Homogeneous catalytic system for the synthesis of low molecular weight branched polyethylene and method for producing low molecular weight branched polyethylene

 

(57) Abstract:

The invention relates to the synthesis of low molecular weight branched polyethylene in the presence of efficient homogeneous catalytic systems based on metallocene or pseudometallic complexes IVC group, alyuminiiorganicheskikh compounds and perftoralkil borates. The invention relates also to a method for producing low molecular weight branched polyethylene. The aim of the invention is a process for the catalytic polymerization of ethylene with the formation of low molecular weight branched polyethylene with high efficiency, comparable to or greater than the activity systems with MAO as socializaton in the synthesis of high molecular weight polyethylene, as well as the development method of producing low molecular weight branched polyethylene. The inventive as the catalytic system used valkirye metallocene or pseudosatellite complexes IVC group, trialkylaluminium and perftoralkil borates. Controlled activity and properties of low molecular weight branched polyethylene synthesis is carried out by selection of the ligand metallocene complex and the conditions the performance of molekulyarnogo branched polyethylene used as adhesive additives, fuel additives and oils as lubricating and polishing materials, comonomers in the process of copolymerization of olefins to obtain the branched polyolefin of low density. 2 S. and 1 C.p. f-crystals, 1 table.

The invention relates to the synthesis of low molecular weight branched polyethylene, namely to highly homogeneous catalytic system based on metallocene or pseudometallic complexes IVB group, alyuminiiorganicheskikh compounds and perftoralkil borates, as well as to a method for producing low molecular weight branched polyethylene.

Similar in nature to catalytic systems proposed in the invention are cationic ORGANOMETALLIC complexes of transition metals with an active metal-carbon bond. Cationic complexes are formed under the action of strong Lisovich acids (polymethylsiloxane (MAO), perftoralkil Baranov and borates, carbonates, and so on) alkyl derivatives complexes by removal of one alkyl ligand. All of the above strong Lisovich acids on the original ORGANOMETALLIC complexes leads to the formation of electron is AI olefins.

Similar in purpose to the catalytic systems of the present invention are diimine complexes of Nickel and palladium with MAO as socialization, which are known as highly efficient catalysts in the synthesis of linear-olefins by oligomerization of ethylene (see, for example, U.S. Patent US 5811379, 1998 [1]; US Patent US 5880323, 1999 [2]; U.S. Patent US 5880241, 1999 [3]; U.S. Patent US 5891963, 1999 [4]).

Close on purpose, in the sense of obtaining a branched polyethylene, are the so-called complexes tense geometry (see, for example, European patent EP 0416815 A2, 1990 [5]; international patent application WO 91/04257 [6]), capable under the influence of MAO and perftoralkil Baranov and borates may lead to the formation of branched polyethylene in the presence of the olefin in the mixture of comonomers, and during homopolymerization ethylene.

Known for high-performance, homogeneous two-component catalytic system of Homo - and copolymerization of olefins based on metallocene complexes of group IVB in combination with MAO. The high activity of these systems provides MAO. Use alyuminiiorganicheskikh compounds (alkyl and chloralkali derivatives of aluminum) as activators of metallocene complexes IVB is on the transition metal by 3-4 orders of magnitude lower than under the action of MAO.

The main disadvantages of catalytic systems using MAO as socializaton are:

1. The need to use large molar relationship socialization/catalyst (Al/M= 1000-10000) for maximum activity of the catalytic system.

2. The high cost of MAO, which makes the relatively high cost of polyolefins obtained on these catalytic systems.

3. MAO is not a connection of a specific composition and structure. Reactivity MAO as socializaton is largely determined by the method of synthesis and, in addition, properties MAO change during storage solution that connection that identifies significant differences in the activity of the catalytic system and the properties of the polymer products obtained on different samples MAO ceteris paribus.

4. Large excess socializaton, providing the maximum activity of the metallocene complexes, require the removal of MAO from the final polymer product.

Also known homogeneous catalytic systems comparable or even exceeding the activity of metallocene complexes of activated Matov (see, for example, Sishta S., Hathorn R. M., T. J. Marks, J. Am.Chem.Soc., 114 (1992) 1112 [7]; Hlatky, G. G., Turner, H. W., R. R. Eckman, J. Am.Chem.Soc., 111 (1989) 2728 [8]; Yang X., Stern, C. L., Marks T., J. Am.Chem.Soc., 113 (1991) 3623 [9]; Chen Y.-X., C. L. Stern, T. J. Marks, J. Am.Chem.Soc., 119 (1997) 2582 [10]).

The main disadvantages of two-component catalytic systems based on dalkilic or dialling derivatives metallocenes and perftoralkil Baranov and borates is the high sensitivity of these systems to impurities moisture. No component in the system is able to react with impurities in water prior to the formation of active centers (as in the case of MAO or aluminum Akilov) creates certain difficulties in carrying out the polymerization process and its optimization. The need for a polymerization process when the concentration of the complex, by 2-3 orders of magnitude greater than the concentration of the complex using MAO as socializaton, creates the possibility of occurrence of side reactions involving neutral dalkilic metallocene complexes.

Close to the claimed are three-component homogeneous catalytic systems based on metallocenes of dichloride, aluminum trialkyls and perftoralkil Baranov and borates (see, for example, Chien, J. C. W., Song W., Rausch, M. D. , J. Polym.Sci. Part A: Polym.Chem., 32 (1994) 2387 [11]; Tsai, W.-M., Chie is the disadvantages of a three-component catalytic systems involving metallocene complex, trialkylamine and perftoralkil borates is the unpredictability of catalyzed reactions and properties of the resulting polymer products due to the poorly understood role of each component of these catalytic systems and reactions leading to the formation of active centers, as well as the possibility of occurrence of several side reactions leading to deactivation of the catalytic system.

Significant is also the fact that all of these catalytic systems under conditions ensuring high activity metallocene complexes lead to the formation of high molecular weight products in the synthesis of polyethylene. This also applies to the ternary catalytic systems on the basis of metallocenophanes, aluminiumrail and perftoralkil borates and demonstrates the data given in Examples 1,2,3. From the Examples it is seen that the molecular weight of the polyethylene produced in these systems by 2-3 orders of magnitude higher than the molecular weight of the polyethylene produced in the catalytic systems proposed in the invention. This also applies to complexes "tense" geometry and illustrated with data of Example 1. Moreover, the "tense" geometry when activated by MAO during homopolymer) chains, relatively small, in contrast to the claimed catalytic systems, and is 5.6 branches per 1000 carbon atoms of the chain polyethylene (Example 3). Branching increases when carrying out the polymerization of ethylene in the presence of olefin to 70/1000C in the presence of propylene and up (20-30)/1000C in the presence of butene-1 [6].

There are various catalytic systems for the synthesis of low molecular weight branched polyethylene and methods of obtaining low molecular weight branched polyethylene in the presence of a homogeneous catalytic systems [see, for example, encyclopedia of Polymers, Ed. Board: C. A. Kabanov and others, Moscow, Soviet encyclopedia, 1977, T. 3 N/I, S. 1004 and 1009 [14]; j. Kennedy, Cationic polymerization of olefins, Moscow, Mir, 1978, S. 57-74 [15]; P. Houwink, A. Staverman, Chemistry and technology of polymers, Leningrad, Chemistry, 1965, T. 1, S. 41 and 506 [16]; P. E. matkovskiy and others, polymer sciense ser. Connect., 17 (1975), 252 [17]).

The closest source of information for said catalytic system under item 1 is the source [17], in which for the synthesis of low molecular weight branched polyethylene using homogeneous catalytic system TiCl4+Al(C2H5)Cl2. The catalytic system active ~ 2.3 kg of low molecular weight (Mn= 102-189 (benzene); Mn= 260-1700 (ethyl chloride)), unbranched (benzene) or hyperbranched to ~ 300 CH3/1000C (ethyl chloride)) polyethylene. The disadvantages of this catalytic system is low activity, the formation of a branched low-molecular-weight polyethylene in the environment of chlorinated solvents is undesirable in industrial synthesis of polyolefins.

The difference between the proposed catalytic system from known is that the catalytic system is a three-component catalytic system, including additional Dulcinea derived metallocene or pseudometrizable complex IVB group and perftoralkil borate or borane.

The closest known solution for the way to obtain low molecular weight polyethylene under item 3 is the source [16], which describes a method of obtaining a low molecular weight branched polyethylene by catalytic polymerization of ethylene in the presence of a homogeneous catalytic system comprising trialkylaluminium.

The difference of the proposed method against known is that the use of three-component catalytic system, including additional Dili borane at a ratio of Zr/B 0.5 - 10.0 mol/mol and Al/Zr 10 to 1000 mol/mol and the method is carried out in a medium of an organic solvent at a temperature of 0-130oC and a pressure of 0.5 to 20.0 ATM.

The present invention is the creation of a fundamentally new three-component catalytic system, allowing the use of low concentrations of metallocene complex, active, comparable to or greater than the activity systems with MAO as socializaton in the polymerization of ethylene and can lead to the formation of low molecular weight branched polyethylene.

The problem is solved, we offer highly active homogeneous catalytic system and method of obtaining low molecular weight branched polyethylene.

The inventive catalyst system of the present invention includes three components. The first component is valkiry pseudomaturity or metallocene complex of the IVB group. The second component is trialkyl aluminum. The third component is perftoralkil Borat or perftoralkil borane.

The first component of the inventive catalyst system is nemotional (L2MAlk2or colophony (BrL2MAlk22Si<, Me2C<, Ph2C<, PhMeC<, etc ). In the cases examined by the catalytic action of the two complexes, Me2SiCp*NtBuZr(CH3)2(1Me) (Cp*= (Me4C5and Me2SiCp2Zr(CH3)2(2Me) (Cp = C5H4).

The second component of the catalytic system is trialkylaluminium, AlR3where R = Me, Et, Pr, iPr, Bu,tBuiBu, mainly AliBu3. Function trialkylamine is the equilibrium formation of heteronuclear complex metallocene (G Henrici-Olive, North Olive, Coordination and catalysis, Moscow, Mir, 1980, S. 259-266 [18]): L2MAlk2+ AlAlk3L2MAlk(Alk)...AlAlk3.

The third component of the catalytic system is kalinganire agent is an organic boron salt, perftoralkil boron or perftoralkil borates. In the examples, triphenylmethylenephosphorane, C(C6H5)3B(C6F5)4(3) and dimethylanilines consists in the formation of the cationic complex when interacting with heteronuclear complex Al-Zr (M Bochmann, Polymeric Materials Encyclopedia, CRC Press, 1996 [19]; M. Bochmann, J. Chem.Soc., Dalton Trans., 1996, 255 [20]).

Analysis of patent and scientific literature showed that the proposed catalytic system and method for producing low molecular weight branched polyethylene meet the criteria of "novelty" and "industrial applicability".

The use of such catalytic systems for the synthesis of polyolefins allows you to:

1. Conducting effective synthesis of low molecular weight branched polyethylene (Cnn>20) with a narrow molecular-mass characteristics and a high degree of branching ((10-100)/1000C).

2. The selection of the specific catalyst structure and reaction conditions can vary in a wide range of molecular weight of polymer product, the branching structure and the type of end groups.

3. To ensure the activity of the metallocene complexes greater than the activity of structurally - similar catalytic systems using MAO as socializaton at low concentrations metallocene.

4. Be used instead of MAO is much cheaper and available trialkylaluminium when the stoichiometric amount of the third component.

5. Substantially the polarization in a molar ratio of acetalization/catalyst=100-500. Thus, purification of the reaction medium from impurities, reduces the cost of the obtained polymer, eliminating the need for special cleaning of polymer from the remnants alyuminiiorganicheskikh connection.

6. Targeted synthesis of such low molecular weight branched polyethylene products effectively and economically to obtain materials that can be used, depending on their molecular weight and structure, as comonomers in the copolymerization processes and cooligomerization olefins, in particular for obtaining branched polyethylene as an adhesive additive, functionalityand fuel additives, lubricants, polishing agents, etc.

The method for the catalytic system by the interaction of the components set forth in the Examples below. The inventive catalytically active system for the synthesis of low molecular weight branched polyethylene is obtained by dissolving the components in the hydrocarbon or aromatic solvents, mainly in toluene, followed by their mixture and carrying out the reaction at 0-100oC, mostly in the 20-30oC. the Molar ratio of acetalization/catalyst: Al/M=10 is the monomer may vary from 0.5 to 50 bar, preferably 10-20 ATM. The polymerization process is conducted in a hydrocarbon and aromatic solvents, mainly in toluene. Synthesis of low molecular weight polyethylene with the use of the inventive catalyst system described in the Examples below. A method of obtaining a low-molecular-weight polyethylene with a controlled molecular weight, the type of end groups and branching set forth in the Examples. Usually, the effect of molecular weight, the type of end groups and branching is achieved by variation of the metallocene type complex type perftoralkil borate and the reaction conditions such as reaction temperature, monomer concentration, concentration trialkylamine and illustrated by Table data.

Thus, the analysis of the existing scientific-technical and patent literature showed that the claimed combination of signs for the first time allows you to achieve a positive effect of the described technical solution, which confirms the compliance of the claimed invention, the criteria of novelty and significant differences.

The invention is illustrated by the following examples. In the examples used connections: pseudosatellite complexes M (1Me); metallocene complexes Me2SiCp2ZrCl2(2Cl), Me2SiCp2ZrMe2(2Me); performancevery CPh3B(C6F5)4(3) and Me2HNPhB(C6F5)4(4).

Example 1 (for comparison, the claimed catalyst system with triple catalytic system comprising dichloride derivative metallocene, triisobutylaluminum and Borat (3), as well as to illustrate the role-linked substituent at the zirconium atom).

In pre-evacuated and filled with argon stainless steel autoclave with a volume of 200 ml, provided with a mechanical stirrer and a system input components of the catalytic system, place the pre-weighed sample of the complex 1Cl, (1.2 mg, 2.910-6mole), sealed in a glass ampoule. The autoclave is pumped at room temperature for 15 min, injected toluene (60 ml) and AliBu3(148 mg, 7.510-4mol). A special device crush the ampoule with the catalyst serves ethylene at a pressure slightly above atmospheric, and at room temperature conduct stirring for 10 minutes Then the autoclave is heated to a temperature of 70oC with simultaneous supply of ethylene to a pressure of 11.5 MPa. At the last stage specia-4mol/l). Introduction borate causes instant absorption of ethylene. The polymerization is carried out at constant pressure of the monomer in the autoclave, equal to 11.5 ATM. The reaction is stopped acidified with HCl in ethyl alcohol in 30 minutes After pressure relief of the reactor open and unload the polymer in a container with 150 ml of ethanol. The polymer is washed, filtered and dried at 60oC in the vacuum oven to a constant weight. The polymer yield 5.8 g Activity 350 kg PE/(mol Zr h ATM). Molecular weight 1827000 (data viscosity measurements of polymer solutions in decaline at 135oC). Linear unbranched polyethylene (IR data).

Example 2 (for comparison, the claimed catalyst system with triple catalytic system comprising dichloride derivative metallocene, triisobutylaluminum and Borat (3), as well as to illustrate the role-linked substituent at the zirconium atom).

The polymerization was carried out similarly to Example 1 with complex 2Cl. The addition of complex 2.0 mg (6.010-6mole). AliBu3595 mg (3.010-3mole). Borat (3), solution in toluene 5.5 mg (6.010-6mole). The reaction temperature 30oC. the Pressure of ethylene 11.5 ATM. The response time of 33 minutes, the polymer Yield 2.8 g Activity 81 kg PE/(mol Zr h ATM). Maderaspatensis polyethylene (IR data).

Example 3 (comparative to compare with activation of MAO and branching of the resulting polyethylene).

In pre-evacuated and filled with argon stainless steel autoclave with a volume of 200 ml, provided with a mechanical stirrer and a system input components of the catalytic system, place the pre-weighed sample of the complex 1Cl, (1.0 mg, 2.410-6mole), sealed in a glass ampoule. The autoclave is pumped at room temperature for 15 min, injected toluene (60 ml) and 4.8 ml of 10% solution of MAO (Witco) in toluene (7.210-3mol). With thermostat, the autoclave is heated to a temperature of 70oC with simultaneous feed of ethylene and stirring for 5 minutes with a Special device crush the ampoule with the catalyst. The polymerization is carried out at constant pressure of the monomer in the autoclave, is equal to 2 ATM. The reaction is stopped podkolennik HCl ethyl alcohol. After depressurization, the reactor opened and unloaded polymer in capacity from 150 ml of ethanol. The polymer is washed, filtered and dried at 60oC in the vacuum oven to a constant weight. The polymer yield 13.2 g Activity 2750 kg PE/(mol Zr h ATM). Molecular weight 152000. The degree of branching 5.6/1000C (IR data).

Example 4 (coloured carried out analogously to Example 1 with complex 1Me. The addition of complex 1.3 mg (3.510-6mole). AliBu3180 mg (9.1 10-4mole). Borat (3), solution in toluene 3.2 mg (3.510-6mole). The reaction temperature 20oC. the Pressure of ethylene 11.5 ATM. The response time of 11 minutes, the polymer Yield 22.5 g Activity 3049 kg PE/(mol Zr h ATM). Molecular weight Mw=1558, Mw/Mn=2.3 (GPC data). The content of double bonds: vinyl type at 1000C 10.0, vinylidene type 1000C 0.3. The degree of branching 67/1000C (data1H NMR).

Example 5 effect of reaction temperature for comparison with Example 4).

The polymerization was carried out similarly to Example 1 with complex 1Me. The addition of complex 1.35 mg (3.610-6mole). AliBu3187 mg (9.4610-4mole). Borat (3), solution in toluene 3.3 mg (3.610-6mole). The reaction temperature 40oC. the Pressure of ethylene 11.5 ATM. The response time of 9 minutes, the polymer Yield 31.3 g Activity 5040 kg PE/(mol Zr h ATM).

Molecular weight Mw= 1925, Mw/Mn=2.6 (GPC data). The content of double bonds: vinyl type at 1000C 5.6, vinylidene type 1000C 1.1.

Example 6 effect of reaction temperature for comparison with Examples 5, 4).

The polymerization was carried out similarly to Example 1 with complex 1Me. The addition of complex 1.3 m the temperature of the reaction 60oC. the Pressure of ethylene 11.5 ATM. The reaction time of 6 minutes, the polymer Yield 29.5 g Activity 7329 kg PE/(mol Zr h ATM). Molecular weight Mw=2303, Mw/Mn=2.6 (GPC data). The content of double bonds: vinyl type at 1000C 3.5, vinylidene type 1000C 0.2. The degree of branching 95/1000C (data1H NMR).

Example 7 effect of reaction temperature for comparison with Examples 4-6).

The polymerization was carried out similarly to Example 1 with complex 1Me. The addition of complex 1.3 mg (3.610-6mole). AliBu3180 mg (9.110-4mole). Borat (3), solution in toluene 3.3 mg (3.610-6mole). The reaction temperature is 0oC. the Pressure of ethylene 11.5 ATM. The reaction time is 15 minutes, the polymer Yield 9.5 g Activity 918 kg PE/(mol Zr h ATM). Molecular weight Mw=1250, Mw/Mn=2.2 (GPC data). The content of double bonds: vinyl type at 1000C 17. The degree of branching 55/1000C (data1H NMR).

Example 8 effect relationships Al/Zr and pressure of ethylene for comparison with Examples 4,5).

The polymerization was carried out similarly to Example 1 with complex 1Me. The addition of complex 1.85 mg (5.010-6mole). AliBu3496 mg (2.510-3mole). Borat (3), solution in toluene 4.6 mg (5.010-6mole). The fact is(mol Zr h ATM). The content of double bonds: vinyl type at 1000C 21.0, vinylidene type 1000C 0.4.

Example 9 effect of pressure of ethylene for comparison with Example 8).

The polymerization was carried out similarly to Example 1 with complex 1Me. The addition of complex 2.0 mg (5.410-6mole). AliBu3534 mg (2.710-3mole). Borat (3), solution in toluene, 5.0 mg (5.410-6mole). The reaction temperature 30oC. the Pressure of ethylene of 5 ATM. The reaction time is 10 minutes, the polymer Yield 16.3 g Activity 3622 kg PE/(mol Zr h ATM). Molecular weight Mw=1800, Mw/Mn= 4.5 (GPC data). The content of double bonds: vinyl type at 1000C 14.0, vinylidene type 1000C 0.5. The degree of branching 20/1000C (data IR and1H NMR).

Example 10 (the pressure of ethylene for comparison with Examples 7, 8).

The polymerization was carried out similarly to Example 1 with complex 1Me. The addition of complex 2.25 mg (6.110-6mole). AliBu3593 mg (3.010-3mole). Borat (3), solution in toluene 5.3 mg (6.110-6mole). The reaction temperature 30oC. the Pressure of ethylene of 20 ATM. The reaction time is 2 minutes, the polymer Yield 15.9 g Activity 3909 kg PE/(mol Zr h ATM). Molecular weight Mw=1500, Mw/Mn= 3.3 (GPC data). The content of double bonds: vinylcolor> Example 11 (the influence of the nature of the complex and the nature of Borat for comparison with Examples 1, 4).

The polymerization was carried out similarly to Example 1 with complex 1Me. The addition of complex 1.5 mg (4.110-6mole). AliBu3210 mg (1.0610-3mole). Borat (4), solution in toluene 3.3 mg (4.110-6mole). The reaction temperature 20oC. the Pressure of ethylene 11.5 ATM. The response time of 12 minutes, the polymer Yield 7.4 g Activity 785 kg PE/(mol Zr h ATM). Molecular weight Mw=1500, Mw/Mn= 2.7 (GPC data). The content of double bonds: vinyl type at 1000C 9.0, vinylidene type 1000C 3.0.

Example 12 (the influence of the complex nature of the claimed catalytic system for comparison with Example 8).

The polymerization was carried out similarly to Example 1 with complex 2Me. The addition of complex 1.75 mg (5.710-6mole). AliBu3563 mg (2.8410-3mole). Borat (3), solution in toluene 5.3 mg (5.710-6mole). The reaction temperature 30oC. the Pressure of ethylene 11.5 ATM. The reaction time is 5 minutes, the polymer Yield 6.5 g Activity 1189 kg PE/(mol Zr h ATM). Molecular weight Mw=15000 Mw/Mn= 3.4 (GPC data).

Example 13 effect of pressure of ethylene for comparison with Example 12).

In an argon box in 80 ml glass reactor,volumes, placed toluene (20 ml) and AliBu330 mg (0.1510-3mole). In a separate container -"the Twister fell off again" - was placed a solution of complex 2Me 0.3 mg (0.910-6mol) in toluene and is connected to the reactor. The reactor is extracted from Boxing, Tegaserod and introducing ethylene to a pressure of 1 ATM and a solution of the complex at a temperature of 15oC. stirring the solution should be performed within 5 min and poured the solution of borate (3) in toluene 0.8 mg (0.910-6mole). Introduction Borat is accompanied by an intense absorption of ethylene. The polymerization is carried out at constant pressure for 30 minutes the Reaction is stopped by acidified ethanol; the polymer is washed, filtered, dried at 60oC in the vacuum oven to a constant weight. The polymer yield 0.32 g Activity 736 kg/(mol Zr h ATM). M= 18000 (data viscosity measurements of polymer solutions in decaline at 135oC).

Example 14 (impact pressure of ethylene for comparison with Examples 12, 13).

The polymerization was carried out similarly to Example 1 with complex 2Me. The addition of complex 1.7 mg (5.510-6mole). AliBu3545 mg (2.7510-3mole). Borat (3), solution in toluene 5.1 mg (5.510-6mole). The reaction temperature 30oC. the Pressure of ethylene of 5 ATM. The reaction time is 5 minutes, the polymer Yield 2.0 g Anticline at 135oC).

Example 15 effect of pressure of ethylene for comparison with Examples 12, 13, 14).

The polymerization was carried out similarly to Example 1 with complex 2Me. The addition of complex 1.8 mg (5.910-6mole). AliBu3575 mg (2.910-3mole). Borat (3), solution in toluene, 5.4 mg (5.910-6mole). The reaction temperature 30oC. a Pressure of 15 ATM ethylene. The reaction time of 6 minutes, the polymer Yield 18 g Activity 2034 kg PE/(mol Zr h ATM). Molecular weight Mw=13000, Mw/Mn= 2.7 (GPC data).

Example 16 effect of pressure of ethylene for comparison with Examples 12,13,14,15).

The polymerization was carried out similarly to Example 1 with complex 2Me. The addition of complex 1.65 mg (5.3610-6mole). AliBu3531 mg (2.6810-3mole). Borat (3), solution in toluene 4.94 mg (5.3610-6mole). The reaction temperature 30oC. the Pressure of ethylene of 20 ATM. The reaction time is 4 minutes, the polymer Yield 25 g of Activity 3498 kg PE/(mol Zr h ATM). Molecular weight Mw=10000, Mw/Mn= 2.4 (GPC data).

Example 17 (the influence of the nature of Borat for comparison with Example 12).

The polymerization was carried out similarly to Example 1 with complex 2Me. The addition of complex 4.5 mg (14.610-6mole). AliBu3730 mg (3.6510-3mole). Borat (4), ri 5 minutes The polymer yield 8.6, the Activity of 614 kg PE/(mol Zr h ATM). Molecular weight Mw=10000, Mw/Mn= 3.5 (GPC data).

The results of the experiments shown in the Table and the Examples clearly show that the inventive homogeneous catalytic system and the inventive method allow for purposeful synthesis of low molecular weight branched polyethylene with high activity, much higher than the activity of the catalytic system prototype [17]; allow selection of the catalyst and the reaction conditions (temperature, pressure, ratio of components) can vary within wide limits the molecular weight of the polymer product, a branched low-molecular-weight polyethylene, the type of end groups. The inventive catalyst system and method for producing low molecular weight branched polyethylene can significantly reduce the concentration alyuminiiorganicheskikh compounds in the reaction medium, eliminating the need for cleaning polymeric products from the residues of the catalyst and reducing the cost of the resulting polymer.

1. Homogeneous catalytic system for the synthesis of low molecular weight branched polyethylene comprising trialkylaluminium, different Toya derived metallocene or pseudometrizable complex IVB group and perftoralkil borate or borane.

2. Homogeneous catalytic system for the synthesis of low molecular weight branched polyethylene under item 1, characterized in that as dealkiller derived metallocene or pseudometrizable complex IVB group contains dimethyl derivative at a ratio of Zr/B 0.5 to 10.0 mol/mol and Al/Zr 10 to 1000 mol/mol.

3. The method of obtaining low molecular weight branched polyethylene by catalytic polymerization of ethylene in prisutstvie homogeneous catalytic system comprising trialkylaluminium, characterized in that use three-component catalytic system, including additional dimethyl metallocene derived or pseudometrizable complex IVB group and perftoralkil borate or borane at a ratio of Zr/B 0.5 to 10.0 mol/mol and Al/Zr 10 to 1000 mol/mol, and the method is carried out in a medium of an organic solvent at 0 - 130oC and a pressure of ethylene of 0.5 to 20.0 MPa.

 

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