WO2000078829A1

WO2000078829A1 - A process for producing polystyrene with predominantly syndiotactic configuration

Info

Publication number: WO2000078829A1
Application number: PCT/CZ2000/000046
Authority: WO
Inventors: Pavel ŠINDELÁŘ; Lenka FRÖHLICHOVÁ; Vojtech Varga; Alexander Pleska; Dušan KONEČNÝ
Original assignee: Kaučuk, A.S.; Unipetrol, A.S.
Priority date: 1999-06-16
Filing date: 2000-06-16
Publication date: 2000-12-28
Also published as: DE10084695T1; CZ291246B6; CZ9902154A3

Abstract

A process for producing of polystyrene with predominantly syndiotactic structure characterized by using a catalytic system consisting of a specific organo-magnesium compound and commonly known components and also characterized by the interaction of the components of the catalytic system in an aliphatic hydrocarbon solvent in the absence of styrene monomer in the specified order. Conversion of the monomer of 68% was reached and polymer with high syndiotacticity (96%) together with the melting point of 267°C and the Mw=236,000 was obtained.

Description

A process for producing polystyrene with predominantly syndiotactic configuration.

The sphere of the technology

The scope of this invention is the method of production of polystyrenes where the syndiotactic configuration of the polymer chain is predominant. This invention is particularly suitable for production of highly crystalline polymers on the base of styrene or its derivatives. The efficiency of formation of the syndiotactic polymer is high.

The contemporary state of the technology

The production of polystyrene through the radical polymerization leads to formation of polymer having the atactic configuration of the polymer chain. This type of polymer is through injection molding, extrusion, blow molding and other treatment techniques made into products having their use in households, in packing technology, in consumer electronics etc.

The cardinal disadvantage of the styrene polymers with atactic configuration of the polymer chains is their low resistance towards chemicals and high temperature.

These disadvantages are eliminated if the process of polymerization is carried out so that the rising polymer chain has predominantly syndiotactic configuration.

Polymers on the base of styrene or their derivatives with predominantly syndiotactic configuration of the polymer chain can be prepared by means of the use of catalytic systems comprising a) compounds of titanium, and b) alkylalumoxane. The use of two-component catalytic systems for the polymerization of the styrene is for instance specified in the following patents: EP 0 224 097 Al, EP 0 271 875 A2, EP 0 328 975 A2, EP 0 210 615 A2, EP 0440 014 A2, EP 0 328 975 A2, EP 0275 943 A2.

The use of catalytic systems on the base of

or CpTiCl₃ in combination with methylalumoxane is described in the patent EP 0224 097 Al. The catalytic system, which rises through interaction of the Ti-component and the MAO in the presence of aliphatic or aromatic solvent, reaches the rate of Al/Ti = 800 and styrene/Ti = 3.16 . 10⁴ and at the temperature of 20°C the activity from 3.7 to 8.3 kgps/gτj.h. The activity of these systems depends on the number of atoms of C in the RO- group and the ratio of RO and Cl ligands in the compound of the titanium. The replacement of the titanium compound of the type of (RO^Ti -_t-_y by the compound of CpTiCl₃ and the rising of the ration of Al/Ti and styrene/Ti led to substantial increase of activity of the catalytic system to the value of 24.8 kgps/gτi-h as well as the conversion of the monomer, which reached almost 15%.

The European patent EP 0 271 875 A2 describes the production of the syndiotactic polystyrene (s-PS) through catalytic system comprising of the compound of transition metal (Ti, V, Zr) and the MAO. The authors of the patent rearranged the procedure of production of s-PS in the way that the components of the catalyst had been given enough time to mutual interaction before styrene was added in the system. Further change compared to the patent EP 0224 097 Al is that the temperature of the reaction mixture was raised very slowly from 20°C to the temperature of polymerization, which is 50°C. The arrangements of the procedure of production of the s-PS showed mainly in the increase of conversion of the monomer, which for the system of (EtO)₄Ti - MAO reached 60%. The activity of this catalyst reached the value of 0.84 kgps/gτi.h with the ratio of Al/Ti = 94 and styrene/Ti = 2780.

The European patent No. 0 328 975 A2 specifies the influence of the technologic parameters such as - the shape of the reactor, the type of the agitator and the speed of stirring - on the yield of the syndiotactic polymer. The authors of the patent used (EtO)₄Ti - MAO as the catalyst to the polymerization of the styrene at the ratios of Al/Ti from 100 to 770 and the styrene/Ti from 1.94.10⁴ to 1.93.10⁵. The polymerization was carried out only in the medium of the styrene, that is without any solvent, in reactors of the volume of 2L, 5L and 10L at the temperature of 50° and 70°C. The lower ratios of Al/Ti and styrene/Ti as well as the lower temperature is applicable in reactors of the volume of 2L and 5L. The higher values are applicable for reactors of the volume of 10L. The examples presented in the patent show that with the use of a suitable type of the agitator and the higher ratios of both the Al/Ti and the styrene/Ti it is possible to reach the high activities of 131.4 kgps/gjj.h even with these simple catalysts. However, for achieving these high activities and the appropriate morphology of particles of the polymer it is necessary to provide the ends of the agitator by scrapers, which trace the inner wall of the reactor.

For the catalytic systems on the base of the compounds of CpTiCl₃ or IndTiC for achieving these high activities it is usually necessary to use a higher ratio of the Al/Ti (see the patent example in EP 0 224 097 A 1 where Al/Ti = 1000 or in the following issues: N. Ishihara et al., Macromolecules, (1996), 19, 2464 - 2465, J.C.W. Chien and Z. Salajka, J. Polym. ScL, Part A: Polym. Chem. (1991), 29, 1253 - 1263, P. Foster, J.C.W.Chien and M. D. Rausch, Organometallics, (1996), 15, 2404 - 2409, where the value of Al Ti vary between 2000 and 4000). In the patents EP 0 389 981 A2 and EP 0 390 000 A2 a procedure is specified where part of the expensive MAO is replaced by adding the tri-isobutylaluminium (TIBA) or the di- isobutylalui-iimum hydride (DIBAH). When the ratio of all the organo-aluminium compounds to the Ti-compound Al/Ti = 400 and the styrene/Ti = 1.74 . 10⁶, with the system of Cp*Ti(MeO) - MAO + TIBA the activity of 98.7 kgps/gτi-h reached and the conversion of the monomer varied within the range of 55 and 70%.

The use of inorganic compounds of magnesium or organo-magnesium compounds as a farther component of the catalytic system is described in EP 0 291 536 BI, EP 0 659 774 A2, EP 0659 775 A2, EP 0 707013 Al, EP 0 739906 Al.

EP 0 291 536 Bl describes preparation of the catalytic system with the use of a carrier system; the compound of titanium is bonded on the compound of magnesium of the type of MgCl₂, Mg(OR)Cl, Mg(OR)₂, Mg(OH)Cl, Mg(OH)₂ or Mg(OCOR)₂. By anchoring of the compounds of titanium - TiCU or Ti(i-PrO)₄ - on surface of the carrier material mainly the effect of reduction of the index of syndiotacticity was reached. During the process of polymerization with this catalyst - Al Ti ~ 50 - 1000 and at the temperature of 50°C - conversion of the monomer of about 10% is reached. Besides the s-PS the polymer contains a variable quantity of the i-PS; the ratio of the respective forms of PS depends on the ratio of Al/Ti.

The authors of the patent EP 0 659 774 A2 describe the preparation of the s-PS as follows. The catalytic system consists of three components A) a compound of titanium, B) a compound able to a) participate at reaction with Ti- compound making a ionic couple or b) containing the group of Al-O- (e.g. MAO) and C) an alkylating agent e.g. TIBA. This catalytic system after its preparation is put in contact with a monomer containing indene in the amount of up to 50ppm. As the alkylating agents the following types of compounds are quoted: a) organo-aluminium having the general formula of R_xAl(OR')yQ₃-_x-_y, R₂Mg or R2Z-1, at the same time for all compounds R is defined as an hydrocarbon residue containing 1 to 8 atoms of carbon. In the patent EP 0 659 775 A2 the preparation of the catalyst as well as its composition is equal as in the patent EP 0 659 774 A2. The use of H₂ as an agent regulating the molecular weight of the polymer is newly subject to the patent.

The patent EP 0 707 013 Al concerns the preparation of the s-PS by means of a catalytic system on the base of a Ti-compound containing substituted indenyl ligand as a π-bonded ligand. The compound of the titanium is alternatively activated by a) mixture of a compound of the boron and the agent of alkylation or b) by the alkylalumoxane. On the patent as another component of the catalyst some organo-metal compounds of Mg or Zn, which are not generally defined, may be used.

The high activities of the catalytic system in the way they are shown in the patent examples or in the quoted publications are related only to the content of the Ti-component in the catalyst and the organo-aluminum component is not taken into consideration, although there is 2 to 3 times higher content of this component in the catalytic system. In view of the fact that the org- o-aluminum component is not completely removed during the process of washing the polymer in methanol acidified by the HC1 or other acid, in the ashes one can find up to 1500 ppm of Al, and it is necessary to remove it additionally as can be seen in the patents EP 497207 A2, EP 566068 and JP 03059012 A2. Besides increasing the cost of production of the polymer the introduction of the process of washing the catalyst residue, mainly the Al, from the polymer poses rising of the possibility of unwanted impact on characters of the polymer, such as the decrease of the molecular weight. We assume solution of this problem in more effective way of activation of the Ti-component of the catalytic system.

Substance of the invention

The scope of this invention is to suggest a procedure of polymerization of the styrene or/and its derivatives with the use of catalytic systems on the base of compounds of the titanium and the MAO. The aim of the use of this procedure is achieving the increase of the activity of catalysts, the increase of the rate of syndiotactic configuration of the polymer chain, and the molecular weight of the polymer as well as reduction of making the deposits on the surface of walls of the polymerization reactor and the agitator. Therefore a new procedure of synthesis of the catalytic system has been developed.

The substance of this invention is stating a suggestion of the new procedure of production of the catalytic system that would consist in the fact that besides the commonly known components as a part of the system a specific organo-magnesium compound is used. This compound in a distinct way increases yield of the syndiotactic polymer during the process of polymerization of the styrene. At the same time it also consists in the interaction of the components of the catalytic system in aliphatic solvent - in the absence of the styrene monomer- and the respective components of the system react in the following order: a) organo-aluminium compound containing in its molecule at least one atom of oxygen bonded either in the form of >Al-O- group or in the form of >Al-O-Al< group, the linear chains are represented by the general formula (I):

w ere R s an a yl group containing 1 to 8 atoms o car on and n shows the rate of polymerization and varies from 2 to 50,

and the cyclic-arranged molecules contain the repeated structure of the general formula (II):

b) a compound of the titanium with the general formulas (III) and (IN): general formula (III):

general formula (IV):

(TV), where the respective substituents R³, R⁴, R⁵ and R⁶ represent the atom of hydrogen, the halogen, the alkyl group containing 1 to 20 atoms of carbon, alkoxy group having 1 to 20 atoms of carbon, the aryl group containing 1 to 20 atoms of carbon, the alkylaryl or arylalkyl group containing 1 to 20 atoms of carbon, the cyclopentadienyl group (Cp) or the Cp group substituted by at least one alkyl group containing 1 to 6 atoms of carbon, an atom of halogen, a, b, c are integers from 0 to 4, and d and e are integers from 0 to 3, and c) an organo-magnesium compound of the general formula (V):

R⁷MgOR⁸ (V), where R⁷ and R⁸ are equal or different alkyl groups containing 1 to 10 atoms of carbon and having linear, branched or cyclic structure. These compounds react with one another in the presence of aliphatic or aromatic solvent at molar ratios of Al/Ti within the range of 1 to 500, most effectively from 5 to 250 and the ratio of Mg/Ti within the range of 0.1 to 20, most effectively from 0.5 to 10.

In the advantageous procedure of preparation of the s-PS in accordance with the invention hereof the organo-aluminum compound contained in the component is a) alkylalumoxane - the preparation of which can be performed by one of the well-known methods e.g.: i) by procedure, in which the organo-aluminum compound is dissolved in an organic solvent and then it is brought in contact with water, ii) by procedure, in which the organo-aluminum compound is in contact with inorganic compound having the crystal water (e.g. CuSO₄ . 5 H₂O) or inorganic or organic sorbent containing adsorbed water or Hi) by procedure, in which organic compounds containing oxygen and the compound of R₃A1 react with each other. The intermediate product of this reaction then is transformed into the required product (Proceedings of the symposium Metallocenes Europe 98,: G. M.Smith, page 149).

In the advantageous procedure in accordance with the patent hereof the component is c) the product of reaction between an dialkyl-magnesium compound and the alcohol R⁷OH, which arises from their mutual reaction at molar ration of both ingredients of 1 : 1.

The advantage of the procedure of synthesis of the catalyst by the invention hereof is that the absence of aromatic compound (styrene monomer or toluene as the solvent) facilitates mutual interaction of the Ti-compound and the alkylating agents. Therefore it is possible to activate the Ti-compound with substantially lower surplus of both the component a) and the component c) reaching high yield of the s-PS at the same time. The procedure of synthesis of the catalyst by the invention hereof then leads to substantial reduction of the content of ash in the polymer, to the increase of the molecular weight, to the increase of the melting point of the polymer and the syndiotacticity of the polymer. Further advantage of the procedure hereof is the substantial improvement of the process of polymerization: The catalytic system in the aliphatic hydrocarbon solvent is nearly insoluble and that is why from the very beginning the polymerization runs in the mode of a suspension process. This is a very substantial change compared to the polymerization with homogeneous catalytic systems where after reaching certain stage of conversion of the styrene (20-30%) the whole mixture in reaction turns in gel and further process of polymerization depends on the perfect stirring up the charge. For this reason all the polymerization reactors working with homogeneous catalysts must be equipped with special types of agitators. Through utilizing the procedures specified in this invention the critical stage is avoided - the phase of gel development - and therefore agitators of simplier construction can be used. Further advantage of the mentioned procedure is the fact that with the choice of aliphatic hydrocarbon solvent with suitable boiling point it is possible to achieve more effective regulation of the temperature of the polymer mixture. The resulting polymer has better moφhology of particles, which will reflect in better mixing of the polymer mixture as well as during the operations subsequent to termination of the polymerization (washing, filtering e.t.c).

Detailed description of the patent

The catalytic system, which in accordance with the patent hereof is used for preparation of syndiotactic polymer, contains, as its main components, the above-specified compound of the titanium, the magnesium and the alkylalumoxane. This compound can either be a) a product of reaction of organo-aluminium compound, with the general formula of R⁹ ₃A1, with the agent of condensation, which usually is water or b) with an organic compound containing oxygen. For preparation of the product of reaction - the alkylalumoxane - various organo-aluminium compounds can be used. Those, in which R⁹ represents the alkyl group containing 1 to 8 atoms of carbon, are preferred. The alkylalumoxane - component a) in accordance with this invention is used for preparation of the catalytic system either by itself or in mixture with organo-aluminium compound of the general formula of R¹⁰ ₃A1 or Rⁿ ₂AJX, where R¹⁰ and R¹¹ are the alkyl groups containing 1 to 8 atoms of carbon. These alkyl groups can be equal or different and the X is F, Cl, Br or I. The ratio of components of the catalytic system can't be pre-determined explicitly as it changes in dependence on the type of the respective compounds used for preparation of the catalytic system as well as the type of the styrene monomer in the initial mixture to polymerization. Usually the respective components of the catalytic system are used in such a ratio that the molar ratio between the alkylalumoxane and the Ti-component formulated by the ratio of Al/Ti ranges from 1 to 500, most effectively from 5 to 250 and the ratio of the organo-magnesium compound component c) to the Ti-component Mg/Ti ranges from 0.1 to 20, most effectively from 0.5 to 10. S

The interaction of the respective components leading to the rise of the catalytic system is according to the invention hereof most effective at temperatures within the range from 10 to 90°C in the presence of a solvent. This solvent may either be a saturated aliphatic hydrocarbon (e.g. butane, i-butane, pentane, i-pentane, hexane, i-hexane, etc.) or an alicyclic hydrocarbon such as e.g. cyclohexane. The method of dosing contributes to reaching the high activity of the catalyst too. During this dosing some time for mutual interaction of the respective components is left before adding further component into the reaction mixture. The times of interaction of the components varies from 1 minute to 60 minutes. The resulting product of the reaction can be either directly used to starting the polymerization of the styrene or it can be removed from aliphatic solvent and thus we obtain the catalyst in the form of loose powder.

The polymerization of styrene or co-polymerization of styrene with 1-alkene aromatic co- monomers can be made by the invention hereof in a block (in the presence of the monomer itself) or in the mixture of monomer with a solvent. The co-monomer can be a compound of the general formula of (VI): CH₂ = CH - R², where R² is an aryl group containing 6 to 20 atoms of carbon, the aryl group substituted by alkyl or alkene residue or halogen with the total number of atoms of carbon from 6 to 30. The cycloaliphatic group is substituted by alkyl residue or the halogen with total number of atoms of carbon from 6 to 30. The molecular weight of the polymer can be regulated by means of techniques commonly used in polymerization with Ziegler-Natta catalysts, for instance by adding the hydrogen.

The temperature of polymerization is not critical and usually ranges from 0° to 140°C, most efficiently from 20° to 100°C.

The characters of crystalline polymers on the base of styrene or the derivatives of the styrene with predominantly syndiotactic structure stated in the following examples were assessed by the methods as follows: a) the molecular weight: the values of the number-average and the weight-average (Mn and Mw) molecular weights were assessed by means of gel permeation chromatography with the apparatus Waters 150 C working at the temperature of 135°C in the presence of 1,2,3-trichlorbenzene. The calibration of the apparatus was adjusted by means of standard samples of atactic PS of the known molecular weight. b) the melting point of the polymer: was assessed by means of DSC analysis with the apparatus Perkin-Elmer DSC-7. Before the measurement itself the sample of the polymer was thermally conditioned in the measurement cell of the DSC apparatus and the melting point was afterwards assessed as the temperature equal to the maximum of the endothermic peak at the speed of heating of 15K min. c) the ratio of the syndiotactic polymer: was assessed from the reduction of the weight of the polymer after extraction of the sample in boiling 2-butanone for the period of 24 hours.

The following examples illustrate the process of preparation of the s-PS without any limitation to the invention.

Example 1 : a) preparation of the organo-magnesium compound of the ROMgR

The alkylalkoxymagnesium compound was prepared in glass vessel of the volume of 100ml equipped with teflone cap and a magnetic agitator in inert atmosphere of ultra-pure nitrogen. The interaction of the R'R⁸Mg compound with the alcohol R⁷OH was carried out in the presence of heptane clear of any impurity. Under intense stirring of the solution of butyloctylmagnesium (6.62 mM) the solution of BuOH (6.62 mM) was added in drops into the vessel at laboratory temperature.

b) polymerization of the styrene

Into the carefully cleaned reactor (the volume of 70 ml) under the stream of the pure nitrogen 30 ml of dry heptane, 1.45 mM of metylalumoxane MAO (related to the content of atoms of Al) were batched and then 5.8 μM of Ti(EtO) was added and after 11 minutes of interaction organo-magnesium compound was batched - the compound was prepared according to the procedure stated in la) in the quantity of 18 μM. After 6 minutes of interaction 10ml (87.1mM) of styrene clear of any impurity was added and the polymerization mixture was then mixed hard for the period of 5 minutes first at the temperature of 25 °C. Then during 5 minutes the temperature was increased to the temperature of the polymerization to the value of 50°C and the process of polymerization at this temperature lasted for 30 minutes. By adding 10ml of methylalcohol (MeOH) acidified by hydrochloric acid the polymerization was terminated. The obtained polymer was washed by pure MeOH. After its drying 1.089g of polystyrene was gained. This represents conversion of the monomer of 12%.

The polymer gained was extracted by 2-butanone in the Soxhlet's extractor. The residue of the polymer after the extraction was 95.4% of the weight of the initial raw polystyrene. By means of the GPC analysis the weight-average molecular weight of Mw 425 070, and the number-average molecular weight of Mn 198 067 were assessed for this polymer. By means of the DSC analysis the melting point of 268.5°C was assessed. Examples 1 to 8 and the Comparative Examples 1 and 7:

The method of preparation of the syndiotactic polystyrene is equal to Example 1 with the exception of the compounds used, their mutual ratios and the conditions of polymerization. These data are shown in Table 1. The yield of the s-PS together with the measured qualities of the polymer are shown in Table 1 , too.

Example 9

Into the reactor of the inner volume of 100L (I itr) under the stream of an inert gas 23.1kg of impurity clear hexane, 0.98M of metylalumoxane (counted for the content of the Al), 5.6mM of the Ti-component (mixture 2:1 of Ti(i-PrO)₄ + CpTiCl₃) were batched. The mixture was stirred for the period of 11 minutes at the temperature of 23°C. Then 14mM of an organo-magnesium compound prepared in accordance with the Example la was batched into the reactor. After 10 minutes 16.65kg of impurity clear styrene was batched. The reaction mixture was left at this temperature for 10 minutes. Then the polymerization reactor was heated to up to 50°C and for 2 hours the polymerization of styrene ran at this temperature. Adding the mixture of methanol and the phosphoric acid deactivated the polymerization mixture. The gained polymer was then washed properly by pure methanol and after its drying it was weighed. The weight of the gained polymer (10.65kg) represents conversion of the monomer of 64%, with the molecular weight Mn = 208 490 and Mw = 436 270, the melting point of 267.6°C and with the ratio of the syndiotactic polymer representing 95.8%.

Example 10:

The method of preparation of the syndiotactic polystyrene is equal to the Example 7 with the difference that instead of the styrene the p-metylstyrene was batched into the reactor. The yield of 2.94g represented conversion of the monomer of 65%, the polymer gained was characterized by Mn = 7 500, Mw = 54 000 and the index of syndiotacticity was 61%, the melting point of 172°C.

Example 11 :

The method of preparation of the syndiotactic polystyrene is equal as in the Example 7 with the difference that instead of styrene the p-chlorstyrene was batched into the reactor. The yield of 0.398g represented conversion of the monomer of 8.2%, the gained polymer was characterized by Mn = 5 800, Mw = 45 000 and the index of syndiotacticity was 92%, the melting point of 292°C.

Table 1: The influence of composition of the catalytic system to the activity of the catalyst and to the qualities of the syndiotactic polystyrene

(s-PS), [Ti] = 5.8 μM,

Al/Ti = 250, Mg/Ti = 3.2 (^a) Al/Ti = 125, Mg/Ti = 1.7), V _totaι = 35 ml, T = 50°C.

Example Ti-compound RO_qMgR₂._q Styrene Yield Conversion Activity Mn D T₂ SN. type rje (ml) (g)^' (Mw/Mn) °C

HOMOGENEOUS CATALYST

Comparative

Example 1 Ti(EtO)₄ ROMgR 10 0.92 10 6 635 53 540 2.12 265.9 95.6

Example 1 Ti(EtO)₄ ROMgR 10 1.08 12 7 765 198 067 2.15 268.5 95.4

Example 2 Ti(EtO)₄ - 10 0.49 5.5 3 592 46 270 2.55 263.5 94.4

Example 3 ^a) Ti(EtO)₄ ROMgR 10 0.57 6.3 4 132 165 800 2.45 265.7 95.1

Example 4 Ti(EtO)₄ R'MgR² 10 0.69 7.1 4 629 47 570 3.5 256.8 85.4

Example 5 CpTiCl₃ ROMgR 10 1.79 39.5 12 876 105 000 2.23 257.9 93.0 to

Example 6 Cp*Ti(OMe)₃ ROMgR 5 1.34 29.7 9 675 375 547 2.06 269.3 96.2

HOMOGENEOUS CATALYST

Comparative

Example 6 Cp*Ti(OMe)₃ ROMgR 5 1.60 35.2 11 518 323 249 2.16 268.9 95.1

Example 7 CpTi(i- ROMgR 5 3.12 68.8 22 445 57 045 2.46 253.3 94.9 PrO)₂Cl HOMOGENEOUS CATALYST Comparative

Example 7 CpTiø- 5 3.05 67.4 21 967 57 262 2.24 255.6 95.8 PrO)₂Cl

Table 2: The influence of the type of the organo-magnesium compound to the qualities of the catalytic system, the conditions of the polymerization: Al/Ti = 250, Mg/Ti = 3.2, styrene = 10ml, T = 50°C

Example R,Mg(OR)2H, Yield Conversion Mn SN. type (g) (%) (%)

Example 1 ROMgR 1.08 12.0 198 067 95.4

Example 4 R'MgR² 0.69 7.1 43 724 85.4

Example 12 (RO)₂Mg 0.66 6.7 41 347 65.3

Claims

CLAIMS OF THE PATENT

1. A process for producing of polystyrene with predominantly syndiotactic structure characterized by using a catalytic system consisting of a specific organo-magnesium compound enhancing the degree of syndiotacticity and commonly known components and also characterized by the interaction of the components of the catalytic system in an aliphatic hydrocarbon solvent in the absence of styrene monomer in the following order:

a) an org-mo-aluj-r-inium compound, which in its molecule contains at least one atom of oxygen bonded either in the form of the >Al-O- group or in the form of the >Al-O-Al< group, linearly arranged chains are represented by the following general formula (I):

where the R¹ is an alkyl group containing 1 to 8 atoms of carbon and the n represents the stage of the polymerization and ranges from 2 to 50, and the cyclic-arranged molecules contain the repeating structure of the following general formula (II):

b) the compound of the titanium of the general formula as shown in (HI) and (IV):

the general formula (HI):

TiR³ _aR⁴ _bR⁵ _cR⁶ _{4 a+b+l3)} (III) or

the general formula (TV):

ON), where the respective substituents R³, R⁴, R⁵ and R⁶ represent an atom of the hydrogen, the halogen, an alkyl group containing 1 to 20 atoms of carbon, an alkoxy group having 1 to 20 atoms of carbon, an aryl group containing 1 to 20 atoms of carbon, the alkylaryl or an arylalkyl group containing 1 to 20 atoms of carbon, the cyclopentadienyl group (Cp) or the Cp group substituted by at least one alkyl group containing 1 to 6 atoms of carbon, an atom of the halogen; a, b, c are integers from 0 to 4, and d and e are integers from 0 to 3, and

c) an organo-magnesium compound of the general formula (V):

R⁷MgOR⁸ (V),

where the R⁷ and R⁸ are equal or different alkyl groups containing 1 to 10 atoms of carbon and having linear, branched or cyclic structure. These compounds react with one another in the presence of aliphatic hydrocarbon solvent at molar ratios of Al/Ti within the range from 1 to 500, most advantageously 5 to 250 and the ratio of Mg/Ti within the range from 0.1 to 20, most advantageously 0.5 to 10.

2. A process according to Claim 1 wherein the organo-aluminum compound in the component a) of the above-mentioned system is the alkylalumoxane - a compound, which in its molecule contains at least one atom of oxygen bonded either in the form of >Al-O- group or in the form of >Al-O-Al< group.

3. A process according to Claim 1 wherein the component c) of the above-mentioned system is a product of the reaction of the dialkyl-magnesium compound with alcohol (of the general formula of ROH) in the ratio of 1 : 1.

4. A process according to Claim 1 wherein the temperature of polymerization ranges between 0 and 140°C.

5. A process according to Claim 1 wherein the pre-polymerization at lower temperature is used before the polymerization.

6. A process according to Claim 1 wherein the catalyst in the form of a loose powder or suspension in aliphatic solvent is used for starting the process of polymerization of the styrene.

7. A process according to Claim 1 wherein the polymerization is carried out in the presence of the hydrogen and that besides the styrene 1-alkene aromatic co-monomer is present.