DE1292637B - Process for the preparation of catalysts for the polymerization of olefinic hydrocarbons - Google Patents

Description

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It is already known to use olefinic hydrocarbons with ethylaluminum dichloride in the presence of materials such as ethylene, propylene, butylene, titanium tetrachloride is required. The obvious guess Hexene, styrene or vinylcyclohexane, in the presence that this polymerizes only on the titanium tetravone Catalysts at elevated temperatures and chloride and the monoethylaluminum dichloride to normal or increased pressure in the presence of 5 has not been confirmed because Polymerize catalysts made from titanium compounds - these two compounds alone do not or olefins fertilize, especially titanium tetrahalide, and hardly polymerize aluminum. Rather, it requires organic polyminium Compounds, especially al- merization of olefins in the presence of the third kylaluminum halide. One receives this component, the brown precipitate from the plastic-like products in good yields. Despite the approximate composition of the titanium trichloride. the great importance that this. Procedure in the subject of. Invention is thus a method

Technology has the disadvantage that its for the production of catalysts for the Polymerisa results olefinic hydrocarbons do not always reproduce uniformly from titanium leaching. The rate of polymerization is trihalide, a titanium tetrahalide and one different from case to case. The product itself has 15 halogenated organoaluminum compounds, if apparently constant conditions are observed, this is characterized by the fact that one is used as a titangung frequently fluctuating molecular weights and trihalide compound any titanium one produced at will very different molecular weight distribution, trihalide, preferably brown titanium trichloride, The invention was based on the working hypothesis, and as a halogen-containing organoaluminum Verdaß these fluctuating results are due to monoalkylaluminum dihalide or alkyl feeds be that one uses aluminum alkoxyl far too little through nature and the molar ratio of the actual catalyst is white and therefore also between titanium trihalide and titanium tetrahalide is unable to achieve the optimal conditions for between 0.1: 1 and 100: 1, preferably between determine the manufacture of the catalyst. 2: 1 and 24: 1. The monoalkylaluminum di-

When mixing titanium tetrahalide, halide is expedient in one of the titanium tetrahalides Titanium tetrachloride, added in an equimolar amount with alkyl aluminum halide, halides, for example dialkylaluminum mono- These catalysts can not only be used for the poly-

chloride, a brown precipitate is known to fall merization of ethylene, but for numerous others from which settles well and easily from the solution olefins and diolefins, such as propylene, can be separated. It was found that this butene, hexene, butadiene, isoprene or styrene turned brown Precipitation approximates the composition.

of titanium trichloride. The titanium trihalide can be formed by precipitating interpret the following equation: titanium tetrahalide with dialkylaluminum monohalo-

τΐΓΊ -i- (r w ■ »δϊγί - Τίπ α. r w AiPi _i_ rw genid, preferably in excess, filter off the

35 resulting brown precipitate and washout

The ethyl radicals released during this reaction until the washing solution is completely halogen-free should either combine to form butane, but instead of Dioder by disproportionation a mixture of alkyl aluminum monohalide also trialkyl aluminum ethane and give ethylene. In fact, nium observed in appropriately dosed limited amounts essentially the escape of ethane. 40, initially dialkylaluminum-Das Ethylene corresponding to this is evidently monohalide which is then formed as described instantly polymerized and. appears therefore no longer responding. But you can also use the brown titantrials Gas. produce halide in other ways, for example

If the reaction is not carried out according to the equation by silent electrical discharge according to F. Bock with equimolar amounts of titanium tetrahalide and 45 and L, M o ser (MONTHS FOR CHEMISTRY, 34 [1913], diethylaluminum chloride, but with an over- S. 1825 to 1833 ). Furthermore, one can see through the addition of aluminum compound, so treatment of vapors of the titanium tetrahalide one recognizes that in the solution the excess diethyl with hydrogen according to K. Blankenstein, Dissaluminiumchlorid besides Monoäthylaluminiumdichlo- tation 1955, TH Hannover, obtained violet titanide is present. In order to clarify which of the three trihalides or the titanium trihalide obtained by reduction with metallic components for the polymerisation effect or elemental silicon is necessary, the brown precipitate was filtered off using the titanium trihalide obtained and carefully washed out. This precipitate can be used to produce the titanium trihalide

ethylene cannot poly- with its activation by titanium tetrahalide at low pressure merize, so that for catalysis a combination of 55 and alkylaluminum halides combine by act of the precipitate with the constituents of the washed-out brown titanium trihalide Solution must be seen as necessary. those with its precipitation from titanium tetrahalide

If the mother liquor formed from the washed-out brown precipitate was mixed with alkyl aluminum halides, of titanium trichloride once diethylaluminum chloride, if necessary with further addition of titanium tetrazum other monoethylaluminum dichloride is added to the halide or monoalkylaluminum dihalide sets, when the diethylaluminum chloride was added, the molar ratio according to the invention was set, always an activation of the titanium trichloride, admits.

while the results with Monoäthylaluminiumdi With the catalyst prepared according to the invention

chloride were different. They depended on the olefinic hydrocarbons which ratio in the manufacture of the titanium tri-65 extraordinarily uniform and reproducible polychloride merize from titanium tetrachloride and diethylaluminum. This can already be seen in the constant chloride was worked, since it was, as further established, the permanent absorption rate of the olefin, for the activation of the brown precipitate see hydrocarbon throughout

Determine polymerization while absorbing the desired mmol amount corresponding volume speed with the previous catalysts suspension and feed it into a 250 ml shaker Dropped sharply at the end. This is presumably due to the cylinder, adding the appropriate amount of titanium, that the new catalyst systems tetrachloride and monoethylaluminum dichloride to, keep their composition constant and therefore fill up to 250 ml with aliphatic and shake the 5 also constant until the end of the reaction mix intensively for 5 to 10 minutes, are sam. The catalyst mixture is added to the 2.251

It is noticeable that aliphatic charged with the new catalysts and already obtained on polymerization polyolefins of particularly high bulk density are temperature (60 ^° C.) preheated polymerization. In the case of ethylene, this bulk density was about 10%. The polymerization can then begin immediately, twice as high as with the known products. . -I ₁
In individual polymerization batches in the normal example 1
Apparatus up to about 800 g of polyethylene could be obtained in 135 ml of a ^{solvent produced according to the instructions given 2 ×} / ₂ 1 and 2 hours. The 0.185 m TiCl ₃ suspension provided in fully hydrogenated The new products also differ in terms of their molecular weight. The protective gas (argon or pure nitrogen) in a division curve are narrower, which can be deduced from the high 250 ml shaking cylinder _{with 3.2 g of Cl 2 AlC 2} H ₅ , bulk density. the mixture made up to 250 ml with aliphatic

Unless otherwise noted, shake well for all and 5 to 10 minutes.

Examples with a titanium trichloride suspension. The mixture prepared in this way is poured into a 5-1 glass

works, which was prepared as follows: vessel transferred together with 2,251 aliphatic.

In a 2-1 three-neck round bottom flask to then be initiated at 6O ⁰ C ethylene. It educates

Solution of 67.7 g (0.552 mol) of diethylaluminum- no or only a few grams of a solid poly-

monochloride in 1.8 l fully hydrogenated via K names.

Alloy (5 parts by weight of K + 5 parts by weight of Na) 25, on the other hand, is given for the same mixture

distilled aliphatic (HC mixture C ₁₀ to C ₁₅ ) addition of the Cl ₂ AlC ₂ H ₅ another 1 ml of a 0.5 Hi-TiCl ₄ -

while stirring and under protective gas (argon or pure solution in aliphatic), shake for 5 to 10 minutes

Nitrogen) at room temperature 35.0 g (0.184 mol) vigorously and proceed as above, so obtained

Titanium tetrachloride was added dropwise and the mixture 10 Mi- man after one hour 118 g of polyethylene with a

utes intensely stirred. The precipitate has a viscosity number (η) - 6.66 and a bulk weight

(TiCl ₃ ) settles within 5 to 8 hours. Those of 0.21 g / cm ³ ,

supernatant mother solution is de- Bis υ ie 1 2 under protective gas
canted, the remaining suspension centrifuged

(Ann., 589 [1954], p. 111) and the brown lower 70 ml of a 0.177 m- _{TiCl 3} suspension in aliphatic

hit by slurrying with about 600 ml 30 35 (12.4 mmol) are together with under protective gas

to 40 ⁰ C warm aliphatic and then 25 ml of a 0.5 M TiCl ₄ solution in aliphatic and 3.2 g

Centrifugation washed six to seven times until Cl ₂ AlC ₂ H _{5 is placed} in a 250 ml shaker cylinder,

the supernatant solution, intensively filled up with weakly saline this with aliphatic to 250 ml and the

shaken with peter acid water, no ionic chlorine mixture shaken well for 5 to 10 minutes,

contains more (test with AgNO ₃ ). With aliphatic 40 Then, as in Example 1, ethylene is polymerized,

_{the brown TiCl 3 is} rinsed in a protective gas. After one hour, 362 g of polyethylene have been removed.

1-1 shaking cylinder and fills up with aliphatic. Instead of divorced. The viscosity number is (η) = 1.86,

of the diethylaluminum monochloride can be any weight 0.265 g / cm ³ ,

dearly dialkyl aluminum monohalide in equimole-. .

cular amounts can be used. 45 B e 1 s ρ 1 e 1 3

^{The Ti 111} content of the suspension is determined by 110 ml of a 0.177 m- _{TiCl 3} suspension in al-tetration of a sample of the suspension. phatin are under protective gas together with 10 ml. For example, 20 ml of the well-shaken O, 5m-TiCl ₃ solution in aliphatic and 3.2 g th suspension with a volumetric pipette under protective gas Cl ₂ AlC ₂ H ₅ in a 250 ml -Shaking cylinder given, removed, made up with an aqueous, air-free FeCl ₃ - 50 of this with aliphatic to 250 ml and shaken vigorously for 5 minutes with vigorous stirring and under protective gas for 10 minutes. It is titrated as in, by _{polymerizing ethylene to the 20 ml TiCl 3} suspension game 1. After one hour in a suitable titration vessel, about 60 ml of one with 440 g of polyethylene have separated out. The protective gas blown out, i.e. air-free 2 η hydrochloric acid viscosity number is (η) = 2.5, the bulk density adds. Two liquid phases are created. The oily 55 0.26 g / cm ³ .
Phase does not interfere with the titration. The titanium trichloride example 4
dissolves quantitatively with light purple color in the

aqueous phase. Now titrate under protective gas. Proceed as in Example 3, but change that

with a 0.1 n FeCl ₃ solution by the prior to the one molar ratio TiCl ₃ / TiCl ₄ , as indicated in Table I,

Position of the titer about 1 hour argon or pure 60 but holds the total amount of titanium, namely 25 mmol,

Nitrogen passed in a vigorous stream of bubbles and the amount of Cl _{2 AlC 2} H ₅ (25 mmol) constant,

became. Towards the end of the titration ⁰ C is membered to 8O After one hour of polymerization obtained

warms and with methylene blue the equivalence point the polyethylene yield given in Table I,

certainly. As an indicator, methylene blue is very good. In column 3 is the viscosity number, in column 4 it is

suitable because the color change from light purple - the bulk weight is given ^{in g / cm 3.}

Methylene blue is ^{decolorized by the titanium ra} solution - The change in yield and viscosity

can be seen very well after blue-green. number with different ratio of TiCl ₃ : TiCl ₄

For the polymerization, one takes from the table.

i 292

Table I.

Molar ratio yield
PÄ Viscosity
number Bulk weight _Τι ΐπ _{/ Τι} ΐν g / hour Gi) g / cm ³ 0.4 42 1.59 0.205 1 362 1.86 0.265 4th 440 2.50 0.26 10 260 3.42 0.215 24 168 5.12 0.215 40 134 6.00 0.24 50 118 6.66 0.21 80 114 7.90 0.27 100 106 8.37 0.21

Example 5

132 ml of a 0.173 m- _{TiCl 3} suspension in aliphatic, prepared in the manner indicated, are dissolved in _{aliphatic and 300 mg of Cl 2} AlC ₂ H ₅ together with 4.5 ml of a 0.5 _{m-TiCl 4} solution in aliphatic and 300 mg of Cl 2 AlC 2 H 5 under ao protective gas 10 ml aliphatic, placed in a 250 ml shaking cylinder, which is then filled up to 250 ml with aliphatic. The procedure is continued as indicated in Example 1 as and obtained after one hour of polymerization 476 g of polyethylene with a viscosity number of (η) = 7.87.

Example6

When using the amount of TiCl ₃ and TiCl ₄ given in Example 5 and changing the amount of Cl ₂ AlC ₂ H ₅ according to Table II (column 1), the yields in grams given in the tables (column 2) are obtained after one hour of polymerization with the viscosity numbers shown in column 3.

Table II

Cl ₂ AlC ₂ H ₅ Yield on PÄ Viscosity number mmol g / hour (Φ 0 0 _ 1.16 200 4.2 2.32 476 7.87 10.0 361 3.62 25.0 260 3.41 50.0 200 3 ₉ 5

Example 7

4.4 g of violet TiCl ₃ , prepared according to K. Blankenstein, dissertation 1955, TH Hannover, is _{filled into a vibrating ball mill under protective gas together with 12 ml of a 0.5 M TiCl 4} solution in aliphatic and 90 ml of aliphatic and milled for 12 hours . The mixture is then mixed with 760 mg of Cl ₂ AlC ₂ H ₅ , dissolved in 25 ml of aliphatic, shaken for 5 to 10 minutes and treated further as described in Example 1. After one hour of polymerization, 76 g of polyethylene with a viscosity number (η) = 2.76 are obtained.

Example 8

2.5 g of brown TiCl _{4 -containing TiCl 3} , produced by silent electrical discharge according to F. Bock and L. Moser, MONTHS FOR CHEMISTRY, 34 (1913), pp. 1825 to 1833, are placed under protective gas in a 250 ml Shaking cylinder suspended in 240 ml of aliphatic, then 1 g of Cl _{2 AlC 2} H ₅ , dissolved in 10 ml of aliphatic, is added, the mixture is shaken for 10 minutes.

telt and further the polymerization of ethylene, as described in Example 1, carried out. After one hour of polymerization, 212 g of solid polyethylene have separated out. The viscosity number of the polymer is (η) = 4.08, the bulk density 0.23 g / cm ³ .

Example 9

130 ml of a 0.173 m- _{TiCl 3} suspension in aliphatic prepared in the manner described are placed under protective gas together with 5 ml of a 0.5 _{m-TiCl 4} solution in aliphatic and 6.3 g of C ₂ H ₅ AlCl ₂ in a 250 ml shaking cylinder. This is then filled with aliphatic up to 250 ml and shaken for 5 to 10 minutes. The mixture is added under protective gas in a 5-1 low-pressure stirred autoclave, add 1000 ml of anhydrous Aliphatin added, presses 520 g of propylene and stirred for 15 hours at 70 to 8O ⁰ C. The pressure falls during this period from 18 to 5 atm . The excess propylene is removed, the polypropylene formed is precipitated by adding methanol, washed and dried. The yield of polypropylene is 260 g.

Example 10

110 ml of a 0.173 m- _{TiCl 3} suspension in aliphatic prepared in the manner described are placed under protective gas with 12 ml of a 0.5 _{m-TiCl 4} solution in aliphatic and 6 g of C ₂ H ₅ AlCl ₂ in a 250 ml shaking cylinder given. The procedure is continued as indicated in example 9 and obtained after 15 hours of polymerization at 70 to 8O ⁰ C. 32 g of solid polypropylene. In addition, 210 g of liquid propylene polymers were formed.

Claims (2)

Patent claims: 1. Process for the preparation of catalysts for the polymerization of olefinic hydrocarbons from a titanium trihalide, a titanium tetrahalide and a halogen-containing organoaluminum Compound, characterized in that the titanium trihalide compound used is any titanium trihalide, preferably brown titanium trichloride, and as a halogen-containing organoaluminum compound Monoalkylaluminum dihalide or alkylaluminumalkoxyl used and the molar ratio between titanium trihalide and titanium tetrahalide between 0.1: 1 and 100: 1, preferably between 2: 1 and 24: 1. 2. The method according to claim 1, characterized in that the monoalkylaluminum dihalide added in an amount equimolar to the titanium tetrahalide. 45