DE2848907A1 - Catalyst for polymerisation of vinyl cpds. - using macro-porous crosslinked polystyrene as carrier, giving increased activity - Google Patents

Abstract

Catalyst for dimerisation, oligomerisation or (co)polymerisation of vinyl cpds., consisting of an active phase of a transition metal of gp IV or V on a macro-porous copolymer carrier from vinyl and divinyl monomers, with surface area 30-700 m2/g., and an organic cpd. of Al as co-catalyst. Used in prond. of ethylene and alpha-oleiene (co)polymers. Catalysts has high activity giving polymers with low ash content without washing, and allowing particle size of the polymer to be controlled.

Description

3description

The present invention relates to the field of polymers, in particular it relates to a catalyst for dimerization, oligomerization, interpolymerization and polymerization of vinyl monomers and has applications in the manufacture of Polymers.

They are catalysts for dimerization, oligomerization, interpolymerization and polymerization of ethylene and α-olefins known, soft from an active Phase, a compound of a transition metal, applied to the surface of inorganic or organic carrier, and various meta-organic compounds exist.

The use of catalysts which contain -inorganic carriers, leads to an increase in the ash content of the polymer and, in some cases, to a deterioration its physical-mechanical properties. For example, it worsens the use as an inorganic carrier of magnesium chloride (USA Pat; entschrift Rr. 3.243.422, patent specification of the Federal Republic of Germany No. 2033468) the dielectric constant of the polymer and causes corrosion of the equipment its processing.

The use of catalysts containing organic carriers is due to the low specific surface and low Sunmarian pore volume the carrier used is not very effective. The said catalyst has a low specific activity.

(see French patent specification No. 1550186).

It is also a catalyst for the polymerization of ethylene and propylene known, which consists of a compound of a transition metal of the IV. bis VI. and VIII. Group of the Periodic Table, applied to polyolefins with a Particle size from 0.25 to 0.5 mm, and a cocatalyst, an organometallic Connection exists. The particles of the polymer being formed have a size from 1.8 to 3.5 mm (patent specification of the Federal Republic of Germany No. 1943751).

The use of a coarse fraction of the polyolefin, for example of polyethylene, used to prepare the catalyst, makes it possible to produce coarse particles of the polymer, however, does not allow the grain composition of the itself by regulating the synthesis forming polymer.

Another disadvantage of the said catalyst is that its specific activity not high, the yield low and the ash content of the obtained Polymers is high.

The purpose of the present invention is to overcome the disadvantages mentioned above to avoid.

The invention was based on the object of a catalyst for dimerization, oligomerization, copolymerization and polymerization of vinyl monomers to develop through the selection of an appropriate carrier for the active phase, which has a high specific activity, regulates the grain composition of the resulting copolymer or polymer guaranteed and makes it possible to use a copolymer or polymer with; low Preserving ash content without laundry.

This object is achieved in that the catalyst for dimerization, Oligomerization, interpolymerization and polymerization of vinyl monomers, the from an active phase, a compound oines transition metal of IV.-V. group of the periodic table, applied to a polymer Carrier, and a cocatalyst, an organoaluminum compound, exists according to the invention a macroporous copolymer of vinyl and divinyl monomer as the polymeric carrier with a specific surface area of 30 to 700 m2 / g.

The technical term macroporous copolymer is used to denote a two-phase system, in which the polymeric material with mutually harmonizing cavities (pores) is interspersed, who are able to deal with the external medium when exchanging it to fill in this medium.

The use in the catalyst of said carrier with a specific surface area of less than 30 m2 / g is inexpedient due to the low Effectiveness of the catalyst. The use in the catalyst of said carrier with a specific surface area of more than 700 m2 / g is more difficult due to technical Complexity of manufacturing such a carrier. It is preferred that the Catalyst; or contains a carrier which has pores of 0.3 to 2.8 cm3 / g.

The use of a carrier with a pore volume less than 0.3 cc / g is inconvenient due to the poor capacity of the carrier compared to the active phase, while the use of a carrier with a pore volume of more than 2.8 em3 / g is more difficult due to the high brittleness of such a carrier It it is useful that the catalyst is a copolymer of styrene and as a support Divinylbenzene, a copolymer of styrene and diisopropenylbenzene, a copolymer from styrene, divinylbenzene and methyl methacrylate or a mixed polymer of styrene, Contains divinylbenzene and vinyl pyridine.

The use as a component of one of the above-mentioned mixed polymers of the vinyl monomer and divinyl monomer makes it possible to have the specific activity of the catalyst to increase significantly.

It is desirable that the catalyst have a particle size of 0.001 to 1 mm.

The use of a catalyst with a particle size of 0.001 up to 1 mm makes it possible to determine the particle size of the polymer obtained and the Width of its distribution to regulate according to the particle size.

It is; expedient that the catalyst is in the form of granules ;.

The regulation of the shape of the catalyst particles makes it possible in In the course of the synthesis of polymer particles of such a shape to obtain the most favorable guaranteed hydrodynamic conditions in the reactor.

It is appropriate that the catalyst is a compound as the active phase of titanium or vanadium, preferably containing their chlorides.

It is appropriate that the content of the catalyst the active phase is 1 to 60 percent by weight.

With a content of chlorides of titanium or vanadium of less than 1 percent by weight, the catalyst has insufficiently high activity while If the content is more than 60 percent by weight, there is a reduction in activity of the catalyst per unit mass of the transition metal (the specific effectiveness of the catalytic converter).

The catalyst is prepared as follows.

Macroporous copolymers are used as the macroporous polymeric carrier of monovinyl monomers such as styrene, ethyl styrene, diethyl styrene, isopropyl styrene, Methyl acrylate, methyl methacrylate with divinyl monomers such as divinylbenzene, ethyldivinylbenzene, Diisopropenylbenzene. Such copolymers are obtained by radical copolymerization in the presence of a pore former.

The specific surface: (m2 / g) and the total pore volume (cm3 / g) the erhalbonen macroporous copolymers depend on the composition of the monomeric mixture from little and are dee by the amount and composition Determined pore former.

Low and high molecular weight substances are used as i1orenbildner, dio i n dont monomeric mixture are readily soluble, do not enter into copolymerization and can be easily removed from the polymer obtained.

The amount of material on the surface of the polymeric support angry Transition metal can be in any ge.

desired boundaries fluctuate.

For the production of a catalyst based on rpitane chloride the above-mentioned support is treated with titanium chloride or solutions thereof in a vacuum or in an inert gas atmosphere at a temperature of minus 70 to plus 18000.

It is possible to manufacture a catalyst based on Titanium chloride by stepwise or simultaneous treatment of the support with titanium chloride and the organoaluminum compound (or solutions thereof) in vacuo or in the inert gas atmosphere at a temperature of minus 70 to plus 180 ° C, Den The catalyst obtained is dried at a temperature of dO to 1800C in vacuo.

In the manufacture of a catalyst based on vanadium chloride the support is treated with vapors or a solution of vanadium chloride and dried under vacuum.

A high activity of the catalyst is achieved by using as Carrier said macroporous copolymer with a surface area of 30 to 700 m2 / g used.

By using a carrier with a high specific surface a catalyst with a finely dispersed crystalline phase of titanium or is obtained Vanadium chloride. This has the effect of increasing the operational efficiency of the connection of Transition metal and leads to an increase in the activity of the catalyst.

The use of macroporous polymeric supports makes it possible to use catalysts with a large content of titanium or vanadium salt. The macroporosity increases the capacity of the carrier compared to the titanium or vanadium chloride.

The use of the carrier according to the invention makes it possible to use a highly active catalyst with surface accessible to the monomer with the To obtain salt of the transition metal coated support.

The catalysts according to the invention are used in the dimerization, Oligomerization, interpolymerization and polymerization of vinyl monomers. These Processes take place at increased pressure and in a vacuum, at concentrations of the monomer from 0.01 to 100 percent by weight and a temperature of minus 70 to plus 1800C.

The processes run through the use of the catalysts mentioned in high yield of dimers, oligomers, copolymers and polymers with low Degree of their contamination with inorganic residues, which makes it possible to use them without additional laundry.

Another advantage is that by regulating the grain composition of the catalyst, the grain composition of the polymer obtained by the synthesis controlled will.

The particle size of the polymer depends on the yield of polymer per unit weight of the catalyst and the grain size of the support. The yield of polymer is in turn determined by the activity of the catalyst, the concentration of the monomer and the polymerization time are determined.

With the same yields, that is, with the same conditions When the polymerization is carried out, the particle size of the polymer is determined by the particle size given by the wearer.

In order to better understand the present invention, the following specific Be games for the preparation and use of the catalyst according to the invention cited.

In Examples 1-27 the particle size of the catalyst is determined by the particle size of the carrier is determined.

Example 1.

irritation of the catalyst 1.18 g of a carrier with a particle size from 0.3 to 0.8 mm in the form of spherical granules, which is a copolymer of styrene (70 percent by weight) and divinylbenzene (30 percent by weight) with a represents a specific surface of 160 m2 / g and a pore volume of 1.65 cm3 / g, placed in a dry flask. The piston with the carrier if vacuumed, the support is treated with titanium chloride vapors in an amount of 0.15 g and cool down. This is then treated with diethylaluminum chloride vapors in an amount of 0.065 g. The catalyst obtained is heated to a temperature of 1800C for 3 hours in a vacuum. According to the results of the analysis, the salary is of the catalyst obtained in titanium chloride 1 percent by weight, that in support 99 Weight percent. The catalyst is spherical granules.

Polymerization of propylene 0.15 g of catalyst, 1.1 g of diethylaluminum chloride, 5.7.10-3 mol of hydrogen and 130 g of propylene are brought into an autoclave; A stirrer with a capacity of 300 ml. The polymerization takes place at a temperature carried out at 600C and at 60 at overpressure. Obtained after a reaction time of 5.5 hours one 16.9 g of polypropylene with a grain size of 1.5 to 4 mm in the form of spherical Granules.

The content of the fraction insoluble in boiling n-heptane is 86 percent by weight. The yield of polymer per 7 g of titanium is; 36.14 kg, the ash content 0.0046 percent by weight.

Example 2.

Polymerization of propylene 0.08 g of catalyst, obtained analogously to Example 1, with a particle size of 0.1 to 0.25 mm, 0.76 g of i) ethyl aluminum chloride, 5.7. 10-3 moles of hydrogen and 130 g of propylene bring one into one An autoclave with a stirrer with a capacity of 300 ml. The polymerization leads one at a temperature of 600C and at 60 atm overpressure.

After a reaction time of 5 hours, 8 g of polypropylene are obtained with a Particle size from 0.5 to 1.4 mm in the form of spherical granules. The yield of polymer per 1 g of titanium is 32 kg, the ash content is 0.0052 g percent by weight. The molecular mass of the polypropylene obtained is 1.5. 106.

Example 3.

Preparation of the catalyst 5 g of a carrier with one particle size from 0.5 to 0.9 mm in the form of spherical granules, which is a copolymer of 60 percent by weight styrene and 40 percent by weight divinylbenzene with a specific Surface area of 274 m² / g and a pore volume of 1.56 cm³ / g, brings one in a dry flask.

The flask with the carrier is vacuumed, the carrier treated with Titanium chloride vapors in an amount of 0.52g and cools. Daim one treats the Carrier with diethyl aluminum chloride vapors in the amount of 0.162 g.

Heat the analyzer; one to a temperature of 180 ° C during 3 hours in a vacuum. According to the results of the analysis, the content of the obtained Catalyst on Titanium chloride 1 percent by weight, based on carrier 99 Weight percent. The catalyst is spherical granules.

Polymerization of propylene 0.1 g of catalyst, 1 g of diethyl aluminum chloride and 130 g of propylene are placed in an autoclave with a capacity of 300 ml. The polymerisation of propylene is carried out at a temperature of 70 ° C. and at 60 at overpressure. After a reaction time of 6.6 hours, 12.8 g of polypropylon are obtained with a small plate size of 2.7 to 5.0 mm in the form of spherical granules. The density of the polymer particles obtained is 0.87 to 0.92 g / cm 3. The yield of polypropylene is 41.1 kg per 1 g of titanium, the ash content is 0.011 percent by weight.

Example 4.

Polymerization of propylene 0.0558 g of catalyst, obtained according to the example 3, with a particle size of 0.25 to 0.5 mm, 0.3093 g of diethyl aluminum chloride and 130 g of propylene are placed in an autoclave of 300 ml capacity. The polymerization is carried out at a temperature of 70 ° C. and at 60 atm overpressure. After a reaction time of 7 hours, 7.3 g of polypropylene having a particle size are obtained from 1.5 to 2.8 mm in the form of spherical granules. The yield of polypropylene 1 g of titanium is 41.5 kg, the ash content 0.0108 weight percent.

Example 5.

Preparation of the catalyst 0.1412 g titanium chloride and 0.0599 g diethyl aluminum chloride it is mixed in a flask of 100 ml capacity at a pressure of 10-2 Torr and a temperature of minus 3000. 1.08 is added to the mixture obtained g of a carrier with a particle size of 0.03 to 1 mm in the form of spherical Granules, which is a copolymer of 60 percent by weight styrene and 40 percent by weight Divinylbenzene with a specific surface area of 360 m2 / g and a pore volume of 1.42 cm3 / g.

The contents of the flask are kept in a vacuum at a temperature of minus 10 ° C. The catalyst obtained is kept at a temperature of 8 ° 10 hours in vacuum.

According to the analysis results, the content of the catalyst is on Titanium chloride 1 percent by weight, the carrier 99 percent by weight. The catalyst represents spherical granules.

Polymerization of propylene 0.12 g catalyst, 0.3 g diethyl aluminum chloride, 5.7. 10-3 ³ mol of water and 130 g of propylene are placed in an autoclave with agitator. The polymerization will at one temperature from 600C and at 60 atm overpressure carried out. After a reaction time of 16.5 hours 27 g of polypropylene with a particle size of 0.2 to 0.7 mm are obtained in the form of spherical granules. The yield of polypropylene was 72.2 kg jo 1 g titanium, the ash content 0.0023 percent by weight.

Example 6.

Preparation of the catalyst 0.3094 g of a particle size carrier from 0.03 to 0.1 mm in the form of spherical granules, which is a copolymer of 85 percent by weight styrene and 15 percent by weight divinylbenzene with a specific A surface area of 97 m² / g and a cover volume of 1.25 cm³ / g brings one into a flask. The flask with the carrier is vacuumed and treated the carrier one after the other with titanium chloride vapors in a quantity of 0.0687g and Diethyl aluminum chloride vapors in a narrow range of 0.0206 g analogous to that in Example 1 described.

According to the analysis results, the catalyst contains 3 percent by weight Titanium chloride, 97 weight percent carrier.

The catalyst is spherical granules.

Polymerization of propylene 0.1 g of catalyst, 0.836 g of diethyl aluminum chloride and 130 g of propylene are placed in an autoclave and an oil stirrer with a capacity of 300 ml a. The polymerization is at a temperature of 700C and carried out at 60 atm overpressure. After a reaction time of 5.9 hours, 7.8 is obtained g of polypropylene with a particle size of 0.15-0.45 mm in the form of spherical Granules. The yield of polypropylene is 8.35 kg per 1 g of titanium, the ash content 0.029 weight percent.

Example 7.

Preparation of the catalyst 0.3301 g of a particle size carrier from 0.25 to 0.4 mm in the form of spherical granules, which is a copolymer of 88 percent by weight styrene and 12 percent by weight diisopropenylbenzene with a specific surface area of 60 m² / g and a pore volume of 1.0 cm3 / g, treated in vacuo with a mixture of 0.2545 g of titanium chloride and 0.0824 g Diethylaluminum chloride analogous to that described in Example 5. According to the analysis results the catalyst contains 9.82 percent by weight titanium chloride and 90.18 percent by weight Carrier. The catalyst is spherical granules.

Polymerization of propylene 0.17 g catalyst, 0.3 g diethyl aluminum chloride and 130 g of propylene are introduced into an autoclave with a stirrer. The polymerization wb'd at a temperature of 700C and at 60 at; Overpressure carried out. After 5.85 Hours of reaction time, 29.5 g of polypropylene having a particle size are obtained from 1.5 to 2.4 mm in the form of spherical granules. The yield of polypropylene is 5.72 kg per 1 g of titanium, the ash content is 0.08 percent by weight.

Example 8.

Polymerization of ethylene 0.1 g of the catalyst obtained according to Example 7 with a particle size of 0.25 to 0.4 mm, 1 g of diethyl aluminum chloride and 110 ml of toluene are placed in a reactor and ethylene is fed to it. The polymerization is oei a temperature of 60 ° C and a constant ethylene pressure of 0.5 at Overpressure carried out.

After a reaction time of 8.5 hours, 7 g of polyethylene are obtained with a Particle size from 1 to 2.0 mm in the form of spherical granules. The rate of polymerization of ethylene is 530 g polyethylene / g titanium St. atm.

Example 9.

Preparation of the catalyst 0.16 g of a carrier in the form of spherical beads Granules, which is a copolymer of 60 percent by weight styrene with 30 percent by weight Divinylbenzene and 10 percent by weight methyl methacrylate with a specific surface area of 134 m² / g and a pore volume of 1.34 cm³ / g is treated with Titanium chloride fumes in a benge of 0.0971 g and holds during the period 5 hours at a temperature of dO0O. According to the analysis results, the Catalyst 5.6 weight percent titanium chloride and 94.4 weight percent support. Of the Catalyst is spherical granules.

Oligomerization of propylene 0.095 g catalyst, 0.94 g diethyl aluminum chloride and 130 g of propylene are introduced into an autoclave with a stirrer. The oligomerizate; ion is carried out at a temperature of 700C and at 60 atm overpressure. After 6.4 Hours of reaction time 11.9 g of liquid oligomer are obtained. The yield of propylene oligomers is 9.1 kg per 1 g of titanium and the molecular weight of the oligomers obtained is cm 150.

Example 10.

Dimerization of ethylene 0.007 g of catalyst, obtained analogously to Example 9, 1.08 g of ethylaluminum dichloride and 0.2 liters of benzene are brought into one An autoclave and this leads to ethylene.

The dimerization takes place at a temperature of 20 ° C, at 25 atm overpressure performed during 2 £ i; unden. During the process, the ethylene pressure becomes constant held.

The butenes yield is 94 percent by weight and the yield of butenes per 1 g of titanium 6100 kg.

Example 11.

Preparation of the catalyst 0.26 g of a particle size carrier from 0.25 to 0.5 mm in the form of spherical granules, which is a copolymer of 60 percent by weight styrene and 40 percent by weight divinylbenzene with a specific Surface of 260 m2 / g and a pore volume of 1.5 cm3 / g- represents, holds one under vacuum for 4 hours at 80 ° C, cooled to room temperature and treated with vanadium chlo ridd vapor in an amount of 0.153 g.

According to the results of the analysis, the content of van din chloride is 32 percent by weight and that of carrier 68 percent by weight. The catalyst provides spherical granules.

Polymerization of propylene 0.045 g catalyst, 0.04 g Al (iso-C4H9) 3 and 50 ml of n-heptane are introduced into a reactor with a stirrer.

At a temperature of 60 ° C., propylene is fed in and the Polymerization at a constant propylene pressure of 470 Tcrr.

After a reaction time of 2 hours, 1.32 g of polypropylene with a Particle size from 2 to 3 mm in the form of spherical granules. The yield at Polypropylene is 0.3 kg per 1 g of vanadium and the speed of polymerization 240 g / g titanium St.atm.

The content of the fraction insoluble in n-heptane is 83 percent by weight. The density of the particles reaches 0.9 g / cm³. The molecular mass of the polymer is ~ 106.

Example 12.

Polymerization of propylene 0.067 catalyst, obtained analogously to Example 11, with a particle size of 0.001 to 0.03 mm, 0.06 g of triisobutyl aluminum and 70 ml of n-heptane are introduced into a reactor with a stirrer. At one temperature of 60 ° C is fed to propylene and the polymerization is carried out at a constant Monomer pressure of 470 torr. After a polymerization time of 2 hours, 2.4 is obtained g of polypropylene in the form of powder with a particle size of 0.2-0.4 mm.

The yield of polypropylene is 0.334 kg per 1 g of vanadium. the The rate of polymerization is 270 g / g Vanadium Ste atm.

Example 13.

Preparation of the catalyst 0.187 g of a particle size carrier from 0.25 to 0.5 mm in the form of spherical granules, which is a copolymer of GO weight percent styrene and 40 weight percent divinylbenzene with a specific surface of 260 m2 / g and a pore volume of 1.5 cm³ / g, is prepared analogously to that described in Example 11 and treated with vanadium chloride vapors in an amount of 0.35 g. The catalyst obtained is vacuumed at a temperature of 80 ° C.

According to the results of the analysis, the content of vanadium chloride is 60 percent by weight, that of carrier 40 percent by weight. The catalyst is spherical Granules.

Polymerization of propylene 0.0873 g catalyst, 0.0927 g Al (iso-C4H9) 3 and 70 ml of n-heptane are introduced into a reactor with a stirrer o. At one temperature of 60 ° C., propylene is fed in and the polymerization is carried out at a constant temperature Monomer pressure of 470 torr.

After a polymerization time of 2 hours, 3.7 g of polymer are obtained a particle size of 2 to 3 mm in the form of spherical granules. The yield of polypropylene is 0.216 kg per 1 g of vanadium. The rate of polymerization is 1Y5; / g vanadium St. atm.

Example 14.

Polymerization of ethylene 0.046 g of catalyst, obtained analogously for example 11, with a particle size of 0.001 to 0.03 mm, 0.025 g Triisobutyl aluminum and 50 ml of n-heptane are introduced into a reactor with a stirrer. At one temperature from 80 ° C, ethylene is converted into Iui (t leads to the polymerization at a constant Monomer pressure of 223 torr.

After a reaction time of 3 hours, 11.1 g of polyethylene are obtained in the form of powder with a particle size of 0.2 to 0.5 mm.

The yield of polyethylene is 2.38 kg per 1 g of vanadium. The rate of polymerization is 2700 g / g vanadium St. atm.

Example 15.

Preparation of the catalyst 0.903 g of a carrier having a particle size from 0.25 to 0.5 mm in the form of spherical granules, which is a copolymer of 60 percent by weight styrene and 40 percent by weight divinylbenzene with a specific Surface area of 260 m2 / g and a pore volume of 1.5 cm3 / g is analogous to that described in Example 11 and treated with vanadium chloride vapors in a weight of 1.01 g. The catalyst obtained is vacuumed at a Temperature of 8000. According to the results of the analysis, the content of vanadium chloride is 47 percent by weight and that of carrier 53 percent by weight. The catalyst provides spherical granules.

Polymerization of ethylene 0.047 g of one particle size catalyst of 0.25 up to 0.5 mm, 0.036 g of Al (iso-C4H9) 3, brings 50 ml of n-heptane one into a reactor with a stirrer. Ethylene is introduced at a temperature of 80 ° C and carries out the polymerization at a constant monomer pressure of 223 Torr. After 6 hours of reaction time; 0.082 g of polyethylene with a particle size is obtained from 0.5 to 2 mm in the form of spherical granules. The yield of polymer is 0.012 kg per 1 g of vanadium. The rate of polymerization is 6.6 g / g vanadium St. atm.

Example 16.

Polymerization of butene 0.02 g of catalyst, obtained according to the example 15, with a particle size of (), 25 to 0.5 mm, 0.042 g of triisobutyl aluminum and 17 ml of n-heptane are introduced into a dilatometer with a stirrer and 0.47 g is introduced liquid α-butene to. The dilatometer is thermostated at one temperature of 5000. After a reaction time of 4 hours, 0.45 g of polybutene iiiite is obtained; one Particle size from 1.5 to 2 mm in the form of spherical granules. The yield of polymer is 0.45 kg per 1 g of vanadium. The rate of polymerization is 41 g / g vanadium St.

Example 17.

Polymerization of ethylene 0.0188 g of catalyst, obtained according to the example 11, with a particle size of () .001 to 0.03 mm, 0.011 g of 'L'riisobutylaluminum and 300 ml of n-heptane are introduced into a reactor with a stirrer. At one temperature of 80 ° C leads; One to tind ethylene leads to the polymerization at a constant Ethylene pressure of 223 Torr. After a reaction time of 25 hours, 39 g of polyethylene are obtained. The yield of polymer is 20.4 kg per 1 g of vanadium. The rate of polymerization is 2780 g / g Vanadium St. atm.

Example 18.

Polymerization of 4-methyl-1-pentene, 0.05 g of catalyst, was obtained according to Example 5, one brings into a dry AmL) u.Lle, gives 0.7 g (C2H5) 2AlCl and 12.5 g of 4-methyl-1-pentene. The ampoule is sealed and placed in a thermostat introduced at a temperature of 500C. Obtained after a reaction time of 3.5 hours 0.2 g of poly-4-methyl-1-pentene. The yield of polymer per 1 g of titanium is 1.28 kg.

Example 19.

Mixed polymerization of ethylene and propylene G4 15 g catalyst, obtained according to Example 5, 0.5 g of (iso-C4H9) AlCl and 50 ml of n-heptane are brought into a hpparat with agitator. At a temperature of 700C one leads the reactor a mixture of propylene with ethylene.

After a reaction time of 4 hours, methyl alcohol is added. The received The copolymer is separated off, dried and weighed.

The yield of the copolymer from ethylene and propylene is 2.12 kg per 1 g of titanium.

Example 20.

Preparation of the catalyst 12,11 a support in the form of spherical Granules, which is a copolymer of 60 percent by weight styrene and 40 percent by weight Divinylbenzene with a specific surface area of 360 m2 / g and a pore volume of 1.42 cm3 / g is treated with titanium chloride vapors analogously to example 9. The titanium chloride content of the catalyst obtained is 48.5 percent by weight. The catalyst is spherical granules.

Dimerization of ethylene 0.0967 g catalyst, 0.417 g (C2H5) 2AlCl and brings 0.2 liters of benzene; into an autoclave with a stirrer.

The dimerization is at a temperature of 800C at a constant Ethylene pressure of 25 -at overpressure carried out. After a reaction time of 2 hours there ile-ethyl alcohol is added to the reaction medium. The products obtained are separated off and identified. The yield of iithylenediners is 32 g, of which 97 percent is by weight 1-butene and 3 percent by weight cis-2-butene.

Example 21.

Preparation of the catalyst 1.08 g of a support in the form of spherical granite lien, which is a copolymer of 50 percent by weight styrene, 20 percent by weight methyl methacrylate and 30 percent by weight divinylbenzene with a represents a specific surface of 197 m² / g and a pore volume of 0.8 cm³ / g, treated analogously with vapors of 0.14 g of titanium chloride and 0.06 g of (C2H5) 2AlCl to example 1.

The catalyst obtained contains 2.5 percent by weight of titanium chloride and represents spherical granules.

Dimerization of ethylene 0.116 g catalyst, 0.41? g (C2H5) AlCl2 and 0.2 liters of benzene are placed in an egg. iien an autoclave with a stirrer.

The dimerization becomes r> el. a temperature of 20 ° C and a Ethylene pressure of 25 atm overpressure carried out for 2 hours.

The yield of 1-butene is 19 g, which is 40 percent by weight of the Ethylene conversion.

Example 22.

Preparation of the catalyst aiysators The catalyst is analogous to the example 9 prepares.

A copolymer of 70 percent by weight is used as the carrier Styrene with 30 percent by weight methyl methacrylate with a specific surface area of 30 m2 / g and a pore volume of 0.9 c cm³ / g, which granules are more arbitrary Represents shape. J) The content of titanium chloride is 5.6 percent by weight. I) no Catalyst represents granules arbitrary shape represents dimerization of ethylene The dimerization is carried out analogously to Example 20. After 2 hours Reaction time, 9.8 g of polyethylene and 533 g of butenes are obtained with the following composition: 1-butene 63.8 percent by weight; ' cis-2-butene 21.7 counter percent, trans-2-butene 14.5 Weight percent. The yield of butenes is 300 kg to 1 g of titanium.

Example 23.

Preparation of the catalyst 7.4 g of a carrier in the form of arbitrary designed granules containing a copolymer of 40 percent by weight styrene 60 percent by weight divinylbenzene with a specific surface area of 360 m2 / g and a pore volume of 1.42 cm3 / g is placed in a flask and treated with 6 g (C2H5) 2AlCl. Mix 0.4 g of the treated rArager with 0.8 g of catalyst, obtained according to Example 9. The mixture is kept for 48 Hours at room temperature and then vacuumed to 2. 10 2 Torr.

The titanium chloride content of the catalyst obtained is 38.7 Weight percent. The catalyst represents granules of arbitrary shape.

Oligomerization on propylene 0.75 g catalyst, 1.4 g (C2H5) 2AlCl and 400 g of propylene are introduced into an autoclave with a stirrer. The Proess will performed at a temperature of? OoO. After a reaction time of 4 hours; 14 g of propylene oligomers.

Example 24.

Preparation of the catalyst 4 g of a carrier with; a particle size from 0.2 to 0.7 mm in the form of spherical granules, which is a copolymer of 50 percent by weight styrene, 20 percent by weight 4-vinylpyridine and 30 percent by weight technical divinylbenzene with a specific surface area of 176 m2 / g and one Pore volume of 1.2 cm3 / g is treated with 0.8 g of Tftanchiorid and 25 g (C2H5) 2AlCl analogous to example 1.

The titanium chloride content of the catalyst obtained is 6 Weight percent. The catalyst is spherical granules.

Polymerization of propylene 0.4 g catalyst, 0.2 g (C2H5) 3Al and 130 g of propylene are introduced into an autoclave with a stirrer. The process will carried out at a temperature voli 70 ° C for 2 hours. The yield of polypropylene is 33 g. The catalyst is spherical granules 1 to 4 mm in size.

Example 25.

Coverage of the catalyst 3.5 g of a particle size carrier of 0.035 up to 0.08 mm in the form of spherical granules, the a copolymer of 70 weight percent styrene and 30 weight percent divinylbenzene with a specific surface of 700 m2 / g and a pore volume of 0.3 cm3 / g is treated with 0.37 g of titanium chloride and 0.15 g of (C2H5) 2AlCl analogously to Example 1. The catalyst obtained. contains 7 weight percent titanium chloride and represents; Spherical granules 0.035 to 0.08 mm in size.

Oligomerization of propylene 0.14 g catalyst, 0.21 g (C2H5) 2AlCl and 130 g of PWolylene are introduced into an autoclave with a stirrer.

The oligomerization is carried out at a temperature of 7000 for 2 hours carried out. The yield of liquid propylene oligomers is 5 g.

Example 26.

Preparation of the catalyst 0.26 g of a support in the form of spherical Granules, which is a copolymer of 70 percent by weight styrene and 30 percent by weight Divinylbenzene with a specific surface area of 26 () m? / G and a pore volume of 1.5 cm³ / g is maintained in vacuo for 4 hours at a temperature of 80 ° C, cools to room temperature and treated with vanadium chloride vapors. The catalyst obtained is vacuumed to 10-3 Torr at a temperature of 8000. The vanadium chloride content of the catalyst obtained amounts to 31.1 percent by weight. The catalyst is spherical granules.

Polymerization of α-butene 0.02 g catalyst, 0.042 g triisobutylaluminum, 17 ml of n-heptane and 0.47 g of liquid g-butene are placed in a stirrer Dilatometer one. jMan thermostats at a temperature of 500C. After 4 hours Reaction time, 0.45 g of poly-α-butene is obtained, which, based on 1 g of vanadium, 225 g.

Example 27.

Preparation of the catalyst The catalyst is prepared analogously Example 26.

A copolymer of 40 percent by weight is used as the carrier Styrene and 60 percent by weight divinylbenzene with a specific surface area of 500 m2 / g and a pore volume of 2.8 cm3 / g with a particle size of 0.035 up to 0.08 mm in the form of spherical granules. The content of the catalyst obtained of vanadium chloride is 10% by weight. The catalyst represents spherical Granules.

Polymerization of propylene 0.303 g catalyst, 0.05 g (iso-C4Hg) 3Al, 50 ml of n-heptane are introduced into a reactor with a stirrer.

Propylene is fed in at a temperature of 600C and leads carried out the polymerization at a constant propylene pressure of 470 torr. The polymerization is carried out for 6 hours. The yield of polypropylene is 1.46 g.

The polypropylene has a particle size of 0.15 to 0.35 mm and represents spherical granules. The rate of polymerization of propylene is 40 g / g vanadium St. atm.

Claims (11)

CATALYST FOR DIMERIZATION, OLIGOMERIZATION, MIXED POLYMERIZATION AND POLYMERIZATION OF VI-NYLMONOMERS Claims 1. Catalyst for dimerization, Oligomerization, interpolymerization and polymerization of vinyl monomers, the from an active phase, a compound of a transition metal of groups IV - V of the periodic table, applied to a polymeric carrier, and a cocatalyst, an organoaluminum compound, there is a -d u r c h e k e n n z e i c h n e t that this polymeric carrier is a macroporous copolymer of Vinyl monomer and divinyl monomer with a specific surface area of 30 to 700 m² / g contains. 2e catalyst according to claim 1, d a d u r c h g e -k e it is noted that it contains a carrier having a pore volume of 0.3 up to 2.8 cm3 / g. 3. Catalyst according to claim 1 and 2, d a d u r c h g e k e n n z E i c h n e t that it is a copolymer of styrene and divinylbenzene as a carrier contains. 4. Catalyst according to claim 1 and 2, d a d u r c h g e k e n n z e i c h n e t that it is a copolymer of styrene and diisopropenyibenzene as a carrier contains. 5. Catalyst according to claim 1 and 2, d a d u r c h g e k e n n z e i c h n e t that it is a copolymer of styrene and divinylbenzene as a carrier and contains methyl methacrylate. 6. Catalyst according to claim 1 and 2, d a d u r c h g e k e n n z e i c h n e t that it is a copolymer of styrene and ethyldivinylbenzene as the carrier and vinyl pyridine. 7. Catalyst according to claim 1 to 6, d a d u r c h g e k e n n z it is certain that it has a particle size of 0.001 to 1 mm. 8. Catalyst according to claim 1 to 7, d a d u r c h g e k e n n z it is clear that it represents granules. 9. Catalyst according to claim 1 to 8, d a d u r c h g e -k e n n z e i n e t that he is the active phase of a connection of titanium or contains vanadium. 10. Catalyst according to claim 1 to 9, d a d u r c h g e -k e n n notices that it is a compound of titanium or vanadium chlorides of the same contains. 11. Catalyst according to claim 1 to 10, d a d u r c h g e k e n n indicate that it contains the active phase in an amount of 1 to 60% by weight.