Copolymers of ethylene and a method of producing polymers based on ethylene

 

(57) Abstract:

Describes a new copolymer is a copolymer of ethylene with co monomer selected from olefins of the formula CH2= CH-CH2R, where R is hydrogen or a linear alkyl radical having from 1 to 20 carbon atoms, with the content of units of ethylene from 80 to 99 mol.% and the content of the links of the specified co monomer is from 1 to 20 mol.%, characterized in that the fractionation temperatureprofiles by elution at least 90 wt.% copolymer aluinum in the temperature range up to 50°C, and the ratio of mass-average molecular mass (Mwto srednetsenovoj molecular mass (Mn) determined by the method of gel chromatography, (Mw/Mn) exceeds 3. Also described is a method of obtaining polymers based on ethylene. The technical result - obtaining copolymers with optimal mechanical properties, in particular, for the production of films. 3 S. and 11 C.p. f-crystals, 2 tab., 3 Il.

The present invention relates to copolymers of ethylene and, in particular, copolymers of ethylene, which provide uniform distribution of parts of the co monomer within the polymer chain and a wide distribution of molecular weight. This invention also concerns a process is that polyethylene can be modified by the addition during the polymerization reaction of small amounts of olefins, usually 1-butene, 1-hexene or 1-octene. This gives the linear copolymers, low density polyethylene, which have short branches along the main chain of units derived from comonomers-olefin.

These branches lead to the fact that the degree of crystallinity and, consequently, the density of the copolymer is smaller than in homopolymer polyethylene. Typically, the copolymers, linear low density polyethylene have a concentration of about 0,910 - 0,940 g/cm3. Consequently, copolymers, linear low density polyethylene have optimal mechanical properties, in particular, for the production of films.

Lowering the degree of crystallinity and density (concentration) of the copolymers is a function of the type and quantity of on-olefins. In particular, the greater the number included-olefin, the lower the resulting degree of crystallinity and density.

These properties of the copolymer depend, in addition to the type and number of included co monomer-olefin, also on the distribution of branches along the polymer chain. In particular, a more uniform distribution of the branches has a positive effect on the properties of the copolymers. In fact, when the same type and number of ukloniti and density.

The copolymers, linear low density polyethylene prepared using known catalysts of the Ziegler-Natta, are characterized by poor uniformity of the composition and, in particular, the presence of serial links, the comonomers in the polymer chain and long sequences of units of ethylene. To obtain copolymers with a low enough density and crystallinity is therefore necessary to use large quantities of co monomer-olefin.

The use of catalysts based on compounds metallocene gave the opportunity to obtain copolymers, linear low density polyethylene with improved uniformity of composition. These copolymers, such as chemical composition, endowed with the best qualities compared to conventional copolymers.

The copolymers obtained with catalysts metallocene, however, have a narrow distribution of molecular weight (RMP). This is expressed in such qualities as poor ability to process what may be feasible in some cases, for example for use as films.

In order to overcome this drawback have been proposed processes for the preparation of SOPs is from about connection metallocene and nepetalactone compounds of titanium.

In U.S. patent N 4701432 described, for example, the preparation of linear low density polyethylene in the presence of catalytic component consisting of dichloride bis(cyclopentadienyl) zirconium and titanium tetrachloride, silicon dioxide as a solid carrier.

European Patent Application EP 439964 describes the preparation of linear low density polyethylene in the presence of a catalyst consisting of compounds of metallocene and compounds based on titanium, magnesium and halogen.

However, the thus obtained copolymers, linear low density polyethylene despite the fact that they have a wide distribution of molecular weight, do not have a satisfactory distribution of the comonomers in the polymer chain.

In another proposed system is ensured by the use of catalysts consisting of two different compounds of metallocene

The authors because Heiland and U. Kaminski in "Macromolecular Chemistry 193, 601 - 610 (1992) describe the reaction of copolymerization of ethylene with 1-butene in the presence of a catalyst consisting of a mixture dichloride rat-ethylenebis(indenyl) zirconium dichloride and rat-ethylenebis(indenyl)hafnium. The copolymers obtained with such catalysis is opredeleniya of comonomers on different polymer chains still does not reach a high level. This is because the values of parameters r1and r2copolymerization characteristic used zirconocene and garretsen significantly differ from one another, as reported on page 607 of the above-mentioned publication.

Therefore, it is necessary to obtain the copolymer linear low density polyethylene, which has an extremely uniform distribution of parts of the co monomer in the polymer chain, as well as a wide distribution of molecular weight.

Starostka metallocene usually prepared as a mixture of racemic and meso forms. Meso form is usually removed by separation of mixtures rat/meso forms, so as soon as chiral racemic form stereospetsifichno. Little is known descriptions of the use of the meso form in the polymerization of olefins.

European Patent Application EP 584609 describes the use of a special class of bis-indenyl metallocene having a molecular bridge connection in the meso form or in meso/rat mix for the preparation of atactic polyolefins having a high molecular weight and narrow distribution of molecular weight (Mw/Mn4). In particular, prepared Homo - and copolymers of propylene.

European Patent Application EP 64307 is their distribution of molecular weight by carrying out the polymerization reaction in the presence of a catalyst based on metallocene, where metallocen stereosushi and present in their meso isomeric form.

Surprised by the fact that the applicant found out here that it is possible to prepare copolymers, linear low density polyethylene having a uniform distribution of parts of the co monomer in the polymer chain and a wide distribution of molecular weight, as well as other polymers based on ethylene by conducting the polymerization reaction in the presence of a catalyst consisting of a mixture of racemic and meso isomers of compounds stereoscope metallocene.

The aim of the present invention, therefore, is a copolymer of ethylene with at least one co monomer chosen from:

(a) -olefins of the formula CH2=CH - CH2R, where R is hydrogen or a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms,

(b) cycloolefins and

(b) a polyene,

content units derived from comonomers-olefin, cycloolefin and/or polyene in the range from 1 to 20 mol.%, preferably in the range of 2 to 15 mol.%, characterized in that

(a) in FTPA analysis (fractionation temperatureprofiles by elution) a number equal to at least 90 wt.% copolymer, eluted in the dark mass and Mn- Brednikova molecular weight, both determined by gel chromatography.

Figure 1 shows the result of fractionation temperatureprofiles the elution (FCPA) of a copolymer of ethylene/1-butene according to the invention.

Figure 2 shows the result of fractionation temperatureprofiles the elution (FCPA) of a copolymer of ethylene/1-butene prepared by the method described by K. Chalandon and U. Kaminski in the above article.

Figure 3 shows the result of fractionation temperatureprofiles the elution (FCPA) of a copolymer of ethylene/1-hexene according to this invention.

Fractionation temperatureprofiles the elution (analysis of FCPA), performed as described by the authors: L. Wilde, T. R. Ryle, D. C. Knobloch and I. R. Peak in the journal Science, Polymer Edition, Polymer Physics, volume 20, 441 - 455 (1982), gives information about the length of the sequences of ethylene and, therefore, on the distribution of units of comonomers within a chain polymers.

In fact, this method makes it possible to fractionate the copolymers on the basis of their ability to crystallize and, consequently, on the basis of the sequences of ethylene between the two otvet who received more limited temperature range, in which eluted polymer.

The molecular weight of the copolymers of the present invention are distributed in a relatively wide range.

One indication of the distribution of molecular weight gives the ratio of Mw/Mnthe copolymers of the present invention is typically greater than 3, preferably greater than 4, and more preferably greater than 5.

Additional information about the distribution of molecular weight in the copolymer of the present invention can be obtained from measurements of the rate of melting. In particular, the ratio between indicators of melting F/E, where F includes a load equal to 21.6 kg, and the condition E includes uploading equal of 2.16 kg are high. For values of indicators melting E approximately about 0.4, the ratio between indicators of melting F/ metrics melting E are typically higher than 50, preferably more than 70, and more preferably more than 100.

Received the melting point of the copolymers of the present invention, which is a function of the type and number of co monomer, typically below 120oC and can reach values below 100oC.

The resulting density of the copolymers of the present invention,elicina below about 0.90 g/cm3.

In particular, according to another particular feature of the present invention the latter refers to a copolymer of ethylene with 1-butene content of units derived from 1-butene in the range from 1 to 20 mol.%, characterized in that

(a) the percentage by weight of 1-butene (1%) determined the carbon NMR analysis (nuclear magnetic resonance, carbon - 13), and density (D) of the copolymer meet the following relationship:

%B+285D 272,

(b) Mw/Mn> 3, where Mw- mass-average molecular weight and Mn- Brednikova molecular weight, both determined by gel chromatography.

The copolymers according to the present invention are also distinguished by low solubility in xylene at 25oC, which is usually below 10 wt.% and can reach values below 5 wt.%.

The copolymers according to the present invention have values characteristic viscosity (H. C.), typically in excess of 0.5 DL/g and preferably in excess of 1.0 DL/g Characteristic viscosity can reach 2.0 DL/g and above.

Examples of olefins of the formula CH2=CH - CH2R, which can be used as comonomers in the copolymers according to nastaran, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 akoten and allylcyclohexane. Preferable are 1-butene, 1-hexene or 1-octene, and more preferably 1-butene.

Examples of cycloolefins are cyclopentene, cyclohexene and norbornene.

The copolymers may also contain units derived from a polyene, in particular paired or unpaired linear or cyclic diene, such as, for example 1,4-hexadiene, isoprene, 1,3-butadiene, 1,5-hexadiene and 1,6-heptadiene.

In the case of use of a polyene that is different from a non-paired-diolefines having 6 or more carbon atoms, they are preferably used in quantities of from 0 to 3 mol.% as the second co monomer-olefin.

Another objective of the present invention is a process for the preparation of ethylene, comprising the polymerization reaction of ethylene in the presence of a catalyst consisting of a reaction product:

(A) a mixture of racemic and meso isomers of compounds stereoscope of metallocene transition metal belonging to groups III, IV or V or lanthanides in the Periodic System of Elements, with two cyclopentadienyl ligands, bound to one another chemical bridge connection, and

(B) is inane metallocene, selected from alumoxanes and compounds capable of forming cation of alkylbetaine.

The reaction of polymerization of ethylene can be carried out in the presence of at least one of the co monomer selected from olefins of the formula CH2= CH - CH2R, where R is a linear, branched or cyclic alkyl radical having from 1 to 20 carbon atoms, cycloolefins and/or a polyene. Thus, it is possible to prepare copolymers of ethylene, which are the aim of the present invention.

Racemic form and the meso form of connection metallocene are present in a weight ratio in the range of 99:1 and 1:99, respectively.

Connection stereoscope metallocene that can be used in the process according to this invention have the formula (I):

< / BR>
in which M is a metal selected from Ti, Zr and Hf, the substituting atoms, R1are C1-C20-alkyl radicals, C3-C20-cycloalkyl radicals, C2-C20alkenyl radicals, C6-C20aryl radicals, C7-C20-alkylaryl radicals or C7-C20-arylalkyl radicals and can contain atoms of Si or Ge;

replacement atoms, R2and R3are atoms of hydrogen, C1-C20aryl radicals, C7-C20-alkylaryl radicals or C7-C20-arylalkyl radicals and can contain atoms of Si or Ge;

if the substitute atoms, R2different from hydrogen, substitute atoms, R1and R2on the same cyclopentadienyl may form a ring containing from 5 to 20 carbon atoms;

R4is divalent group selected from (CR25)n, (SiR25)n, (GeR25)n, NR5or PR5where replacement atoms, R5that may be the same or different, are C1-C20-alkyl radicals, C3-C20-cycloalkyl radicals, C2-C20alkenyl radicals, C6-C20aryl radicals, C7-C20-alkylaryl radicals or C7-C20-arylalkyl radicals and, if R4is (CR25)n, (SiR25)nor (GeR25)ntwo replacement atom, R5on the same carbon atom, silicon or germanium can form a ring containing from 3 to 8 atoms, n is an integer ranging from 1 to 4, preferably from 1 to 2;

replacement atoms X1and X2are hydrogen atoms or halogen, R6hypoxia, are C1-C20-alkyl radicals, C3-C20aryl radicals, C2-C20alkenyl radicals, C6-C20aryl radicals, C7-C20-alkylaryl radicals or C7-C20-arylalkyl radicals and can contain atoms of Si or Ge.

Preferred are those compounds stereotactic metallocenes, which have the formula (II)

and the formula (III)

< / BR>
where in formulas (II) and (III) M, R3, R4X1and X2described above and substituting atoms, R7are hydrogen, C1-C20-alkyl radicals, C3-C10-cycloalkyl radicals, C2-C10alkenyl radicals, C6-C10aryl radicals, C7-C10-alkylaryl radicals or C7-C10-arylalkyl radicals and can contain atoms of Si or Ge and, in addition, two neighboring substitutional atom R7can form a ring having 5 to 8 carbon atoms.

Particularly suitable for the process are those compounds stereotactic metallocene formula (II) or (III) in which M is Zr, the substituting atoms, R3are hydrogen atoms or C1-C20-alkyl, substitutional atoms, R7groups are hydrogen or methyl, replacing atoms X1)2the radical.

According to the present invention examples metallocenes suitable for use in the process, but not limiting essence of the invention are the following:

C2H4(Ind)2MCl2,

C2H4(Ind)2M(NMe2)2,

C2H4(H4Ind)2MIU2,

Me2Si(Ind)2MCl2,

Ph(Me)Si(Ind)2MCl2,

C2Me4(Ind)2MCl2,

C2H4(2-MeInd)2MCl2,

C2H4(5,6-Me2Ind)2MCl2,

C2H4(2-MeH4Ind)2MCl2,

C2H4(2,4,7-Me3H4Ind)2MCl2,

C2H4(2-Me-Benz[e]Ind)2MCl2,

Me2Si(4,7-Me2Ind)2MCl2,

Me2Si(2,4,7-Me3Ind)2MCl2,

Me2Si(4,7-Me2H4Ind)2MCl2,

Me2Si(Bena[e]Ind)2MCl2,

C2H4(Ind)2MMe2,

C2H4(H4Ind)2MCl2,

C2H4(H4Ind)2M(NMe2)OMe,

Me2Si(Ind)2MMe2,

Ph2Si(Ind)2MCl2,

Me2SiCH2(Ind)2MCl2,

C2H4(4,7-Me2H4Ind)2MCl2,

C2H2(Benz[e]Ind)2MCl2,

Me2Si(2-MeInd)2MCl2,

Me2Si(5,6-Me2Ind)2MCl2,

Me2Si(2-MeH4Ind)2MCl2,

Me2Si(2,4,7-Me3H4Ind)2MCl2,

Me2Si(2-Me-Bens[e]Ind)2MCl2,

where Me is methyl, Cp is cyclopentadienyl, Ind - indenyl, Ph is phenyl, H4Ind - 4,5,6,7-tetrahydroindene and M is Ti, Zr or Hf, preferably Zr.

Especially preferred for use in the process according to the present invention the connection metallocene is dichloride, ethylene-bis(4,7-dimethyl-1-indenyl)zirconium.

The molecular ratio between aluminum alumoxane and metal connection metallocene is in the range of 5:1 and 10000:1 and preferably within about 20:1 and about 5000:1.

Alumoxane that can be used in the process according to the present invention is, for example, linear, branched or cyclic and contain at least one group of type (IV):

< / BR>
where replacement atoms, R8that may be the same or different, are R1or the group - O-Al(R8)2and, if you must, n is rmula (V):

< / BR>
where n is 0 or an integer between 1 and 40 in the case of linear compounds, or alumoxane formula (VI):

< / BR>
where n is an integer ranging from 2 to 40 in the case of cyclic compounds.

For use in the process according to the present invention are particularly suitable alumoxane, in which the radicals R1are the groups methyl, i.e methylalumoxane (MAO). They can be obtained by the reaction of trimethylaluminum (TMA) with water.

Examples of compounds that are not limiting of the invention serving for the formation of cation alkylbetaine are the compounds of formula Y+Z-where Y+is acid Bronsted able to give a proton and to enter into an irreversible reaction with substituted atom X1and X2the compounds of formula (I), and Z-is a compatible anion, which is not coordinated and is able to stabilize the active catalytic isotopes obtained from the reaction of the two compounds, and which is quite unstable, so that it can replace the olefinic substrate. Preferably the anion Z-consists of one or more boron atoms. More preferably the anion Z-is an anion of the formula BAr4(.), rotten, pentafluorophenyl or bis (trifluromethyl) phenyl. The most preferred tetrakis-pentafluorophenyl Borat. In addition, successfully can be used compounds of the formula BAr3. Compounds of this type are described, for example, in published International Patent Application WP 92/00333, the content of which is included in the description of the present invention as a reference material.

The catalysts used in the process according to the present invention may also contain one or more ORGANOMETALLIC aluminum compounds of the formula AlR39or Al2R69in which substitute atoms in R9that may be the same or different, are defined as replacement atoms, R1or are hydrogen atoms or halogen.

Examples of aluminum compounds and not limiting of the invention, of the formula AlR39or Al2R69following:

Al(Me)3, Al(Et)3, AlH(Et)2, Al(iBu)3, AlH(iBu)2, Al(iEs)3, Al(C6H5)3, Al(CH2C6H5)3, Al(CH2CMe3)3, Al(CH2SiMe3)3, Al(Me)2iBu, Al(Me)2Et,

AlMe(Et)2, AlMe(iBu)2, Al(Me)2iBu, Al(Me)2Cl, Al(Et)2

The catalysts used in the process according to the invention can expediently be used on inert media (substrates). They are obtained by deposition connection metallocene or its reaction product with socialization or socializaton and then connect metallocene on inert carriers, such as silicon dioxide, aluminum oxide, copolymers of styrene/divinylbenzene or polyethylene.

A particularly suitable class of inert carriers which may be used in the process according to the present invention are porous organic carriers, which functionalities groups with active hydrogen atoms. Especially preferred those in which the organic carrier is a polymer of styrene with partial intermolecular bonds. These media are described in Italian Patent Application N M 193A 001467, the content of which is included in the description of the present invention as a reference material.

Thus obtained solid compound in combination with the further addition of compounds alkylamine as such or the last pre-treatment water can also be used in gas phase polymerization.

the e, but also in the liquid phase in the presence of an inert aromatic hydrocarbon solvent, such as toluene, or preferably in an aliphatic solvent, such as, for example, propane or n-hexane.

The polymerization temperature is usually in the range of 0oC to 200oC, in particular from 20oC to 100oC and more preferably between 30 and 80oC.

The results of polymerization depend on the purity of the component metallocene catalyst. Connection metallocene obtained by the process according to the present invention can therefore be used as such or be processed by the clearing.

The components of the catalyst can be introduced into contact with one another prior to polymerization. The contact time is from 1 to 60 minutes, preferably from 2 to 20 minutes.

This is followed by examples illustrating the purpose of the invention, without limiting its essence.

Characteristics.

The presence of functional groups on the media (substrates) confirms the analysis by infrared spectroscopy method. Quantification of functional groups containing active hydrogen atoms is getvaluestring measurement after reaction with todom BET with the use of device "Sociopatic 1900" by Carlo Erba and mercury porosimetry using Porosimeter 2000 firms Carlo Erba.

Characteristic (own) viscosity (H. C.) is measured in tetraline at a temperature of 135oC.

Index (index) melting point (PP) is measured under the following conditions:

the condition E (I2standard American society for testing and materials: ASIM D-1238) at a temperature of 190oC with a load of 2.16 kg;

the condition F (I21standard American society for testing and materials: ASTM D-1238 with a load of 21.6 kg;

- the ratio of the melt flow (CTP) is equal to the ratio F/e

The content of groups of co monomer in the copolymers is determined by analysis of nuclear magnetic resonance, carbon-13 with the help of the device brouckère (200 MHz) using as solvent C2D2Cl4at a temperature of 110oC.

The ratio of meso forms and racemic forms of the compounds of metallocene was determined by analysis of nuclear magnetic resonance hydrogen - 1, (NMR), held in CDCl3at a temperature of 25oC, taking as a reference signal CDCl3at 7.25 ppm. The maximum limit of the meso form is 2.54 ppm, and the maximum limit racemic form is 2.72 ppm. From the ratio of the area of these before is by immersion of the sample extruded copolymer in the column density gradient in accordance with the method of ASTM D-1505.

Apparent bulk density (PLO) was determined by the method of DIN 53194 (German industrial standard).

Measurements of differential scanning calorimetry (DSC) was performed on the device "DSC-7" by Perkin Elmer Co. Ltd., as follows. About 10 mg of sample was heated to 180oC at a scan rate of 10oC/min, the sample was incubated for 5 minutes at a temperature of 180oC and then cooled at a scanning rate equal to 10oC/min. the Second scan is then performed in the same order as the first. For the report are indicators that obtained in the second scan.

The solubility in xylene at 25oC was determined as follows. About 2.5 g of polymer and 250 ml of xylene are placed in a flask equipped with cooler and a reflux condenser and kept under a protective layer of nitrogen. Then heated to 135oC with stirring for approximately 60 minutes. The composition is left to cool to 25oC, without stopping the stirring, then filtered and after evaporation of the solvent from the filtrate until reaching a constant weight get a lot of soluble material.

FTPE analyses were conducted using a device containing two columns of stainless steel, is made of small glass beads, coated with silane. The sample is dissolved in O-xylene (stable 0.03 weight. % antioxidant Irganox 1010) at a concentration of 7.5 mg/ml at a temperature of 140oC. the resulting solution is loaded into the column temperature 125oC and then cooled in the following sequence: 125-90oC after 30 minute, 90 - 10oC after 14 hours. After cooling is prolonged elution O-xylene at a rate of 10 ml/min, and the fraction of sampled every 20 minutes. During elution, the column temperature slowly rises from 10oC to 103oC with a speed of 0.15oC/min and then from 103oC to 125oC with a speed of 2.2oC/min

Preparation of media.

Polystyrene

An aqueous solution consisting of:

- 11 l of distilled water,

400 ml of 5% by weight aqueous solution ROAGIT SVM (Pohm),

- of 55.5 g PPOLIT C10 (Caffaro),

- 11 g sodium chloride,

was introduced under nitrogen atmosphere into a glass reactor with a capacity of 30 litres, equipped with a thermometer, a reflux condenser, a rod stirrer and a thermal control system. The solution is prevented (350 rpm) for one hour at room temperature and then introduced organic solution consisting of

- 5,55 l n-octane

- 1,85 l of toluene,

- 1tx2">

The reactor temperature was brought to 80oC for 1 hour and was maintained for 8 hours and then decreased to room temperature. The resulting product was repeatedly washed with distilled water, then carried out the extraction with methanol at 50oC and then dried at 100oC at a residual pressure of 1 mm Hg. This gave 2.7 kg product microspheroidal morphology, with the following characteristics:

Specific surface area: 370 m2/g (BET), 126 m2/g (RT.cent.).

Porosity: 1,74 ml/g (BET), 1,92 ml/g (RT.cent.).

The average radius of pores: 94 (angstroms) (BET), 305 (PT.cent.).

The particle size distributions (RRC):

0,8% > 300 μm;

2,2% 300 250 µm;

7% 250 - 180 microns;

10.5% of 180 - 150 microns;

73,2% 150 - 106 microns;

5,5% 106 - 75 microns;

0,8% < 75 microns.

Preparation funkzionirovanija media (Al)

(a) Acylation.

300 ml of carbon disulfide and 30 g of polystyrene was introduced in the conditions of a nitrogen atmosphere in a glass reactor with a capacity of 750 ml, equipped with a thermometer, a reflux condenser, a rod stirrer and a thermal control system. After establishing a constant temperature of 12oC was added 66 g (0,49 mol) pre-shredded AlCl3and seriali for 6 hours while stirring.

The mixture is then moved at constant stirring in a 3-liter flask containing a mixture of about 1 kg of crushed ice and 300 ml of HCl (37%) and then prevented another 30 minutes. The product recovered after filtration, was repeatedly washed with distilled water and then with acetone and, in the end, the methanol. After drying obtained 34 g of the product spheroidal morphology. Analysis by the method of infrared spectroscopy showed the band in the center at 1685 cm-1characteristic carbonyl.

(b) Recovery.

15.2 g of acetylated polymer obtained according to process (a), 100 ml of dioxane, 100 ml of distilled water and 15 g of NaBH4was introduced in a glass reactor with a capacity of 500 ml equipped with a thermometer, a reflux condenser and a rod stirrer. The mixture was continuously hampered for 50 hours at a temperature of 25oC and then was further added 4 g of NaBH4, continuing to interfere 70 hours. The polymer recovered after filtration, repeatedly washed with distilled water, then with acetone and finally with methanol. After drying, was restored to 13.4 g of the product spheroidal morphology. Infrared spectroscopy showed widened the band in the center at 3440 cm-1characteristic guimera, obtained in the process (a). The content of hydroxyl groups defined gas-volumetric titration with triethylaluminium was 3.3 macv per gram of polymer.

Preparation funkzionirovanija media (A2)

(a) Acylation.

4300 ml of methylene chloride and 225 g of polystyrene was introduced into the reactor with a capacity of 6 liters, equipped with a mechanical stirrer and a thermostat system. The mixture was cooled to 10oC and quickly added 580 g shredded AlCl3. Maintaining an internal temperature in the range of 10oC, was added dropwise 230 ml of acetyl chloride for 1 hour. The reaction mixture was constantly disturbed at a temperature of 25oC for another 24 hours. The mixture is then carefully poured into a slurry consisting of 2160 ml of distilled H2O, 2160 ml of ice and 2160 ml of 37% HCl solution. Once stopped adding, continued to obstruct another 30 minutes and the solid residue was then filtered and repeatedly washed with distilled water, then acetone, and at the end of the methanol. The obtained product was dried at 60oC; was restored 260 g of the product. Infrared spectroscopy showed the band in the middle at 1680 cm-1belonging to a carbonyl group.

the (a), introduced into a 3-liter flask equipped with a mechanical stirrer, thermometer and thermostat system. Maintaining the temperature of the suspension in the range below 35oC, for two hours gave a solution consisting of 138 g of NaBH4, 170 ml of NaOH (20%) and 1060 ml of distilled water. The mixture was left to react for 48 hours at a temperature of 25oC and then slowly added to 260 ml of acetone for the destruction of excess NaBH4. The polymer was filtered and repeatedly washed in the following order: distilled water, acetone, methanol and acetone. The product was dried in vacuum at 60oC for 24 hours. It was restored 234 g of the product. Analysis of methods infrared spectroscopy showed extended bandwidth at the center at 3440 cm-1, while the carbonyl band disappeared. The content of hydroxyl groups was determined by gas-volumetric titration with triethyl-A, giving 1.9 macv. per gram of polymer. Particles of spherical shape had an average size of 150 μm with the following characteristics surface area and porosity: 327 m2/g and 0.7 ml/g with an average pore diameter of 43 angstroms and 144 m2/g and 1.53 ml/g in pores 212 (angstroms) (PT. Art.) (used Porosimeter "Sociopatic 1900" BET).

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(a) Preparation of 4,7-dimethylindole

The synthesis was carried out in accordance with the method described in "Organometallics" 1990, 9, 3098" (54% output p-xylene).

(b) Preparation of 1,2-bis(4,7-dimethyl-3-indenyl)ethane.

38,2 g (265 mmol) of 4,7-dimethylindole dissolved in 350 ml of tetrahydrofuran and the temperature of the solution was brought to 0oC. Over 2.5 hours was added dropwise 165 ml of n-utility (1.6 M in hexane, 264 mmol). After reaching room temperature, continuing to interfere solution for 4 hours, got a bright red solution of 4,7-dimethylindole. The solution was cooled to -70oC and processed the fed drop by drop within 35 minutes of 25.3 g of 1,2-dibromoethane (135 mmol) in 15 ml of tetrahydrofuran. After returning to room temperature received the clear yellow solution, to which was added water. The organic phase was collected and dried over Na2SO4. Then vacuum evaporated solvent, and then received 20 g of product (yield 48%).

(C) Preparation dichloride rat/meso-ethylene-bis (4,7-dimethyl-1-indenyl)zirconium (B1).

A suspension of 10 g of 1,2-bis(4,7-dimethylindole) ethane (to 31.8 mmol) in 80 ml of tetrahydrofuran was added via cannula into a solution 2,82 g KH (70,3 mmol) in 160 ml of tetrahydrofuran with itca KH. This solution and a solution of 12 g ZrCl4(THF)2(to 31.8 mmol) in 250 ml of tetrahydrofuran was added dropwise within 3 hours via cannula into a flask containing 50 ml of tetrahydrofuran, with rapid stirring. Turned yellow solution and precipitate. After removal of solvent in vacuo, a yellow-orange residue (a mixture of racemic and meso isomers in a ratio of 2.33:1 in accordance with the hydrogen NMR analysis) was subjected to extraction with CH2Cl2until then, until all the orange product is not fully dissolved. Yellow solid (1.7 g) were single stereoisomer, namely meso isomer (yield of 11.3%). After evaporation of CH2Cl2from the orange solution was obtained 4.9 g of a yellow-orange solid corresponding to a mixture of 93,7% racemic isomer and 6.3% of the meso isomer, as determined by h-NMR analysis.

(g) Preparation dichloride rat/meso-ethylene-bis(4,7-dimethyl-1-indenyl)zirconium (B2).

Continued process (), but extraction with CH2Cl2continued until until received of 5.1 g of a yellow-orange solid corresponding to a mixture of 90.6% racemic isomer and 9.4% meso isomer, as determined by h-NMR analysis.

(d) Preparation of dihl the CE (g), was subjected to recrystallization from toluene at -20oC. 0.3 g of orange crystals were separated and it was found that they consist of pure dichloride rat-ethylene-bis (4,7-dimethyl-1-indenyl) zirconium, as determined by analysis of nuclear magnetic resonance of hydrogen (NMR).

Dichloride, ethylene - bis (indenyl)hafnium/zirconium.

(a) Preparation of 1,2-besondereiten.

Continued preparation which gives j. Even in the journal of the American Chemical Society, 1987, 109, 6544.

50,8 g of indene (437 mmol) was dissolved in inert atmosphere conditions in 500 ml of tetrahydrofuran in a 2-liter flask with two necks and cooled to a temperature of -78oC. Slowly (over hours) was added dropwise 175 mm n-utility (2.5 M in hexane, 437,5 mmol). Gave the mixture to warm to room temperature and prevented another 4 hours. Cooled it to -78oC and added dropwise (over 20 minutes) was added 40,42 g 1,2 - dibromoethane (215 mmol), dissolved in 100 ml of tetrahydrofuran. At the end of the addition the temperature was brought to 50oC continued to obstruct 12 hours, then the mixture was cooled to room temperature, after which was added 20 ml of water. The organic phase was dried and the residue was extracted pentadienyl) hafnium/ethylene dichloride - bis (indenyl) zirconium.

7,13 g (27.8 mmol) of 1,2-besondereiten and 50 ml of anhydrous tetrahydrofuran was placed in a flask with a capacity of 250 ml with two necks. The yellow solution was cooled to -78oC and added to 34.5 ml of n - utility (1.6 M in hexane, 55.2 mmol). It gave a reddish-brown solution, which was heated under reflux for 1 minute and then left to cool to room temperature.

8,84 g anhydrous HfCl4(27.6 mmol) was placed in a flask with four necks, equipped with a cooler, and was dissolved at a temperature of -180oC in 70 ml of tetrahydrofuran. Then the solution was heated under reflux for 30 minutes, getting brownish-purple suspension was left to cool to ambient temperature, vigorously stirring.

Solution was added lithium salts of besondereiten approximately 2 minutes and continued to obstruct another 2 hours and 30 minutes. The resulting solution became yellow-brown color. Bubbling gaseous HCl gave a yellow-orange suspension. The solvent was removed under vacuum, was added 100 ml of ethyl ether, and leave the mixture overnight at a temperature of 0oC. the Residue was filtered from the ether solution was dried in vacuum and IDate in the sediment, which was filtered off.

This gave to 1.15 g of the product, which, as shown by h-NMR analysis, consisted of 96% of ethylene dichloride bis (indenyl) hafnium and 4% ethylene dichloride bis (indenyl) zirconium.

Methylalumoxane (MAO). Used commercial product of the firm Schering (now With MW1400) in the form of a 30% by weight solution in toluene. After removal of the volatile fractions in vacuum semi-crystalline material was crushed to yield a white powder, which is then treated under vacuum (0.1 mm Hg) for 4 hours at a temperature of 40oC.

Triisobutylaluminum (TIBAL). Used commercial product (Schering, now Witco) in the form of a 20% weight - volume solution in hexane.

The polymerization.

All the processes of the preparation of the catalysts was carried out in an atmosphere of anhydrous nitrogen.

Example 1.

(a) Preparation of catalyst on the carrier (substrate).

100 ml of anhydrous toluene and 5.2 g of carrier (A1) was placed in a glass reactor with a capacity of 350 ml, equipped with a thermometer, reflux condenser, rod stirrer and a thermal control system. 30 ml methylalumoxane (MAO) in 1 M solution of toluene (157 mg A1/g media) was added during 40 mintemperature -5oC, then for one hour at a temperature of 0oC, for 1 hour at a temperature of 30oC and then for 4 hours at a temperature of 80oC. After cooling to 25oC the solid residue was filtered and washed with 100 ml of toluene and again dispersible in 100 ml of toluene. Then was cooled to 0oC and after 55 minutes was added 50 ml of toluene containing 224,2 mg dichloride mixture rat/meso - ethylene - bis (4,7 - dimethyl-indenyl) zirconium (B1) (8,3 mg Zr/g of carrier). The temperature was brought to 30oC and the mixture is prevented for 2 hours. After this happened suspension reddish color, which was allowed to settle, resulting in the obtained residue and colorless solution, which was poured the water trap. The precipitate was repeatedly washed anhydrous toluene and then dried in vacuum. It was restored to 7.0 g of the product microspheroidal morphology, having the following composition by weight: 9,6% Al, 0.7% Of Cl, 0,44% Zr.

(b) Polymerization.

Steel autoclave with a capacity of 2.5 liters, equipped with a core magnetic agitator, pressure gauge, temperature indicator, system of submission of the catalyst, the feed monomer and thermostatic jacket, purified by washing with propane at a temperature of 70oC, p is OPANA and ethylene, 1 - butene and hydrogen in amounts specified in table 1, and the reactor was heated to 45oC.

The suspension of catalyst prepared in vitro (type Shlensky tubes) with a drain tap at the bottom. Consistently at a temperature of 25oC was injected 5 mmol of triisobutylaluminum in 5 ml of hexane and then 92 mg of the catalyst on the carrier obtained by the process (a).

The reagents are left in contact for 5 minutes, and then the suspension was injected into the autoclave under pressure of ethylene.

The temperature is then brought to 50oC and maintained constant during the entire polymerization process. The total pressure was kept constant by feeding a mixture of ethylene/1-butene in a molar ratio equal to 18. Polymerization was stopped by the introduction of 0.6 l CO in the autoclave after cooling to 30oC.

Then the reactor was left for slow degassing, and the resulting polymer was dried at a temperature of 60oC in vacuum.

The conditions of polymerization are shown in table 1, and data relating to the polymer, are shown in table 2.

Example 2.

(a) Preparation of catalyst on the carrier.

300 ml of toluene and 30.2 g of the carrier (A2) was injected into the reactor with a temperature-controlled jacket capacity is 2">

The temperature of the suspension was maintained with the help of thermostatic regulation is equal to -10oC and after 70 minutes was added 200 ml of 0.9 M methylalumoxane (MAO) (160 mg Al/g of carrier). The mixture for 60 minutes kept at a temperature of -10oC, 60 minutes at 0oC and another 60 minutes at a temperature of 30oC and 240 minutes at a temperature of 80oC. the Suspension was filtered at 50oC and washed two times with 200 ml of anhydrous toluene and then dried in vacuum. Restored to 66.8 g of spheroidal particles containing 7.5 percent by weight Al and 27,0% by weight of solvent.

100 ml of anhydrous toluene and 4.9 g the spheroidal particles were introduced into the reactor with a shirt with a capacity of 350 ml, equipped with air stirrer, thermometer, reflux condenser and thermal control system.

The suspension was cooled to 0oC and after 30 minutes was added 30 ml of toluene containing 0.1 g of the mixture dichloride rat/meso - ethylene - bis (4,7 - dimethyl - indenyl) zirconium (B1) (6,1 mg Zr/g of carrier).

The suspension is an orange-red color prevented further 3 hours at 30oC. After separation from the solid material, the liquid was filtered and the residue was washed 2 times with 100 ml of toluene and twice in 100 ml of hexane and then dried in vacuum at 2598% Cl, 0,36% Zr.

(b) Polymerization.

The process described in section (b) of example 1 was continued, using 105 mg of the catalyst on the carrier obtained in the process (a).

The conditions of polymerization are shown in table 1, and data relating to the polymer, are shown in table 2.

Examples 3.

(a) Preparation of catalyst on the carrier.

The process described in section (a) of example 2, was continued, but with 9.6 mg Zr/g of carrier. Restored to 3.3 g of the product microspheroidal morphology, having the following composition by weight: 8,6% Al, 1,05% Cl, 0,44% Zr.

b) Polymerization.

The process described in section (b) of example 1, continued using 106 mg of the catalyst on the carrier obtained in the process (C).

The conditions of polymerization are shown in table 1, and data relating to the polymer, are shown in table 2. The result of FCPA analysis is indicated in Fig. 1.

Example 4.

(a) Preparation of catalyst on the carrier.

The process described in section (a) of example 2, continued, but using a mixture dichloride rat/meso - ethylene (4,7 - dimethyl - indenyl) zirconium (B2) (7.8 mg Zr/g of carrier) instead of the mixture (B1). Restored to 5.4 g of the product microspheroidal morphology, the second section (b) in example 1, continued using 267 mg of the catalyst on the carrier received by the processor (s).

The conditions of polymerization are shown in table 1, and data related to the polymer, are shown in table 2.

Example 5.

The process described in section (b) of example 1 was continued, but in the absence of triisobutylaluminum using methylalumoxane (4.2 mmol Al) and 0.5 mg of the mixture (B1) for the preparation of the catalyst.

The conditions of polymerization are shown in table 1, and data related to the polymer, are shown in table 2.

Example 6.

The process of the previous example continued, but using 0.1 mmol methylalumoxane and adding 5 mmol of triisobutylaluminum in the autoclave.

The conditions of polymerization are shown in table 1, and data related to the polymer, are shown in table 2.

Examples 7-8 (for comparison).

Continued the process of example 5, but in the presence of methylalumoxane using 2.1 mmol of triisobutylaluminum and 1.0 mg metallocene (B3). Then, the autoclave was added 1.05 mmol H2O.

The conditions of polymerization are shown in table 1, and data related to the polymer, are shown in table 2.

Example 9 (for comparison).

The process of example 5 continued, isbis (indenyl) hafnium and 4% ethylene dichloride - bis (indenyl) zirconium.

The conditions of polymerization are shown in table 1, and data relating to the polymer, are shown in table 2. The result of FCPA analysis shown in Fig. 2.

Example 10.

The process described in section (b) in example 1, continued, but carrying out the polymerization reaction at a temperature of 70oC using 0,95 l anhydrous hexane instead of propane and 42 mg of the catalyst on the carrier obtained in section (a) of example 3.

The conditions of polymerization are shown in table 1, and data relating to the polymer are shown in table.2.

Example 11.

The process of the previous example continued, but at the same time carrying out the polymerization reaction at a temperature of 80oC and using 16,4 kg of catalyst on the carrier.

The conditions of polymerization are shown in table. 1, and data related to the polymer are shown in table. 2.

Example 12.

(a) Preparation of catalyst on the carrier.

The process described in section (a) of example 2, continued, but using a mixture dichloride rat/meso - ethylene - bis (4,7 - dimethyl - indenyl) zirconium (B2) (7.8 mg Zr/g of carrier) instead of the mixture (B1). Restored to 5.4 g of the product microspheroidal morphology, having the following composition by weight: 8,1% Al, 1,09% Cl, is a magnetic agitator, the monometr, thermometer, feed system catalyst, the feed line of the monomer and the temperature-controlled jacket, purified by washing with propane at a temperature of 70oC.

When the ambient temperature is introduced 280 ml of anhydrous 1-hexene (distilled over LiAlH4), 5 mmol triisobutylaluminum in 5 ml of hexane, 640 ml of propane and the monomer in amounts specified in table 1, and the reactor then was heated to 55oC.

Prepared separately, the suspension of catalyst added to the test tube with the outlet in the bottom 5 mmol of triisobutylaluminum in 5 ml of hexane and 190 mg of the catalyst on the carrier received by the processor (a) at a temperature of 25oC.

Components are left in contact for 5 minutes at ambient temperature before they were introduced into the autoclave under pressure of ethylene.

The temperature was raised to 60oC and kept constant over the course of the polymerization. The total pressure was maintained at a constant level during continuous feeding of ethylene.

The polymerization was stopped by the introduction of 0.6 l CO in the autoclave, and then quickly cooled to 30oC. the Reactor was left for slow degassing and the resulting polymer is of iMER, shown in table 2. The result of FCPA analysis shown in Fig. 3.

Example 13.

(a) Preparation of catalyst on the carrier.

The process continued, was described in section (a) of example 12, but using 12,2 mg Zr/g of carrier.

Restored 5.6 g of the product microspheroidal morphology, having the following composition by weight: 9,3% Al, 1,03% Cl, 0.51% of Zr.

(b) Polymerization.

The process described in section (b) of example 12, continued, but with the use of 132 mg of the catalyst on the carrier obtained by the process (a).

The conditions of polymerization are shown in table 1, and data relating to the polymer, are shown in table 2.

Example 14.

Steel autoclave with a capacity of 2.5 liters, equipped with a core magnetic agitator, pressure gauge, temperature indicator, system of submission of the catalyst, the feed monomer and thermostatic jacket, cleaned by washing with ethylene at 70oC.

Into the autoclave was introduced 5 mmol of triisobutylaluminum in 1070 ml of hexane at ambient temperature and after heating to 70oC and injection of ethylene under pressure 16,8 bar was introduced hydrogen under pressure 1,73 bar. Then, the autoclave was cooled to 65oC.

oC was injected 5 mmol of triisobutylaluminum in 5 ml of hexane and then 500 mg of the catalyst on the carrier obtained by the process (a) of example 13. Components remained in contact for 5 minutes, and the slurry is then introduced into the autoclave under pressure of ethylene.

The temperature was raised to 70oC and the total pressure is maintained at a constant level by continuous feeding of ethylene. After 100 minutes the polymerization was stopped by cooling to 30oC and the introduction of 0.6 l CO.

The polymer suspension was filtered and the obtained polymer was dried in an oven at 60oC in vacuum. This gave 440 g of spheroidal granules having the following characteristics:

index (index) melting E(I2) = 0,34

the ratio of the melt flow = 84

absolute density = 0,9623 g/ml

apparent bulk density = 0.35 g/ml

TM=134oC(

1. A copolymer of ethylene with co monomer selected from olefins of the formula CH2= CH - CH2R, where R is hydrogen or a linear alkyl radical having from 1 to 20 carbon atoms, with the content of units of ethylene from 80 to 99 mol.% and the content of the links of the specified co monomer is from 1 to 20 mol.%, characterized in that the fractionation temperatureprofiles lirovannomu molecular mass (Mwto srednetsenovoj molecular mass (Mndetermined by means of gel chromatography (Mw/Mn) exceeds 3.

2. A copolymer of ethylene under item 1, characterized in that the ratio of the rate of melting (F/E) is greater than 100, where F corresponds to the load equal to 21.6 kg, and E corresponds to the load equal of 2.16 kg

3. A copolymer of ethylene under item 1 or 2, characterized in that it has a density of less than 0.94 g/cm3.

4. A copolymer of ethylene under item 1 or 2, characterized in that it has a solubility in xylene of less than 10% by weight at 25oC.

5. A copolymer of ethylene under item 1 or 2, characterized in that as co monomer used 1-butene.

6. A copolymer of ethylene with 1-butene content of units 1-butene from 1 to 20 mol.%, characterized in that the percentage by weight of 1-butene (%) determined by the method of nuclear magnetic resonance, carbon-13, and the density (D) of the copolymer corresponds to the following value: % B + 285 D 272, and the ratio of Mw/Mn> 3, where Mwand Mnpreviously defined.

7. The method of copolymerization of ethylene with co monomer selected from olefins of the formula CH2= CH - CH2R, where R is hydrogen or a linear alkyl radical, amicucci and mesosomal connection stereoscope metallocene transition metal IV B group of the Periodic system of elements with two cyclopentadienyl ligands, connected by a chemical bridge connection, and at least one socializaton able to activate as racemic form, and mesoform connection metallocene selected from alumosilicates and compounds capable of forming cation of alkylbetaine, characterized in that the copolymer under item 1.

8. The method according to p. 7, characterized in that the racemic form and mesoform connection metallocene present in the range from 99:1 to 1:99.

9. The method according to p. 7, characterized in that the connection metallocene represented by formula

< / BR>
where M is a metal selected from the group consisting of titanium, zirconium and hafnium;

R3is a hydrogen atom;

R4is divalent group selected from (CR25)nwhere replacement atoms, R5are hydrogen atoms; n is an integer ranging from 1 to 2, substituting atoms X1and X2are the atoms of halogen;

R7is hydrogen, C1- C10- alkyl radicals.

10. The method according to p. 9, characterized in that the connection uses metallocene is dichloride, ethylene-bis(4,7-dimethyl-1-indenyl)zirconium.

11. The method according to p. 7, characterized in that as with the ATOR, deposited on an inert carrier.

13. The method according to p. 12, characterized in that use porous organic carrier having functional groups containing active hydrogen atoms.

14. The method according to p. 13, characterized in that the use of a polymer of styrene with partial intermolecular bonds.

 

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