DE1135174B - Process for the polymerization of olefinically unsaturated hydrocarbons - Google Patents

Description

Process for the polymerization of olefinically unsaturated hydrocarbons Process for olefin polymerization at low pressures and temperatures below Use of catalysts made from heavy metal halides and organometallic compounds of metals from I. to III. Group of the periodic table, the metals themselves or whose hydrides have been produced are from the laid out documents of Belgian patents 533 362, 534 792, 534 888 and 538782 already known. The after The polymers obtained by this process are relatively low Molecular weight. However, it is often expedient to use polymers with a relatively high molecular weight to produce that have better thermal stability or high impact resistance.

It has now been found that such property improvements by the addition of peroxide to the known catalyst components can be achieved can.

The invention therefore relates to a process for olefinic polymerization unsaturated hydrocarbons, optionally in the presence of diluents, using a catalyst made from the following ingredients has been: firstly from at least one halide of titanium, zirconium, hafnium or germanium and secondly from at least one of the following components: a) an organometallic halide of the formula RXMXy, in which R is a saturated acyclic, saturated cyclic or aromatic hydrocarbon radical or combinations of these radicals, M aluminum, gallium, indium, thallium or beryllium, X a halogen atom means and in which x and y are integers, the sum of which is equal to the valence of the metal M is, b) a mixture of an organic halide and at least one of the metals sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, Zinc, cadmium, mercury, aluminum, gallium, indium or thallium and c) one complex hydride of the formula M'M "Hz, in which M'an alkali metal and M" aluminum, gallium, Indium or thallium means and x is equal to the sum of the valences of the two Metals M 'and M "is.

The method is characterized in that the catalyst at least a peroxide of the formula R'O OR ', in which R'hydrogen, an alkyl, aralkyl, alkaryl, Cycloalkyl, acyl, alkynyl or aryl radical has been added and the Polymerization with this catalyst at a temperature of -157 to + 260 ° C and a pressure of 1 to 2100 atmospheres.

As an example of peroxides of the formula R'O O R ', those mentioned in R' Residues with 1 to 20, but preferably 2 with no more than 10 carbon atoms means, the following may be mentioned: hydrogen peroxide, methyl hydroperoxide, Isopropyl hydroperoxide, tert-butyl hydroperoxide, cyclohexyl hydroperoxide, - dimethyl-p-isopropylbenzyl hydroperoxide, Dimethyl peroxide, di-n-propyl peroxide, di-tert.-butyl peroxide, methyl ethyl peroxide, 3-methyl-3-hydroperoxy-butyn- (l), 2-methyl-butyn- (3) -yl-hydroperoxide, bis [2-methylbutyn- (3) -yl] peroxide, dibenzoyl peroxide, diacetyl peroxide, dipropionyl peroxide, N, x-dinaphthyl peroxide, Peroxyformic acid, peroxyacetic acid, peroxybutyric acid, peroxybenzoic acid, peroxycinnamic acid and diperoxyterephthalic acid.

Catalyst mixtures falling within the scope of the invention and preferred because of their use in the polymerization of olefins leads to polymers with a relatively high molecular weight and / or the application relatively low reaction temperatures and pressures allowed are the following : A mixture of titanium tetrachloride and benzoyl peroxide with an approximately equimolar Mixture of ethyl aluminum dichloride and diethyl aluminum chloride, a mixture of Zirconium tetrachloride and benzoyl peroxide with an approximately equimolar mixture of ethylaluminum dichloride and diethyl aluminum chloride, a mixture of titanium tetrachloride, benzoyl peroxide and Lithium aluminum hydride, a mixture of titanium trichloride and benzoyl peroxide with one approximately equimolar mixture of ethyl aluminum dichloride and diethyl aluminum chloride, a Mixture of titanium tetrachloride and di-tert-butyl peroxide with an approximately equimolar Mixture of ethyl aluminum dichloride and diethyl aluminum chloride and a mixture of titanium tetrachloride, benzoyl peroxide, ethyl chloride and elemental sodium.

The amount of each used in the polymerization of olefins Catalyst ingredients can vary over a wide range. Relatively small amounts of catalyst give the desired activation effect when the polymerization reaction in batch mode with continuous addition of the olefin depending on is carried out from the course of the polymerization reaction. It can be 50 to 2000 g Polymer / g of the catalyst mixture used in the reaction are obtained.

When working with a continuous flow, the concentration lies of the total catalyst mixture usually in the range of from 0.01 to 1.0 percent by weight.

The amount of peroxide used is generally in the range of 0.05 to 50, preferably 0.2 to 3 moles of peroxide / mole of metal halide. The amount of organometallic halide is 0.05 to 50, preferably 0.2 to 3 mol per mol of metal halide. The quantities the organic halide, metal and metal halide are in the range of 0.02 up to 50 moles of organic halide per mole of metal halide and from 0.02 to 50 moles Metal per mole of metal halide. A preferred ratio is from 0.2 to 3 Moles of organic halide per mole of metal halide and from 0.2 to 3 moles of metal each Moles of metal halide.

The amount of complex hydride is generally in the range of 0.05 to 50, preferably 0.2 to 3 moles per mole of metal halide.

The polymerizable hydrocarbons are olefins that have a CH2 = C radical included. Preference is given to 1-olefins with up to 8 carbon atoms used per molecule. In particular, it is found that ethylene with the invention Catalyst mixture can be polymerized at lower temperatures and pressures than the above-mentioned known methods. Examples of other polymerizable Hydrocarbons that can be used in the process according to the invention, are: propylene, butene (l), hexene (l) and octene (l). Branched-chain olefins, z. B. isobutylene, and 1, 1-dialkyl-substituted and 1,2-dialkyl-substituted ethylenes such as butene (2), pentene (2), hexene (2), heptene (3), 2-methylbutene (1), 2-methylhexene (1) and 2-ethylheptene- (I) can be used. As examples of di- and polyolefins, in which the double bonds are in non-conjugated positions and those according to the invention can be used are 1,5-hexadiene, 1,4-pentadiene and 1,4,7-octatriene called. Cyclic olefins such as cyclohexene can also be used.

Mixtures of the aforementioned hydrocarbons can be present in the presence of the new catalyst are polymerized to solid polymers, for example Mixtures of ethylene with propylene, ethylene with butene- (l), propylene with butene- (l) or propylene with a pentene. Also aryl olefins, e.g. B. styrene and alkyl-substituted Styrenes can be polymerized to solid polymers by the process according to the invention will. The process can also be applied to the polymerization of conjugated dienes with 4 up to 8 carbon atoms are used. Examples of conjugated dienes are 1,3-butadiene, 2-methyl- 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2-methyl-3-ethyl-1, 3-pentadiene or 2-phenylbutadiene called.

It is also within the scope of the present invention to conjugate these Serve either alone or in admixture with one another and / or in admixture with one or several other compounds which contain a CH2 = C group and with these are copolymerizable to polymerize. These latter compounds include Monoolefins such as those described above.

One of the most important in the polymerization of olefins in the presence the advantages achieved by the new catalyst mixture is that lower temperatures and pressures than can be used in the aforesaid known methods. the Temperature can still be varied over a fairly wide range, for example from -157 to 260 ° C.

The preferred temperature range is 10 to 149 ° C. Although pressures can be used in the range from atmospheric pressure up to 2100 atü Pressures from atmospheric pressure up to 70 atmospheres are preferred, with a pressure in the range from 7 to 49 atm is even cheaper.

In this connection it should be mentioned that it is advantageous to carry out the reaction in the presence of a hydrocarbon as an inert organic diluent perform at a high enough pressure to keep the diluent in the to keep liquid phase. But the reaction also takes place in the gas phase without it Thinner.

The preferred pressure range given above results as stated solid polymers of olefins in excellent yields.

Suitable diluents are paraffins, cycloparaffins and / or aromatic hydrocarbons that are proportionate under the process conditions are inert, harmless and liquid.

The process according to the invention can be carried out in batches by adding the Olefins in a catalyst and optionally containing diluent Reaction vessel are run. Also, the process can be continuous by sustaining the above-described concentrations of the reactants in the reaction vessel for a suitable length of stay.

When charging the reaction vessel with the catalyst components a working method is to be preferred in which it is guaranteed that the peroxide lasts for a long time not in the reaction vessel with the organometallic halide, the mixture of an organic Halide and a metal and / or the complex hydride is present until the Metal halide is also located in the reaction mixture. With that in mind it is advisable to mix the metal halide and the peroxide before charging or to bring in these two components at the same time.

After completion of the polymerization reaction, the recovery of the Polymer carried out in a known manner.

The following examples illustrate the invention without restricting it.

Example 1 In a 2700 cc stainless steel reaction vessel ethylene was polymerized according to the procedure described below.

2.42 g (0.01 mol) of benzoyl peroxide were added to 100 cc of benzene (over sodium dried and distilled), which is mixed with 0.949 g (0.005 mol) of titanium tetrachloride was given. This mixture was taken under purified nitrogen for 20 minutes Heated to reflux and was very dark orange brown in color. It was then under Pressure of purified nitrogen along with another 380 cc of benzene into the reaction vessel brought in. 4 cc of ethyl aluminum sesquichloride was mixed with 20 cc of benzene and placed in the reaction vessel. The reaction vessel was then placed on a shaker brought and adjusted with ethylene to a pressure of 21 atm.

An electric heater attached to the reaction vessel became used to maintain a temperature of 149 ° C. From time to time it has been Ethylene depending on the course of the reaction and the temperature drop in the reaction vessel pressed in.

After 3 hours and 52 minutes, the reaction vessel was filled with ethylene brought back to a pressure of 38.7 atmospheres. The reaction continued overnight. After a total reaction time of 161/2 hours, the reaction vessel was cooled and open. The resulting dark brown polymer became after addition of methyl alcohol instantly white. The polymer was in a mixer together with 500 ccm Methyl alcohol introduced and at speeds ranging from 8,000 to 16,000 Rev / min crushed. The polymer was then filtered off on porcelain plates placed in a vacuum oven and dried at 75 ° C for 24 hours. It was something like that 50 g of polymer obtained.

The properties of a sample of the one prepared as described above Ethylene polymer can be seen from Table I below.

Table I Molecular weight (determined from the melt index) ......... 38 575 density, grams per cubic centimeter at room temperature .......... 0.960 flexibility good impact resistance (ball drop method)> 183 cm melt index .................. 1.198 Melting point .................. 1221 ° C Compressibility good Example 2 In one Ethylene was added to the 1400 cc stirred reaction vessel according to the procedure described below polymerized.

In this example the 400 cc of cyclohexane (dried over sodium and distilled) containing reaction vessel with 2.42 g benzoyl peroxide, 0.949 g titanium tetrachloride and 4 cc of ethyl aluminum sesquichloride are charged. After all catalyst components have been introduced ethylene was injected into the reaction vessel until a pressure of 21 atm at 38 ° C was reached. The heater with which the reaction vessel was equipped, was started and the response was found to be almost instantaneous began as this from the pressure drop in the reaction vessel and the simultaneous Temperature rise was evident.

A maximum temperature of 149 ° C was reached during the polymerization achieved. After 50, 57 and 80 minutes, the reaction vessel was filled with ethylene back on brought a pressure of 21 atm. 45 minutes after the last time the The heat source was removed with the pressure in the reaction vessel.

After the reaction vessel was allowed to cool and opened, it was found that this filled with a tough, fibrous polymer swollen with cyclohexane was.

This polymer was removed from the reaction vessel into a Waring mixer with excess methyl alcohol and ground for about 30 minutes. The polymer was then collected by filtration and taken up overnight Vacuum oven held at 75 ° C.

The properties of a sample of the one prepared as described above Ethylene polymer are shown in Table II below.

Table II Molecular weight (determined from inherent viscosity) 35 964 density, grams per cubic centimeter at room temperature .......... 0.957 impact strength (Falling ball method) 122cm melting point *) ................. 119 1.5 ° C inherent viscosity *) 1.471 *) The intrinsic viscosity was measured at 130 ° C using a solution of 0.2 g of the polymer determined in 100 ml of tetrahydronaphthalene.

Comparative experiment in a 1200 cc shaking autoclave made of stainless steel Steel became ethylene in the presence of a mixture of 3.55 g of titanium tetrachloride and 4 g of a mixture of diethyl aluminum chloride and ethyl aluminum dichloride Polymerized catalyst. The catalyst was dissolved in 500 cc of benzene (over sodium dried) and introduced into the autoclave, the autoclave under a nitrogen atmosphere was held. The ethylene was prior to entering the autoclave to remove Oxygen, carbon dioxide and water vapor passed through a cleaning system. That The cleaning system contained a pyrogallol solution, a sodium hydroxide solution and Desiccant. The ethylene was introduced into the autoclave, with catalyst and diluents were maintained at atmospheric pressure. The polymerization of the Ethylene began immediately and the temperature rose depending on the supply of ethylene of the reaction mixture rapidly to 79 ° C. The ethylene was as fast as it was the dimensions of the cleaning system allowed to be introduced into the autoclave. The one in the autoclave maximum pressure reached was 21 atm. After a reaction time of 15 minutes the autoclave was opened. There was an ethylene polymer as a suspension in the Benzene solution. 100 cc of butyl alcohol were used to inactivate the catalyst placed in the autoclave. The solid polymer was from the benzene-alcohol mixture filtered off and then washed with isopropyl alcohol. After filtering off the polymer of the isopropyl alcohol it was placed in a vacuum oven at about 60 ° C overnight dried.

In this way about 100 g of polyethylene was obtained.

The properties of a sample of the one prepared as described above Ethylene polymer are summarized in Table III below.

Table III (comparative experiment) Molecular weight (from the melt index determined) ......... 9.025 density, grams per cubic centimeter at room temperature .......... 0.941 flexibility very brittle impact strength (ball drop method) break at 15.24 cm Melt index .................. 445.0 Melting point .................. 1171 ° C Intrinsic viscosity 0.451 color ......................... light brown As the examples show, arises by adding a peroxide to the other components of the catalyst Polymer of much higher molecular weight than if a catalyst mixture which does not contain peroxide is used. So if like in the comparative example a catalyst composed of titanium tetrachloride and ethylaluminum sesquichloride for polymerization of ethylene is used to obtain a solid polymer which is a comparatively has a low molecular weight. If, on the other hand, a peroxide, such as benzoyl peroxide, used in conjunction with titanium tetrachloride and ethylaluminum sesquichloride, see above possesses the polymer obtained, as can be seen from Examples 1 and 2, a much higher molecular weight, which makes the product much more useful will. As you can see after checking the test data, this has after the procedure polymer produced according to the invention has a much higher impact resistance and others improved properties.

The polymers produced in this way are suitable for all areas of application, where solid plastics are used, useful. You can use it for impregnation used by paper and woven fabrics and made into any molded article Shape how bottles and other containers for liquids are pressed. Further they can be formed into tubes by extrusion.

PATENT CLAIM: 1. Process for the polymerization of olefinically unsaturated Hydrocarbons, optionally in the presence of diluents, using a catalyst made from the following components: first of at least one halide of titanium, zirconium, hafnium or germanium, and second, from at least one of the following components: a) an organometallic halide of the formula R., MXy, in which R is a saturated acyclic, saturated cyclic or aromatic hydrocarbon radical or combinations of these radicals, M aluminum, Gallium, indium, thallium or beryllium, X is a halogen atom and in the x and y are integers, the sum of which is equal to the valence of the metal M, b) a mixture of an organic halide and at least one of the metals Sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, zinc, cadmium, Mercury, aluminum, gallium, indium or thallium and c) a complex hydride of the formula M'M "HZ, in which M'an alkali metal and M" aluminum, gallium, indium or Thallium means and x is equal to the sum of the valencies of the two metals M ' and M ", is characterized in that at least one peroxide is added to the catalyst Formula R'O O R ', in which R'is hydrogen, an alkyl, aralkyl, alkaryl, cycloalkyl, Acyl, alkynyl or aryl radical has been added and the polymerization with this catalyst at a temperature of -157 to + 260 ° C and a pressure of 1 to 2100 atm.

Claims (1)

2. The method according to claim 1, characterized in that as olefinic unsaturated hydrocarbon an aliphatic 1-olefin with up to 8 carbon atoms is used per molecule. Publications considered: Documents laid out by the Belgian Patent Nos. 533 362,534 792,534 888,538 782; "Angewandte Chemie", 67 (1955), Pp. 541 to 556; Chemiker-Zeitunge, 79 (1955), pp. 657 to 633.