DE1183479B - Process for the preparation of catalysts for the polymerization of olefins and diolefins - Google Patents

Description

Process for the preparation of catalysts for the polymerization of Olefins and Diolefins The invention relates to a process for the preparation of Catalysts for the production of predominantly solid, highly crystalline polymers linear Structure made from monoolefinic and diolefinic hydrocarbons through polymerization.

It has been widely proposed in catalysts for polymerization of olefins obtained from a reaction product of aluminum chloride with powdered aluminum in a weight ratio of 10: 1 to 1: 1 and one lower olefin and compounds of metals of IV., V. or VI. Subgroup of the periodic table.

This older proposal also relates to a method of manufacture of catalysts for the polymerization of olefins, in which aluminum chloride and aluminum powder in a weight ratio of 10: 1 to 1: 1 with a lower one Olefin brought into contact and simultaneously or subsequently with a metal compound the IV., V. or VI. Subgroup of the periodic system is treated.

Such catalysts can be used at low pressures and temperatures between about 20 and 600 C high molecular weight α-olefin homo- or mixed polymers with high Establish crystallinity and other valuable properties.

The invention relates to a process for the production of catalysts for the polymerization of olefins of the general formula CH2 = CHR, in which R is hydrogen or a lower alkyl radical, or of conjugated diolefins with at least a vinyl double compound from compounds of metals from IV. to VI. Subgroup of the Periodic Table of the Elements and Metals of the II. or III. Group of Periodic table in the presence of lower olefins, which is characterized is that one ferric chloride, boron trichloride, bismuth trichloride or titanium trichloride as anhydrous or partially hydrated halides, optionally in the presence of saturated aliphatic hydrocarbons, which are liquid at room temperature are, or of liquid aromatic hydrocarbons and metals of II. or III. Group of the periodic table, also in the presence of HCI, in weight ratio between 10: 1 and 1: 1 with a lower olefin and simultaneously or subsequently with compounds of metals from IV. to VI. Subgroup of the periodic system brings together.

The positive influence of small amounts of water on the formation of the catalysts is due to the hydrogen chloride released as a result, the as is well known has an activating effect on Friedel-Krafts catalysts.

The preferred metal of II. And III. Group is aluminum that preferred lower olefin ethylene, the preferred compounds of the metals of IV. To VI. Subgroups are a titanium or a vanadium halide.

The preparation of the catalysts can be carried out in one or in two stages take place, d. that is, all of the reactants can mix and match at the same time be reacted under pressure at high temperatures of 100 to 2000 C, or that Metal of II. Or III. Group is made with ferric chloride, boron trichloride, bismuth trichloride or titanium trichloride and the lower olefin first at temperatures from 20 to 2500 C, preferably 150 to 2000 C, and pressures of 50 to 100 atm. implemented and the reaction product obtained in this way, preferably after separating off the solid residue, with the compounds of metals from IV. to VI. Subgroup implemented.

The two-stage process in which the most favorable for each stage Process conditions selected becomes essential because of the resulting benefits more active catalysts are preferred. The crude product of the first stage generally contains solid residues of the halide of the metal used.

The removal of these residues before the start of the second stage of the process has the double advantage that the formation of oily polymers during the polymerization of olefins is avoided and the purification of the polymeric product is facilitated.

The various components of the catalysts can be in the following Weight ratios are present: 10 to 100 parts by weight of metals of II. And III. Group of the Periodic Table, preferably 30 to 50 parts, per 100 parts by weight FeCl3, BCl3, BiCl3 or TiCl3. The compounds of metals from IV. To VI. Subgroup are used in amounts corresponding to a molar ratio of the metal, e.g. B. of aluminum, for the connection of the transition metal of 0.5: 10.

Of the halides suitable for the preparation of the catalysts ferric chloride is the most active.

But they are also effective with the other halides listed Polymerization catalysts obtained, although they react more slowly. Interesting is the use of titanium trichloride, which is also a halide of the Friedel-Krafts type and a compound of a metal, IV. to VI. Subgroup is. In this way can after the first process stage, in which the conversion of TiCl3, Al and ethylene is carried out in solution at 130 to 2000 C, passed directly to the polymerization and introducing the olefin at temperatures of about 700 ° C. with no other intermediate reactions will.

The catalysts of the invention are particularly active and theirs Production costs especially when using cheaper halides such as ferric chloride, extremely low. In addition, they are not as dangerous as others, e.g. B. Polymerization catalysts made directly from alkylaluminum compounds. The catalysts can not only polymerize ethylene, but also of olefins such as propylene and butene-1, alone or in admixture with one another will. Diolefins can also be polymerized or copolymerized with these catalysts will.

The invention is illustrated in the following examples, wherein no protection is desired for the polymerization.

Example 1 250 cc of n-heptane, 5 g of aluminum powder and 30 g of ferric chloride with a content of 0.5 o of water are placed in a 0.5-1 shaking autoclave. After removing the air by repeated washing with ethylene, the autoclave becomes heated to 1500 C and ethylene up to a pressure of 50 atm. introduced.

This pressure is gradually increased by further additions of ethylene for the absorbed ethylene kept constant. After 2 hours the autoclave is cooled, the remaining gas was discharged and 8.7 g of titanium tetrachloride were sucked into the autoclave. The temperature is increased to 750 C while in the autoclave by adding ethylene corresponding to the ethylene absorption a pressure of 10 atm. is maintained.

After 6 hours the reaction is stopped by introducing 20 cc of methanol canceled in the autoclave. After cooling down, the remaining gases are blown off and the autoclave opened. The raw polymer is cleaned with methanol and hydrochloric acid and here 88 g of pale brown colored polyethylene obtain. The polymer has a Intrinsic viscosity of 1.41, is soluble to 30.2ovo in acetone and contains due to the Action of the ferric chloride not completely converted in the first process stage a large amount of low molecular weight polymer on the course of the polymerization.

Example 2 280 cc of n-heptane, 50 g of aluminum powder and 150 g of 0.5 o / o Ferric chloride containing water is placed in a 1.1 liter autoclave equipped with a stirrer given. After a reaction time of 7 hours at 1500 C under a pressure of 80 atm. in the presence of ethylene the autoclave is cooled, the reaction product taken and the liquid phase consisting of a brown product containing of 5.9% dissolved aluminum and 12.3% chlorine, decanted off.

4.5 g of this solution are mixed with 250 cc of n-heptane and 0.95 g of titanium tetrachloride placed in an autoclave.

Ethylene is used up to a pressure of 10 atm. introduced and 2 hours polymerized at 700 C while maintaining a constant pressure.

There are 200 g of polyethylene obtained after washing with methanol and hydrochloric acid are completely white. The intrinsic viscosity is 4.12. The one in acetone soluble fraction is 2.2 01o of the total product, which according to X-ray analysis has a crystallinity of 81ein.

Example 3 24 g of the catalyst solution prepared according to Example 2 with a content of 5.9% Al and 12.3eo Cl are with 4.4 g TiCls and 750 ccm Put n-heptane in a 3-liter autoclave. 390g propylene are added and the Polymerization carried out at 700 ° C. for 12 hours. Then the reaction terminated by introducing 50 cc of methanol, the mixture cooled and the remaining gas removed. After washing the polymer with methanol and hydrochloric acid 81 g of powdery white polypropylene with an intrinsic viscosity of 4.57 were obtained. According to X-ray analysis, the product has a crystallinity of 60%.

Example 4 7.9 g of the catalyst solution prepared according to Example 2 with a content of 5.90 / 0 Al and 12.3e / 0 Cl are put together in a 1-liter autoclave given with 1.62 g of VCl4 and 150 ccm of n-heptane. Then 150 g of butadiene added and the mixture reacted at 300 ° C. for 14 hours.

After the reaction has ended, 14 g of polybutadiene are obtained, according to Infrared analysis predominantly from a linear polymer with a 1,4-trans linkage and minor amounts of a 1,2-linked polymer and a crosslinked polymer exist.

Example 5 14 g of the catalyst solution according to Example 2 are added Put 2.6 g of VOR13 and 500 cc of n-heptane in a 3-liter autoclave. In a second The autoclave is a mixture of 292 g propylene and 29 g Ethylene (in a molar ratio of propylene to ethylene of about 6: 7) heated to 1000 C, so that all of the olefin is converted into the gaseous state.

The gaseous mixture is passed through a connecting pipe and a supply pipe from the second autoclave into the first autoclave until a pressure of 6 atm. is reached, with gas continuously at a rate of 84 1 / h. deducted to keep the pressure constant. The temperature will be throughout Maintained reaction time of about 45 minutes at 40 to 500.degree. After that the polymerization terminated by introducing 20 cc of methanol into the autoclave, and the mixture was cooled and a viscous solution of the polymer is withdrawn from the autoclave. The solution will be Purified by washing with hydrochloric acid and then the polymer by treatment precipitated with methanol. Here, 35 g of a white product with excellent obtained elastic properties.

The polymer has an intrinsic viscosity of 1.77 and is in benzene completely soluble. According to X-ray analysis, it is a completely amorphous copolymer from ethylene and propylene.

Example 6 3 g of aluminum powder, 3 g of Bs13, 1 g of HC1 and 50 cc of n-heptane are placed in a 1200 cc autoclave. The mixture is in the presence for 2 hours of ethylene at a pressure of 20 atm. heated to 1500 C while maintaining fresh ethylene slowly introduced at constant pressure to replace the absorbed will.

At the end of this process stage it is cooled to 900 C and the rest Gas blown to remove all of the ethylene and boron chloride. After further Cooling to room temperature, 3.4 g of titanium tetrachloride are introduced.

The catalyst obtained is used for the polymerization of ethylene. After 4 hours of reaction at 700 ° C. and a constant pressure of 25 atm. will 20 cc of methanol introduced and the reaction terminated. The reaction mass will washed with methanol and hydrochloric acid, and 55 g of a white polyethylene powder are obtained with an intrinsic viscosity of 3.65 which, according to X-ray analysis, has a crystallinity of 80 ovo has.

Furthermore, 30 g of an oily polymer are obtained.

Example 7 75 g BiCl3, 0.2 g water, 5 g aluminum powder and 250 cc of n-heptane are introduced into a 500 cc autoclave. The mixture becomes 430 Minutes in the presence of ethylene at a pressure of 50 atm. heated to 1800 C. Thereafter, the reaction product is taken out under nitrogen, and the liquid Phase is decanted from the solid phase.

150 ccm of the liquid are mixed with 250 ccm of n-Hep- tan and 7.1 g TiCl4 placed in the same autoclave. Ethylene is 4 hours at 750 C and a pressure of 10 atm. polymerized with this catalyst. There are 49 g of a solid polymer and 5.5 g of an oily polymer were obtained. The intrinsic viscosity of the solid polymer is 1.83 and its crystallinity according to X-ray analysis 83%.

Example 8 5 g of aluminum powder, 35 g of TiC13 and 250 cc of n-heptane become placed in a 500 cc autoclave. The mixture is heated to 1500 C and at this temperature for 3 hours with stirring at a pressure of 50 atm. in present held by ethylene.

Thereafter, the temperature is reduced to 800 C and the polymerization of ethylene at a pressure of 30 atm. carried out for 5 hours.

There are 15 g of solid polyethylene with a very high molecular weight and an intrinsic viscosity of 10.45. The product has according to X-ray analysis a crystallinity of 870 / o.

Claims (2)

Claims: 1. Process for the production of catalysts for the polymerization of olefins of the general formula CH2 CHR, in which R is hydrogen or a lower alkyl radical, or of conjugated diolefins with at least a vinyl double bond from compounds of metals from IV. to VI. Subgroup of the Periodic Table of the Elements and Metals of the II. or III. Group of Periodic table in the presence of lower olefins, d u r c h marked, that one ferric chloride, boron trichloride, bismuth trichloride or titanium trichloride as anhydrous or partially hydrated halides, optionally in the presence of saturated ones aliphatic hydrocarbons that are liquid at room temperature, or of liquid aromatic hydrocarbons and metals of II. or III. group of the periodic table also in the presence of HC1, in a weight ratio between 10: 1 and 1: 1 with a lower olefin and simultaneously or subsequently with Compounds of metals from IV. To VI. Subgroup of the periodic system. 2. The method according to claim 1, characterized in that the lower Olefin used at superatmospheric pressure and temperatures between 50 and 2000 C. and by bringing the halide into contact with the metal of II. or III. group and the lower olefin obtained reaction product at temperatures between room temperature and 760 C with the compound of a metal of IV. to VI. Subgroup brought together will. Documents considered: Belgian patent specification no. 538782.