/O

Ether extract

I M I Mw

Fractions of the product obtained

Heptane extract
Vo M MW

Residue% I M I M.w.

Without carrier
With carrier
8th

96
39.0

4 14.7

0.29 I 5000

16.8

0.49

10700

29.5

2.3

115000

table

Fractionation of propylene polymers obtained under comparable conditions using catalysts made _{from TiCl 4} and aluminum triethyl or from alkoxides on carrier material and aluminum triethyl

catalyst
and example Accton
extract Ether extract Vo 0.46 Fra ctioning of the product received
rTeptane extract M.W. of Vo Backstanc 1 M.W. Vo M.W. Vo M. M. TiCl ₁ and 38.4 21500 27.6 UOOO Al (C ₂ Hs) ₃ 9.4 10,000 24.6 0.77 2.24 Titanium alkoxide on carrier 1.47 and 1.10 Al (C ₂ H ₅ ), 44.3 1.34 226000 29.2 400,000 1 14.0 43.9 1.40 57600 12.5 3.60 112000 28.0 5.20 251000 2 9.15 41.9 37000 19.1 2.25 197000 24.0 3.85 355000 3 13.9 55.3 50000 20.2 3.30 257000 21.0 4.80 395000 13th 5.6 52500 18.0 3.80 5.17

table

Dependence of the conversion and the composition of the polymerization product on the degree of dispersion

of catalysts of the same type on a carrier material

Xrascr ε Around
change Acetone-
extract Vo Fraction of polymer obtained M.W. Heptane extract Vo M. M.W. Vo Residue VT. W. example Titanium-
propylate g Vo 44.5 ^ the extract 57600 12.5 3.60 226000 29.2 bü 400,000 . 2.50 20th 14.0 43.9 M. 37000 19.1 2.25 112000 28.0 5.20 251000 1 3.33 28.5 9.15 63.0 1.47 18800 25.5 2.33 118000 9.3 3.85 220000 2 25.00 50.2 12.1 63.0 1.10 18100 23.2 2.01 94000 6.3 3.53 130000 6th 33.30 54.5 7.5 0.71 3.20 5 0.69

example 1

In a 2080 ml shaken autoclave, 15 g of a silica and Aluminiumdioxyd in a weight ratio of 0: 1 introduced containing feinzermahlenen and activated in advance in a muffle furnace at 550 ⁰ C-containing solid support. The autoclave is evacuated, whereupon a solution of 6 g of titanium tetraisopropoxide in 100 ml of pentane is added. The autoclave is ^{heated to 55 3} C for 30 minutes; Solvent and formed isopropano! are then removed in vacuo (20 mm Hg). A solution of 11.4 g of aluminum triethyl in 1000 ml of heptane and then 256 g of a propylene-propane mixture containing 88 percent by volume of propylene are then added. The whole is heated with stirring 10 hours at 9O ⁰ C, free the unreacted gases are removed and the resulting product of organometallic compounds by shaking vigorously with acidified water.

Two phases separate. The poly contained in the heptane phase, which also contains the carrier

* ^ mere is made by adding methanol and acetone completely coagulated and by successively dissolving several times in tetrahydronaphthalene from the support separated and allowed to coagulate in acetone and methanol. In this way 44 g of pure propylene monomer becomes separated, which is then fractionated by extracting with hot solvents, wherein Acetone, ether and heptane are used one after the other.

The acetone extract corresponds to 14.0% of the polymer and consists of oily and semi-solid products with low molecular weight. The ether extract corresponds to 44.3% of the polymer and consists of solid Polypropylene, which is amorphous according to X-ray analysis and the appearance of unvulcanized elastomers has. The intrinsic viscosity in tetrahydronaphthalene at 135 ° C is 1.47 corresponding to a molecular weight of 57600. The heptane extract corresponds to 12.5% of the polymer and consists of polypropylene, which according to X-ray analysis is partially (15%) crystalline. This fraction has an intrinsic viscosity of 3.60

■■ * corresponding to a molecular weight of approx 226000. The extraction residue corresponds to 29.2% of the total polymer, according to X-ray analysis crystalline and has an intrinsic viscosity of 5.20 (molecular weight about 400,000).

Example 2

50

In a 1780 ml shaking autoclave are 20 g a solid support according to Example 1 in the form of granules with a diameter of 2 to 3 mm, the had previously been calcined in a muffle furnace at 500 ° C, introduced. The autoclave is evacuated, then a solution of 6 g of titanium tetraisopropoxide in 100 ml of pentane was added. The autoclave is 30 minutes heated to 50 ° C. and the solvent and isopropanol formed removed in vacuo (20 mm Hg). Then 11.4 g of aluminum triethyl, dissolved in 1000 ml of heptane, and 182 g of a propylene-propane mixture, which contains 88 percent by volume propylene, added one after the other. The mixture is stirred Heated to 95 ° C. for 10 hours and then removed the reaction product. The polymer is made by decanting and treatment with n-heptane separated from the support and from inorganic substances, which by the catalyst decomposition occurred, purified by treatment with water and hydrochloric acid. The Polymer is precipitated from the heptane phase by adding methanol and acetone. When converting from about 29% of the monomer used, about 45 g of propylene polymer is obtained.

The pure polymer thus obtained is obtained by extracting with hot acetone, ether, heptane and toluene fractionated.

The acetone extract corresponds to 9.15% of the polymer and consists of oily semi-solids that have a low molecular weight. The ether extract corresponds to 43.9% of the polymer and consists of solid polypropylene which, according to X-ray analysis, is amorphous and has the appearance of non-vulcanized elastomers. In tetrahydronaphthalene at 135 ⁰ C, this fraction shows an intrinsic viscosity of 1.10 corresponding to a molecular weight of about 37000. The heptane extract corresponds to 19.1% of the polymer and is made of polypropylene which, according to X-ray analysis partially (20%) is crystalline. This fraction has an intrinsic viscosity of 2.25 (molecular weight 112,000). The toluene extract, which makes up almost all of the residue from the heptane extraction, has an intrinsic viscosity of 3.85 and a molecular weight of about 251,000.

Example 3

Six stainless steel balls with a diameter of 25 mm and 3 g of a solid support according to Example 1, which has previously been calcined in a muffle furnace at 500 ° C, are in a nitrogen atmosphere into a 2000 ml shaking autoclave, which is available as Ball mill acts, introduced. A solution of 3 g of titanium monochlorotributylate is then produced under oxygen-free conditions introduced in 100 ml of heptane. The autoclave is closed, heated and 30 minutes emotional. The solvent is then formed along with that in vacuo (20 mm Hg) Isopropanol removed.

A solution of 5.7 g (0.05 mol) of aluminum triethyl in 1000 ml of n-heptane is then added and the autoclave is moved again and heated to about 90 ° C. 15 minutes after the introduction of the aluminum triethyl 150 g of a propylene-propane mixture containing 88 percent by volume of propylene are added. The autoclave is moved at 90 ° C. for 1 hour. The unreacted gas is then mixed with the polymerization product, which is separated off as in Example 1, removed. 24.5 g of polymer are obtained.

The polymer is fractionated by extracting with hot acetone, ether and heptane. The acetone extract corresponds to 13.9% of the polymer and consists of an oily, semi-solid product with a low Molecular weight. The ether extract corresponds to 41.9% of the polymer and consists of polypropylene, which according to X-ray analysis is amorphous and has the appearance of unvulcanized elastomer. This faction has an intrinsic viscosity of 1.34 measured in a tetrahydronaphthalene solution at 135 ° C. The molecular weight is about 50,000. The heptane extract corresponds to 20.20% of the polymer and consists of a partially crystalline polymer. This fraction has an intrinsic viscosity of 3.30 corresponding to one Molecular weight of about 197,000. The residue (24%) is highly crystalline and has a very high molecular weight.

109 541/345

Example 4

20 g of a granular carrier material of the composition described in Example 1, which has previously been calcined in a muffle furnace at about 500 ⁰ C, are introduced into a 435-ml SchütteIautoklav. The autoclave is evacuated and then a solution of 3 g of titanium monochlorotributylate in 50 ml of pentane is added.

The autoclave is heated to 50 ° C. for about 30 minutes and the solvent is then heated under vacuum removed (20 mm Hg). Then a solution of 5.7 g of aluminum triethyl in 200 ml of n-heptane and 85 g of a propylene-propane mixture with a content of 88 percent by volume propylene were introduced.

The total mass is heated to 95 ° C. with agitation for 24 hours and the reaction product is then removed. The polymer is separated off as in Example 2; 42.4 g of pure polymer, corresponding to a conversion of about 57% of the monomer used, are obtained. The polymer is fractionated by extracting with hot acetone, ether and heptane. The acetone extract corresponds to 30.4% of the total polymer and consists of oily, semi-solid products with a low molecular weight. The ether extract corresponds to 38.2% of the polymer and is amorphous according to X-ray analysis. It has in tetrahydronaphthalene at 135 ^C C has an intrinsic viscosity of 0.90 corresponding to a molecular weight of about 27,400th The heptane extract is 19% of the total polymer. According to X-ray analysis, it is partially crystalline and has an intrinsic viscosity of 1.50 (molecular weight about 59,000). The residue (12.4%) consists of a highly crystalline polymer with a high molecular weight.

Example 5

100 g of a granulated carrier material as in the previous example are under nitrogen in a Bottle with a 3% solution of titanium tetraisopropoxide in anhydrous n-heptane for about 1 hour Treated reflux condenser. The solvent is distilled off in vacuo (20 mm Hg) and from the with granules impregnated with titanium alkoxide several times with anhydrous heptane washed. In this way, excess tetraisopropoxide is completely removed. The mass obtained shows a titanium content of 1.77%.

This mass is introduced into an evacuated 1780 ml shaking autoclave and successively a solution of 11.4 g of aluminum triethyl in 1000 ml of n-heptane and 180 g of a propylene-propane mixture containing 88 percent by volume of propylene and the autoclave at one temperature moved from about 90 ⁰ C. After 12 hours, the autoclave is emptied and the polymer is separated off as in Example 2. 85 g of pure polymer, which looks like unvulcanized elastomers, are obtained. The yield corresponds to about 54% of the monomer used.

The pure polymer thus obtained is fractionated by extracting with hot solvents. Acetone, ether and heptane are used one after the other. The acetone extract corresponds to 7.5% of the polymer and consists of oily and semi-solid products of low molecular weight. The ether extract corresponds to 63.0% of the polymer and consists of solid polypropylene which, according to X-ray analysis, is amorphous and looks like non-vulcanized elastomers. This fraction has in tetrahydronaphthalene at 135 ⁰ C has an intrinsic viscosity of 0.69 (molecular weight 18000). The heptane extract corresponds to 23.2% of the total polymer. According to X-ray analysis, it is partially crystalline and has an intrinsic viscosity of 2.01 (molecular weight about 94,000). The residue (6.3%) is highly crystalline and has an intrinsic viscosity of 3.20 (molecular weight about 190,000).

Example 6

100 g of a granulated carrier consisting of silicon dioxide and aluminum oxide in the ratio given in Example 1, which has previously been ^{calcined at 500 °} C. in a muffle furnace, are placed in an air-free 2000 ml shaking autoclave, then a solution of 4 g of titanium tetraisopropoxide in 100 ml of heptane were introduced and the autoclave was heated to 70 ° C. for about 30 minutes while shaking. Solvent and isopropanol formed are removed in vacuo (20 mm Hg). Then a solution of 0.06 MoI triethylaluminum in 1000 ml n-heptane is added, the autoclave again shaken and heated to 95 ⁰ C. After 10 minutes, 195 g of a propylene-propane mixture containing 88 percent by volume of propylene are added. The autoclave is ^{shaken at 95 °} C. for 12 hours. The polymer obtained is separated as described in Example 2, 86 g of polypropylene being obtained with a conversion of about 50.2%. The polymer is fractionated by extracting with hot acetone, ether and heptane.

The acetone extract corresponds to 12.1% of the polymer and consists of oily semi-solid products of very low molecular weight, the ether extract corresponds to 53.1% of the polymer and consists of solid Polypropylene, which is amorphous according to X-ray analysis and the appearance of unvulcanized elastomers indicates. In tetrahydronaphthalene, this fraction has an intrinsic viscosity of 0.71 at 135 ° C a molecular weight of about 18,800. The heptane extract corresponds to 25.5% of the polymer; he is in accordance X-ray analysis partially crystalline and has an intrinsic viscosity of 2.33 (molecular weight approx 11800). The residue (9.3%) consists of a highly crystalline product and has an intrinsic viscosity of 3.53 (molecular weight about 220,000).

Example 7

50 g of the granulated carrier used in the preceding examples, previously calcined in a muffle furnace, are introduced into a 435 ml shaking autoclave which is evacuated. A solution of 0.02 mol of vanadyl isopropoxide (VO (OC ₃ H ₇ ) ₃ ) in 100 ml of pentane is then added. The autoclave is heated for 30 minutes 6O ⁰ C and kept in motion. The solvent is removed in vacuo (20 mm Hg), then introduced a solution of 5.7 g (0.05 mol) of triethylaluminum in 200 ml of n-heptane and the temperature raised to 90 ⁰ C. Then 90 g of a propylene-propane mixture with a propylene content of 88 percent by volume are added.

The whole is heated to 90 ° C. for 24 hours with agitation and the reaction product is removed. The obtained polymers is, as described in Example 2, separated, 31 g of propylene polymer at a Conversion of 39.3% can be obtained.

The pure product obtained in this way is fractionated by extraction with hot acetone, ether and heptane.

11 12

ned. The acetone extract corresponds to 39 ° / ₀ of the poly as described in Example 1, separated from the Tränieren and consists of oily and semi-solid production ger the product. 28 g of low molecular weight polypropylene are obtained. The Ätherex- which is fractionated by extracting with hot acetone, ether and tract corresponds to 14.7% and consists of solid poly-heptane. The acetone extract is depropylene, which is amorphous according to X-ray analysis. 5 speaks 9.8% of the total polymer and consists of this fraction in tetrahydronaphthalene at 135 ° C oily and semi-solid products with a low molecular weight an intrinsic viscosity of 0.29 corresponding to a molecular weight. The ether extract corresponds to 83.3% of the molecular weight of about 5000. The polymer heptane extract is solid and amorphous according to X-ray analysis, corresponds to 16.8% of the total polymer and has the appearance of non-vulcanized elastomer and consists of polypropylene, which according to X-ray analysis is partly in Tetrahydronaphthalene is crystalline at 135 ° C an intrinsic viscosity and an intrinsic viscosity of 0.49 tat of 1.42 (molecular weight of about 55,000). The corresponding to a molecular weight of about heptane extract corresponds to 6.7% of the polymer, is 10,700. The residue (29.5%) is highly crystalline, partially crystalline and has an intrinsic viscosity of and has an intrinsic viscosity of 2.3, corresponding to 3.50 (molecular weight about 218,000). After the hepa molecular weight of about 115,000.15 tan extraction, no residue remains.

Examples Example 10

8 g of a granulated silica gel, previously activated at 9 g in a muffle furnace at 400 ^{0 C SiIi-}

500 ⁰ C has been calcined for several hours, cium dioxide are introduced into a rotating 2000 ml in a 435 ml shaking autoclave. This autoclave, which acts like a ball mill, is vented in such a way and then a solution of 3 g of titanium is added so that the silicon dioxide granules finely zermonochlorotributylate in 80 ml of pentane are added. That will grind.

,. <"$ The whole is heated to 50 ° C for 30 minutes and the solution is then a solution of 1.4 g of titanium tetraiso-

solvent then removed in vacuo (20 mm Hg). propylate in 100 ml n-heptane were added, the car is then heated, a solution of 5.7 g (0.05 mole) of 25 klav at 50 ⁰ C and the solvent in the aluminum triethyl in 200 ml of n-heptane was added, the vacuum part, aborted (20 mm Hg). Then raised temperature to 90 ⁰ C and 105 g of a propylene is added a solution of 5.7 g of aluminum triethyl in len-propane mixture having a content of 88 Vo- 1000 ml n-heptane and 170 g added to a propylene-Propanlumprozent propylene. The mixture is agitated mixture with a content of 88 percent by volume for 24 hours at 90 ⁰ C and then the reaction propylene is added. The product is removed from the autoclave for 12 hours. As in Example 2, it is heated to 95 ° C. while rotating, then no processing takes place, 24.2 g of polypropylene being obtained and these converted gases and the reaction products to be fractionated by extraction with hot solvents continued working, being rened. Acetone and ether, 26.0 g of propylene polymer are separated off one after the other and used with up and heptane. 35 successive extraction with hot acetone,

The acetone extract corresponds to 25.2% of the polyme- ether and heptane are fractionated, and consists of oily, semi-solid products from The acetone extract corresponds to 5.6% of the total

low molecular weight. The ether extract depolymerizes and consists of products with a low level 38% of the polymer and consists of some molecular weight. The ether extract corresponds solid product which, according to X-ray analysis, is amorphous 40-55.3% of the polymer, according to X-ray analysis and what non-vulcanized elastomer looks like. amorphous and has the appearance of unvulcanized This fraction has elastomers in tetrahydronaphthalene at 135 ° C. The intrinsic viscosity is in tetraeine Limiting viscosity of 0.765 corresponding to a hydronaphthalene solution at 135 ° C corresponding to 1.40

-y Molecular weight of about 21,100. The heptane extract has a molecular weight of about 52,000. The Hep corresponds to 24.1% of the polymer, is according to X-ray 45 tan extract corresponds to 18% of the polymer, is partly crystalline according to analysis and has an intrinsic viscosity X-ray analysis partly crystalline and has a Grenztät of 1.32 corresponding to a molecular weight corresponding to a viscosity of 3.90 Molekularvon about 48 500. The residue consists of a high-weight of about 257,000th The residue (21 ° / ₀₎ is crystalline product with a high molecular weight. highly crystalline and has an intrinsic viscosity of 5.17

_,. . , - 5 ° corresponding to a molecular weight of about

Example 9 3 _95,000

Six stainless steel balls (diameter..

ser 25 mm) and 8 g powdery aluminum oxide, example

that previously in a muffle furnace at 450 ° C some 50 g of a granulated, a few hours in one

Hours has been calcined, in a 200 ml 55 muffle furnace calcined support material made of silicon

rotating autoclave, which works like a ball mill, dioxide and aluminum oxide in weight ratio

given, and then a 3 g of titanium tetraisopropoxide of 9: 1 are placed in a 2000 ml shaking autoclave

introduced into 100 ml of solution containing heptane, which led. After evacuating the autoclave, a

Autoclave closed and evacuated. Solution of 1 g vanadium acetylacetonate in 50 ml ben-

The autoclave is added for about 30 minutes with agitation 60 zol, the autoclave for 30 minutes with loading

heated to 50 ° C and then the solvent is heated to 50 ° C in the vacuum and the solvent

kuum removed (20 mm Hg). Then one is finally removed in vacuo (20 mm Hg). After that

Solution of 5.7 g of aluminum triethyl in 1000 ml of η-Hep- is a solution of 5.7 g of aluminum triethyl in

tan added and after 10 minutes 180 g of a pro 1000 ml of n-heptane introduced and after a few minutes

pylene-propane mixture with a content of 88 vol- 65 minutes with 180 g of a propylene-propane mixture

lum percent propylene. The autoclave is 18 hours a content of 88 percent by volume propylene. the

moves at about 90 ^{° C.} The unreacted gas and the autoclave are moved for 18 hours at 90 ^° C., then that

the polymerization product is precipitated and unreacted gas is drawn off and the polymer in

usually separated. There are 12 g of propylene polymer obtained which are fractionated by extracting with hot acetone, ether and heptane.

The acctone extract corresponds to 40.0% of the total polymer and consists of semi-solid products with a low molecular weight. The ether extract corresponds to 26.0 ° / g of the polymer and is solid and amorphous according to X-ray analysis. Its solution in Telrahydronaphthalin at 135 ¹ C has an intrinsic viscosity of 0.28 corresponding to a molecular weight of about 4800. The heptane extract (26 ° / ₀₎ is according to X-ray analysis partially crystalline and has an intrinsic viscosity of 0.54 corresponding to a molecular weight of about 12,800th the residue (8 ° / ₀₎ consists of crystalline polypropylene of high molecular weight.

Example 12

A 2000 ml autoclave with a liquid circulation system was introduced into the stirrer and heating jacket. This is ^{heated to 55 3} C and the solvent is removed after about 1 hour in vacuo (20 mm Hg). A solution of 11.4 g (0.1 mol) of aluminum triethylin 800 ml of n-heptane is added under a nitrogen atmosphere, and ethylene is then introduced at 60 to 65 ° C. for about 4 hours, the pressure being kept at 10 atmospheres. After that, existing

ίο drawn off hot gases containing 2 g of butene. The procedure is as in the previous examples and 105 g of polyethylene with a crystallinity of over 80 ° / _{0 is} separated off according to X-ray analysis. If you work under the same conditions, but in the absence of carrier material, you get butene with only traces of polyethylene.

120 g of the granulated carrier used in the preceding examples are calcined for a few hours at about 500 ° C. in a muffle furnace and then introduced into a 2000 ml autoclave equipped with a propeller stirrer. After evacuating the autoclave, a solution of 2 g (0.007 mol) of titanium tetraisopropoxide in 200 ml of n-heptane is added, the autoclave is heated to 50 ° C. for about 2 hours while stirring and then the solvent is driven off in vacuo (20 mm Hg). Thereafter, a solution of 5.7 g (0.05 mol) of triethylaluminum in 800 ml of n-heptane and 15 minutes is then introduced ethylene continuously at 6O ⁰ C while maintaining the pressure at 10 atm. is held. The feed of monomers is ended after 6 hours and the unconverted gases, which do not contain any higher olefins such as butene, are drawn off. The procedure is as in the previous examples and about 100 g of polyethylene are separated off, which, measured in tetrahydronaphthalene, has an intrinsic viscosity of 13.2 at 135 ° C. The reaction product does not contain any low molecular weight ethylene polymers.

If you work under the same conditions, but in the absence of carrier material, the implementation results predominantly 1-butene.

Example 13

120 g of a carrier containing silicon dioxide and aluminum oxide in a weight ratio of 9: 1 and a solution of 2 g (about 0.007 mol) of titanium tetraisopropoxide in 150 ml of n-heptane is poured into a

Claims (2)

Patent claims: 1. Process for the preparation of catalysts for the polymerization of aliphatic olefins of the general formula CH ₂ = CHR, in which R denotes a V hydrogen atom or an alkyl radical, by reacting compounds of metals of IV., V. and VI. Dissolved in organic solvents. Subgroups of the periodic system that contain organic radicals bonded to the metal via an oxygen atom, and alkyl compounds of metals from II. And III. Group of the Periodic Table and a support at temperatures between 20 and 100 ⁰ C, characterized in that solid inorganic, optionally calcined, porous support materials are used and the compounds of the metals of IV. to VI. Subgroup of the periodic system adsorbed and only then reacted with the metal alkyl compounds, the weight ratio of carrier mass to compound of the metals of IV. To VI. Subgroup should be in the range between 1: 1 and 100: 1. 2. The method according to claim 1, characterized in that the inorganic carrier masses Silica or alumina or mixtures thereof and as a metal compound of IV. To VI. Subgroup Alkoxides, haloalkoxides and acetylacetonates of titanium or vanadium are used. 1 sheet of drawings