Components of catalyst for polymerization of olefins, catalyst, method for preparing propylene polymers and propylene polymer

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to the catalyst component used in polymerization of olefins comprising Mg, Ti, halogen and at least two electron-donor compounds wherein indicated catalyst component and at least one of electron-donor compounds repenting in the amount in the range from 20 to 50 mole% with respect to the complete amount of donors are chosen from succinic acid esters that are not extractable by above 25 mole% and at least one additional electron-donor compound that is extractable by above 35 mole%. Indicated components of catalyst provides preparing polymers possessing good insolubility level in xylene, high content level of stereoblocks and broad MWD value that is suitable for preparing polymers used in the region using bi-oriented polypropylene films. Also, invention relates to catalyst used in polymerization of olefins, methods for preparing propylene polymers and propylene polymer.

EFFECT: improved preparing method, valuable properties of catalyst.

24 cl, 3 tbl, 17 ex

 

The present invention relates to the components of the catalyst for polymerization of olefins, in particular propylene containing media based dihalogenide Mg, which cause the connection Ti, which has at least one link Ti-halogen, and at least two electron-donating compound selected from certain classes. The present invention additionally relates to the catalysts obtained from the above components, and their use in methods for the polymerization of olefins. The catalysts of the present invention allow to obtain the propylene homopolymers with high yields with good levels of insolubility in xylene, a wide range of isotacticity and, in specific conditions, a very high content of stereoblock.

The components of the catalyst for stereospecific polymerization of olefins is widely known at the present level of technology. The most widespread family of catalytic systems includes a solid component of catalyst containing dihalogenide magnesium, which caused a compound of titanium and an internal electron-donor compound used in combination with Al-alkyl compound. But usually, if you want a higher degree of crystallinity of the polymer, in order to get a higher isotactic the , also necessary and the external donor (for example, alkylalkoxysilane). One of the preferred classes of internal donor is formed by esters of phthalic acid, and used to the greatest extent is diisobutylphthalate. This catalytic system allows to achieve very good performance, expressed through activity, isotacticity and the level of insolubility in xylene, using the external electron-donor compounds. If the external donor is not used, it will have low yields, poor level of insolubility in xylene and unsatisfactory isotacticity. On the other hand, if the external donor is used, good levels of insolubility in xylene will be obtained only with high isotacticity. In addition, the molecular weight distribution (MWD) in a typical single-stage polymerization Nishioka (polydispersity is in the range of 3.6 to 4.5). These characteristics, although suitable for certain applications, is undesirable in some other areas, such as getting devuono-oriented polypropylene films (VOR). For use in this area, in fact, requires that polypropylene would be broad MWD (measure of polydispersity greater than 5), the lower module is progoti bending (obtained by reducing the degree of crystallinity of the polymer) while maintaining at the same time a good level of insolubility in xylene. In addition, it was found that the polymers suitable for use in the field, are those for which, in addition to the above requirements is also relatively high content of so-called stereoblock, i.e. fractions of the polymer, which, despite the prevailing isolationist contain negligible amount neizotermicheskikh sequences propylene units. In conventional fractionation techniques, such as TREF (fractionation by elution with increasing temperature), such elution fractions occurs at temperatures lower than the temperatures required for more isotactic fractions. In EP 658577 describes a method for PP-homopolymers with high content of stereoblock. It includes the polymerization of propylene in the presence of a catalyst containing (i) a solid component of catalyst, in which the connection Ti and diisobutylphthalate applied to the carrier MgCl2(ii) Al-alkyl compound as socializaton and (iii) 3,3,3-cryptochromes(alkyl)dimethoxysilane as an external donor. In example 1 you can see that despite the fact that the polymerization is carried out in two successive stages under different conditions, MWD obtained bimodal polymer is not wide enough (polydispersity 4,7). To the ome, in the case of bimodal polymers may have problems with uniformity due to the presence of appreciable quantities of fractions with a pronounced difference in average Mw. In this example the mass percentage fraction of stereoblock measured using TREF for polymer after a light cracking, is approximately equal to 31%, then in another run (table 2) the content of the fraction stereoblock was approximately 26%. Given the above, it would be desirable to have a component of the catalyst is further improved characteristics and which, in particular, would make it possible to obtain polymers with a good level of insolubility in xylene, a high content of stereoblock and broad MWD that is suitable for polymers used in the sector of application of war.

Nowadays was unexpectedly discovered component of the catalyst having the above advantages, which contains Mg, Ti, halogen and two electron-donating compound selected from certain classes. Therefore, the object of the present invention is a catalyst component for polymerization of olefins CH2=CHR, in which R represents hydrogen or a hydrocarbon radical comprising 1 to 12 carbon atoms, containing Mg, Ti, halogen and at least two electron-donating compound, and pointed to by the y component of the catalyst differs that at least one electron-donating compounds, which is present in a quantity ranging from 15 to 50% (mol.) in relation to the total number of donors, which are selected from esters of succinic acids that cannot be proektirovanii, in the conditions described below, by more than 20% (mol.), and at least one electron-donating compounds, which can be proektirovanii in the same conditions for more than 30% (mol.).

In accordance with the present invention the esters of succinic acid, is not extractable by more than 20% (mol.), will be called extrapyramidal succinate. Electron-donating compounds extractable by more than 30% (mol.), will be called extractable electron-donor compounds. The number extragenomic of succinate preferably is in the range from 20 to 45, and more preferably from 22 to 40% (mol.) in relation to the total number of electron-donor compounds. In the preferred implementation uses succinate, which cannot be proektirovanii by more than 15%, and another electron-donating compound, which can be proektirovanii more than 35%.

Among the above extragenomic of succinate particularly preferred succinate described by the following formula (I)

in which the radicals R and R2identical or different, denote C1-C20linear or branched alkyl, alkenylphenol, cycloalkyl, aryl, arylalkyl or alcylaryl group, optionally containing heteroatoms, and the radicals R3and R4identical or different, denote C1-C20alkyl, cycloalkyl, aryl, arylalkyl or alcylaryl group, optionally containing heteroatoms, provided that at least one of them is a branched alkyl; moreover, these connections are to the two asymmetric carbon atoms indicated in the structure of the formula (I), stereoisomers related to the type (S,R) or (R,S)that are present in pure form or as mixtures.

R1and R2preferably are C1-C8alkyl, cycloalkyl, aryl, arylalkyl and alcylaryl groups. Particularly preferred compounds in which R1and R2selected from primary Akilov and, in particular, of branched primary Akilov. Examples of groups suitable for R1and R2are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred ethyl, isobutyl and neopentyl.

Particularly preferred compounds in which the radicals R3and/or R4the two who are secondary alkilani, like isopropyl, sec-butile, 2-pentile, 3-pentile, or cycloalkyl such as cyclohexyl, cyclopentyl, cyclohexylmethyl.

Examples of the above compounds are of the form (S,R) (S,R), pure or as a mixture, optionally in the form of a racemate, diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2,3-bis(2-ethylbutyl)succinate, diethyl 2,3-divineislam, diethyl 2,3-Diisopropylamine, Diisobutyl 2,3-Diisopropylamine, diethyl 2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-diisobutylamine, diethyl 2,3-dineopentyl, diethyl 2,3-Dicyclopentadiene, diethyl 2,3-dicyclohexylamine.

Among the extracted electron-donating compounds are particularly preferred esters of one - and dibasic organic carboxylic acids, such as benzoate, maleate, phthalates and succinate. Among malonate particularly preferred compounds are described by formula (II):

where R1means N or C1-C20linear or branched alkyl, alkenylphenol, cycloalkyl, aryl, arylalkyl or alcylaryl group, R2means C1-C20linear or branched alkyl, alkenylphenol, cycloalkyl, aryl, arylalkyl or alcylaryl group, R3and R4identical or different, denote C1-C20 3-C20cycloalkyl group.

R3and R4preferably are primary, linear or branched C1-C20alkyl groups, more preferably when they are the primary branched C4-C20alkyl groups, such as isobutylene or neopentylene group.

R2in particular, if R1means H, preferably means a linear or branched C3-C20alkyl, cycloalkyl or arylalkyl group; R2more preferably, means3-C20secondary alkyl, cycloalkyl or arylalkyl group.

Preferred esters of aromatic carboxylic acids are selected from C1-C20alkyl or aryl esters of benzoic and phthalic acids, possibly substituted. Preferably alkalemia esters of these acids. Particularly preferred C1-C6linear or branched alkalemia esters. Specific examples are ethylbenzoic, n-butylbenzoate, p-methoxyaniline, p-amoxicillinsee, isobutylbenzene, ethyl p-toluate, diethylphthalate, di-n-propietat, di-n-butylphthalate, di-n-interftet, diisopentylphthalate, bis(2-ethylhexyl)phthalate, utilizability, ethyl n-butylphthalate, di-n-hexylphthalate, diisobutylphthalate.

Among succinato them which is a lot of subclasses of compounds, which can be used as extracted donors in accordance with the present invention. One of the preferred groups of compounds is the group described by formula (III)

in which the radicals R3-R5mean hydrogen, a R6means branched alkyl, cycloalkyl, aryl, arylalkyl and alcylaryl radical containing from 3 to 10 carbon atoms. Particularly preferred are compounds in which R6means branched primary alkyl group or cycloalkyl group containing from 3 to 10 carbon atoms. Specific examples are diethyl second-butylamine, diethyl-tert-hexylamine, Diethylenetriamine, Diethylenetriamine, diethyl - (10)-perhydroanthracene, diethyltoluenediamine, diethylmethoxyborane, diethyl-p-methoxyphenylacetone, diethyl-p-chlorpheniramine, diethylethanolamine, diethylsiloxane, diethylaniline, diethyl (cyclohexylmethyl)succinate, diethyl-tert-butylamine, diethylethanolamine, diethylethanolamine, Diethylenetriamine.

Another preferred subclass of compounds is that subclass, described by formula (III)in which R3and R4mean hydrogen, a R5and R6selected and the C 1-C20linear or branched alkyl, alkenylphenol, cycloalkyl, aryl, arylalkyl or alcylaryl group, optionally containing heteroatoms. Specific examples of suitable 2,2-disubstituted succinates are: diethyl 2,2-dimethylsuccinic, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-Isopropylamine, diethyl 2-{cyclohexylmethyl)-2-isobutylamino, diethyl 2-cyclopentyl-2-n-profilaktika, diethyl 2,2-diisobutylamine, diethyl-2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2,2-diisopropylphenyl-2-isobutyl-2-ethylsuccinate, diethyl 2-(1,1,1-Cryptor-2-propyl)-2-methylsuccinate, diethyl 2-isopentyl-2-isobutylamino, diethyl-2-phenyl-2-n-butylacrylate, Diisobutyl 2,2-dimethylsuccinic, Diisobutyl 2-ethyl-2-methylsuccinate, Diisobutyl 2-benzyl-2-Isopropylamine, Diisobutyl 2-(cyclohexylmethyl)-2-isobutylamino, Diisobutyl 2-cyclopentyl-2-n-profilaktika.

In addition, the preferred form (S,S), (R,R) or meso-forms of succinate described by the above formula (I).

As extragenomic donors can be used a mixture of different succinato described by formula (I), and can also be used a mixture of extractable donors. In particular, it was found that particularly advantageous to use succinate described by formula (I), in which the R 3and R4same, as as extracted, and as extragenomic electron donor. In fact, compounds described by formula (I)in which R3and R4the same, are often mixtures of meso-form (S,S and R,R) and racemic form (S,R, and R,S), which is a direct result of the way they are received. Therefore, in certain cases, the experts in this field already have a mixture of extractables and extragenomic donors for use in obtaining the catalyst of the present invention. Depending on the specific amounts of individual donors in mixtures may require additional amounts of extractable donors to enter the final composition of the catalyst to within the range suggested above.

Particularly interesting was recognized using the catalyst containing racemic form diethyl or Diisobutyl 2,3-Diisopropylamine as dextrogirum donor and meso-form diethyl or Diisobutyl 2,3-Diisopropylamine together with alkylphenate as extracted donors.

As already explained above, the components of the catalyst of this invention contain in addition to the above electron donors Ti, Mg and halogen. In particular, the components of the catalyst include a compound of titanium, which has a p is at least one link Ti-halogen, and the above electron-donor compound supported on a carrier, the Mg halide. The magnesium halide is preferably MgCl2in the active form, which is widely known in the patent literature as a carrier for catalysts of the Ziegler-Natta. Patents USP 4298718 and USP 4495338 were the first, in which is described the use of these compounds in catalysis Ziegler-Natta. Of these patents, it is known that dihalogenide magnesium in the active form used as the carrier or joint media components of catalysts for the polymerization of olefins, characterized by x-ray spectra in which the most intense diffraction line observed in the spectrum of active halide, decreases in intensity and is replaced by halo, the maximum intensity of which is shifted towards smaller angles with respect to the position of the more intense lines.

The preferred titanium compounds used in the catalyst component of the present invention are TiCl4and TiCl4; in addition, can also be used and galogenangidridy Ti formula Ti(OR)n-yXywhere n denotes the valence of titanium, y denotes a number in the range from 1 to n-1, X means halogen, a R means a hydrocarbon radical containing from 1 to 10 carbon atoms.

Getting Tverdov the catalyst component can be carried out in several ways. In accordance with one of these methods, the magnesium dichloride in an anhydrous state, the connection of titanium and electron-donating compounds grind with each other under conditions in which activation of the magnesium dichloride. Thus obtained product can be treated one or more times with an excess of TiCl4at a temperature in the range from 80 to 135°C. After this treatment lavage is carried out in hydrocarbon solvents until then, until there is no chloride ions. In accordance with another method, the product obtained as a result of joint grinding of magnesium chloride in an anhydrous state, the titanium compounds and electron-donating compounds, is treated with halogenated hydrocarbons such as 1,2-dichloroethane, chlorobenzene, dichloromethane and the like. The treatment is carried out during the period of time from 1 to 4 hours and at a temperature in the range from 40°C to boiling point of the halogenated hydrocarbon. The resulting product is then typically washed with an inert hydrocarbon solvent such as hexane.

In accordance with another method, magnesium dichloride is pre-activated in accordance with well known methods and then treated with excess TiCl4at a temperature in the range from about 80 to 135°in the presence of electrondonor what's connections. Processing using TiCl4repeated and the solid is washed with hexane to remove unreacted TiCl4.

Another method comprises conducting the reaction between the alcoholate or chloralkali magnesium (especially chloralkali received in accordance with USP 4220554) and excess TiCl4in the presence of electron-donating compounds at a temperature in the range from approximately 80 to 120°C.

In accordance with the preferred method of the solid catalyst component can be obtained by the reaction of titanium compounds of formula Ti(OR)n-yXywhere n denotes the valence of titanium, and the mean number in the range from 1 to n, predpochtitelno TiCl4with magnesium chloride, resulting from an adduct of formula MgCl2d, where p denotes a number in the range from 0.1 to 6, preferably from 2 to 3.5, a R means a hydrocarbon radical containing 1-18 carbon atoms. The adduct can be appropriately obtained in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct during the process in terms of mixing with the melting temperature of the adduct (100-130°). Then the emulsion is rapidly cooled, thus stimulating the solidification of the adduct in form of spherical particles. Examples of the spherical is duchow, obtained in accordance with the method described in USP 4399054 and USP 4469648. Thus obtained adduct can be directly introduced into the reaction with the compound of Ti, or it may be first subjected to dealcoholization in a thermally controlled conditions (80-130° (C) thus, to obtain an adduct in which the number of moles of alcohol in the General case is less than 3, preferably is in the range from 0.1 to 2.5. The reaction with the compound of Ti can be the result of the suspension of the adduct (dealcoholizing or as such) in cold TiCl4(usually at 0°C); the mixture is heated up to 80-130°C and maintained at this temperature for 0.5-2 hours. Processing using TiCl4it is possible to carry out one or more times. Electron-donating compounds may be added during processing using TiCl4. They can be added together during the same processing using TiCl4or separately in two or more treatments.

Obtaining catalyst components in spherical form are described, for example, in European patent applications EP-A-395083, EP-A-553805, EP-A-553806, EPA-601525 and WO 98/44009.

The solid components of the catalyst obtained in accordance with the above method, characterized by the value of the square of the specific surface (according to brown the ware-Emmett-teller) is usually in the range from 20 to 500 m 2/g, preferably from 50 to 400 m2/g and a total porosity (according to the method of Brunauer-Emmett-teller)exceeding 0.2 cm3/g, preferably in the range from 0.2 to 0.6 cm3/year Porosity (mercury method)due to pores with radius up to 10000 Å, is usually in the range from 0.3 to 1.5 cm3/g, preferably from 0.45 to 1 cm3/year

Another method of obtaining a solid component of catalyst of the present invention includes halogenoalkane derived dihydrogenmonoxide magnesium, such as dialkoxy or diarylike magnesium solution of TiCl4in aromatic hydrocarbon (such as toluene, xylene and the like) at temperatures in the range from 80 to 130°C. Processing using TiCl4in the solution of aromatic hydrocarbon can be repeated one or more times, and during one or more data processing type electron-donating compound.

In any of these ways to get the desired electron-donating compounds and, in particular, those selected from esters of carboxylic acids, can be added as such, or alternatively they can be obtained by using an appropriate precursor capable to be transformed in the desired electron-donating compound in the result, e.g. the, known chemical reactions such as esterification, transesterification, and the like.

Regardless of the used method for obtaining a finite number of two or more electron-donor compounds is such that the molar ratio in the calculation of the MgCl2is in the range from 0.01 to 1, preferably from 0.05 to 0.5.

The solid components of catalyst corresponding to the present invention, become catalysts for polymerization of olefins as a result of their reaction with alumoklyuchevskite compounds in accordance with known methods.

In particular, the object of the present invention is a catalyst for polymerization of olefins CH2=CHR, in which R means hydrogen or a hydrocarbon radical containing 1-12 carbon atoms, which contains the reaction product between:

(i) a solid catalyst component described above

(ii) ORGANOMETALLIC compound and

(iii) an external electron-donor compound.

The ORGANOMETALLIC compound (ii) is preferably chosen among the Al-alkyl compounds and, in particular, among the derivatives of trialkylamine, such as, for example, triethylamine, triisobutylaluminum, tri-n-bucillamine, tri-n-hexylamine, tri-n-octylamine. You can also use halides alkylamine, hydrides alkylamine of elisashvili alkylamine, such as AlEt2Cl and Al2Et3Cl3possibly in a mixture with the above trialkylaluminium.

Suitable external electron donors (iii) include silanes, ethers, esters, amines, heterocyclic compounds and ketones. A particular class of preferred external donor compounds is that class of silanes of the formula Ra5Rb6Si(OR7)cwhere a and b denote integers ranging from 0 to 2, p means an integer in the range from 1 to 4 and the sum (a+b+C) is 4; R5, R6and R7mean alkyl, alkylene, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred silicon compounds in which a is 1, b is 1, is 2, at least one of R5and R6selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms, optionally containing heteroatoms, a R7means C1-C10alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexanecarboxylic, dicyclopentadienyliron.

Although the above-described catalysts allow to obtain propylene polymers with a good level of insolubility in xylene, a high level is the obsession of stereoblock and broad MWD, it was found that polymers with a particularly increased levels stereoblock and broad MWD can be obtained by using as an external donor specific silanes described by the above formula, with relatively low ability stereoregularity. The term "low ability stereoregularity indicated silanes, which in standard conditions of polymerization, described below, allow you to obtain propylene polymers with levels of the pentad (mmmm), equal to or less than 97%. The person skilled in the art will easily be able to characterize the ability of stereoregularity corresponding silanes, having made the test polymerization under the conditions described below. In addition, it was found that the group of silanes with low ability stereoregularity are silanes described by the formula above, in which R5means methyl, R6means C1-C15linear alkyl, and R7means linear C1-C4alkyl. Preferred examples of such silanes are n-propylmethyldimethoxysilane; n-butylethylmagnesium; n-intermediolateral; n-getselectedindexes; n-octylpyrimidine; n-decimeterlevel. Another group of silanes with low ability stereoregularity is a group, the prescription formula, the above, in which equal 3 or 4. Particularly preferred allyltriethoxysilane and tetraalkoxysilane, in which R7means linear C1-C8alkyl.

Another group of silanes with low ability stereoregularity are silanes described by the formula above, in which R5means triptorelin group, optionally substituted, R6means C1-C6linear alkyl or piperidino group, optionally substituted, and R7means linear C1-C4alkyl. Preferred examples of such silanes are (3,3,3-Cryptor-n-propyl)(2-ethylpiperidine)dimethoxysilane, methyl(3,3,3-Cryptor-n-propyl)dimethoxysilane.

Electron-donating compound (iii) is used in such amount to provide a molar relationship between alumoorganic connection and the specified electron-donor compound (iii) in the range from 0.1 to 500, preferably from 1 to 300, and more preferably from 3 to 100.

The polymerization method may be implemented in accordance with known techniques, for example, suspension polymerization using as a diluent inert hydrocarbon solvent or the polymerization in mass, using as the reaction medium liquid monomer (for example, propylene. In addition, it is possible to implement a method of polymerization in the gas phase, conducting the reaction in one or more reactors in a fluidized or mechanically mixed layer.

The polymerization is in General carried out at a temperature in the range from 20 to 120°C, preferably from 40 to 80°C. If the polymerization is carried out in a single phase, the working pressure will typically be in the range of from 0.5 to 5 MPa, preferably from 1 to 4 MPa. When curing in mass operating pressure is typically in the range from 1 to 8 MPa, preferably from 1.5 to 5 MPa.

As already explained above, the catalysts of this invention when used for polymerization of propylene allow to obtain polymers with a range of isotacticity (expressed through the percentage of the mmmm pentad), MWD, levels stereoblock, such that they are particularly suitable for use in applications of Warr. In particular it should be noted that high values of the indicator of polydispersity (P.I.) is obtained by polymerization in a single phase, that is, when essentially modal distribution that helps to prevent any problems caused by the heterogeneity of the product.

Therefore, another object of the present invention is a propylene polymer with the following characteristics is:

the levels stereoblock 18% or higher as measured by the TREF method described below;

the rate of polydispersity at least equal to 5, and

the percentage of the pentad (mmmm), measured by NMR, less than or equal to 97.

The levels stereoblock preferably higher than 20, and more preferably higher than 22. P.I. preferably higher than 5,3, and the percentage of the pentad preferably less than 96,5, and more preferably less 95,5. In addition, it was found that particularly interesting polypropylene are those that are described above and which is additionally characterized by the fact that the discover in the analysis according to the method TREF presence faction, eluruumi at a temperature in the range from 110° to 114°S, which accounts for more than 25% of the total weight of the polymer. It preferably accounts for more than 33%. Also preferred polypropylene with TREF profile, such that the fraction elyuirovaniya at a temperature in the range from 115° to 120°With, have a value in the range from 0.1 to 10%, preferably from 0.5 to 5% of the total weight of the polymer.

METHODS OF CHARACTERIZATION.

Test extractibility electron-donating (ED) connections.

A. preparation of solid catalyst component.

In purged with nitrogen chetyrehosnuju round flask with a volume of 500 ml at 0&x000B0; With introduced 250 ml of TiCl4. When mixing was introduced 10.0 g microspheroidal MgCl2·2,8C2H5OH (obtained in accordance with the method described in example 2 in USP 4399054, but when carrying out the reaction at 3000 rpm instead of 10000). Also added 4.4 mmol selected electron-donating compound.

The temperature was increased to 100°and this temperature was maintained for 120 minutes and Then the stirring was stopped, gave the opportunity for a solid product to settle and the supernatant liquid poured the water trap.

Added 250 ml of fresh TiCl4. The mixture was subjected to reaction at 120°C for 60 minutes under stirring and then the supernatant liquid was poured siphon. Solid phase (A) was washed six times with anhydrous hexane (6×100 ml) at 60°C, dried in vacuum and analyzed for the quantitative determination of the content of Mg and electron-donating compounds. The type electron-donating compound and its molar ratio per Mg (a) are shown in table 1.

C. Treatment of the solid phase A.

In a glass reactor with a shirt, a mechanical stirrer and a filtration membrane with a volume of 250 ml in a nitrogen atmosphere was introduced 190 ml of anhydrous n-hexane, 19 mmol AlEt3and 2 g of catalyst component obtained as described in A. the Mixture was heated at 60°C for 1 hour with stirring (soon the be mixing at 400 rpm). The mixture is then filtered, washed four times with n-hexane at 60°and, finally, dried in vacuum for 4 hours at 30°C. Then the solid phase was analyzed to quantify the contents of Mg and electron-donating compounds. The type electron-donating compound and its molar ratio per Mg (ratio) shown in table 1. The extractibility of electron-donor compounds was calculated according to the following formula: % extracted ED = (A - ratio)/ratio A.

The microstructure of the polymer.

50 mg of each fraction insoluble in xylene, was dissolved in 0.5 ml of C2D2Cl4.

Spectra13With NMR were obtained using the device Bruker DPX-400 (100,61 MHz, pulse 90°delay between pulses 12). For each spectrum collected approximately 3000 transient States; as peak comparisons used the peak of the mmmm pentad (at 21.8 ppm).

Analysis of the microstructure was performed as described in the literature (Polymer, 1984, 25, 1640, by Jnoue Y. et al. and Polymer, 1994, 35, 339, by R. Chujo et al.).

The determination of the level of insolubility in xylene (X.I.).

2.5 g of polymer was dissolved in 250 ml of o-xylene under stirring at 135°C for 30 minutes, then the solution was cooled to 25°and after 30 minutes the insoluble polymer was filtered. The resulting solution was evaporated in a stream of nitrogen, and the OST is OK was dried and weighed to determine the percentage of soluble polymer, and then the difference X.I. in %.

Method TREF.

Fractionation of the polymer by the method TREF conducted by dissolving 1 g of a propylene polymer in o-xylene at 135°and With slow cooling (20 hours) up to 25°on a column filled with glass beads. Elution o-xylene (600 ml/h) first performed at 25°C for 1 hour to obtain a fraction soluble in xylene. The column temperature was then increased from 25 to 95°with a speed of 0.7°C/min without elution and the temperature was maintained at 95°C for 2 hours, then was suirable at this temperature for 1 hour to obtain individual fractions. Finally, elution was continued by increasing the temperature from 95 to 120°With speeds of 3°C/h, collecting individual fractions for temperature intervals of 1°C. In accordance with the present invention, the content of stereoblock is considered as the full weight of the fractions, insoluble in xylene at 25°With that suiryudan at a temperature of less 100°With, in the total weight of the polymer.

Indicator definition polydispersity (P.I.).

This property is rigidly connected with the molecular weight distribution of the considered polymer. In particular, it is inversely proportional to the creep resistance of the polymer in the molten state. Specified soprotivlenie, called separation modules with a low modulus value (500 PA), was determined at a temperature of 200°using plastomer with parallel plates model RMS-800 supplied by the company RHEOMETRICS (USA), operating at a frequency which increases from 0.1 rad/sec to 100 rad/sec. From the magnitude of the separation modules can be obtained P.I. using the equation:

P.I.=54,6·(separation modules)-1,76,

where separation of modules is defined as:

separation modules = frequency at G'=500 PA/frequency at G"=500 PA,

where G' is the storage modulus, a G" is the loss modulus.

Standard test polymerization to determine stereoregularity silane.

Preparation of solid catalyst component.

In purged with nitrogen chetyrehosnuju round flask with a volume of 500 ml at 0°were injected With 250 ml of TiCl4. When mixing was introduced 10.0 g microspheroidal MgCl2·2,8C2H5OH (obtained in accordance with the method described in example 2 in USP 4399054, but when carrying out the reaction at 3000 rpm instead of 10000) and 10.1 mmol of diisobutylphthalate. The temperature was increased to 100°C and maintained for 120 minutes and Then the stirring was stopped, gave the opportunity for a solid product to settle and the supernatant liquid poured the water trap. Then add 250 ml of fresh TiCl4. Homes evaluation of the Gali reaction at 120° C for 60 min and then the supernatant liquid was poured siphon. The solid phase was washed six times with anhydrous hexane (6×100 ml) at 60°C. Finally, the solid was dried in vacuum.

In purged by a stream of nitrogen at 70°C for one hour, the autoclave with a volume of 4 liters in a stream of propylene at 30°were injected With 75 ml of anhydrous hexane containing 800 mg AlEt3the silane in an amount such that the gain ratio Al/Si is equal to 20, and 10 mg of solid catalyst component obtained as described above. The autoclave was closed. Added to 1.5 N. hydrogen and then with stirring was applied at 1.2 kg of liquid propene. The temperature was increased to 70°With five minutes and the polymerization was carried out at this temperature for two hours. Unreacted propylene was removed, the polymer was collected, dried at 70°C in vacuum for three hours, weighed and determined the level of insolubility in xylene. The insoluble portion was analyzed to determine the percentage of the pentad (mmmm) in accordance with the method described above.

Examples 1-4 and comparative examples 1-3.

Preparation of solid catalyst components.

In purged with nitrogen chetyrehosnuju round flask with a volume of 500 ml at 0°were injected With 250 ml of TiCl4. When mixing was introduced 10.0 g microspheroidal MgCl2·2,8C2H5OH (obtained in the fit is shown by the way that described in example 2 in USP 4399054, but when carrying out the reaction at 3000 rpm instead of 10000). As an internal donor (donor) was also introduced to 7.6 mmol previously obtained mixture of esters. The type (s) internal donors and the amounts given in table 2.

The temperature was increased to 100°and maintained the temperature for 120 minutes and Then the stirring was stopped, gave the opportunity for a solid product to settle and the supernatant liquid poured the water trap.

Added 250 ml of fresh TiCl4. The mixture was subjected to reaction at 120°C for 60 min and then the supernatant liquid was poured siphon. The solid phase was washed six times with anhydrous hexane (6×100 ml) at 60°C. Finally, the solids were dried in vacuum and analyzed. The types and amounts of esters (% (wt.)) and the amount of Ti (% (wt.)), contained in the solid component of catalyst are shown in table 2.

Examples of polymerization of 5 to 17 and comparative examples C4-C10.

In purged by a stream of nitrogen at 70°C for one hour, the autoclave with a volume of 4 liters in a stream of propylene at 30°were injected With 75 ml of anhydrous hexane containing 7 mmol AlEt3the external donor (type and amount are shown in table 3) and 10 mg of solid catalyst component. The autoclave was closed. Added to 1.5 N. hydrogen and then with stirring was applied at 1.2 kg of liquid propylene. Temp is the temperature increased to 70° With five minutes and the polymerization was carried out at this temperature for two hours. Unreacted propylene was stravovali, the polymer was recovered and dried at 70°C in vacuum for three hours, and then weighed and fractionally using o-xylene to determine the number of fraction insoluble in xylene (X.I.) at 25°and its microstructure.

The results of polymerization are shown in table 3.

Table 1.
EDThe ratio of A ED/Mg (mmol/g-atom)Attitude And ED/Mg (mmol/g-atom)Extracted ED (% (mol.))
Type
Racemic diethyl-2,3-Diisopropylamine65,262,84
Meso-diethyl-2,3-Diisopropylamine39,323,939
Diisobutylphthalate48,88,882

Table 2.
Conditions of receivingComposition
ExampleServed upon receivingTiN is extracted succinate Extractable ED% dextrogirum succinate per full content

donor
Extragonadal succinateExtractable ED
No.TypemmolThe type (s)mmol% (mass.)Type% (mass.)Type% (mass.)% (mol.)
1And0,76In6,843,3And2,4In7,624
2And1,14In6,46the 3.8And3,24In7,5630
3And1,67In1,374,2And3,53In1,1730
DIBP4,56DIBP7,6
41,25D1,793,4 4,4D1,4633
DIBP4,56DIBP6,6
C1------In7,6the 3.8---In10,7---
C2And2,8In4,83,5Andof 7.75In7,4551
C3------DIBP7,62,5---DIBP7,1---
A = racemic diethyl-2,3-Diisopropylamine.

In = meso diethyl-2,3-Diisopropylamine.

C = the racemic Diisobutyl 2,3-Diisopropylamine.

D = meso Diisobutyl 2,3-Diisopropylamine.

DIBP = diisobutylphthalate.

1. Solid catalyst component for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical comprising 1 to 12 carbon atoms containing compound of titanium, which has at least one link Ti-halogen, and at least two electron-donating compound, Unesennye media dichloride Mg, the total number of electron-donor compounds is in a molar ratio to the MgCl2, comprising from 0.01 to 1, characterized in that at least one electron-donating compounds, which is present in a quantity in the range of 15-50 mol.% in relation to the total number of donors, which are selected from esters of succinic acids, which are extrapyramidal, more than 20 mol.%, and at least another electron-donating compound, which is selected from esters of mono - or dicarboxylic organic acid, which is extracted in more than 30 mol.%, where extractibility is calculated by the formula:

% extracted Elektrodinamika connection = ((A - ratio)/(a)·100%,

where a is the molar ratio Elektrodinamika connection to magnesium determined after receipt of the test component catalyst comprising TiCl4and MgCl2·C2H5OH;

the ratio In molar ratio of the same Elektrodinamika connection to magnesium determined after additional processing of the above test component of the catalyst triethylaluminium;

thus extrapyramidal Elektrodinamika connection is defined in the same terms as the extractibility.

2. A solid component rolled atora according to claim 1, characterized in that the number dextrogirum succinate is in the range from 20 to 40 mol.% in the calculation of the total number of electron-donor compounds contained in the catalyst.

3. A solid component of catalyst according to claim 1, characterized in that extragenomic succinate can be proektirovanii not more than 15 mol.%.

4. A solid component of catalyst according to claim 1, characterized in that the extracted electron-donating compound can be proektirovanii more than 40 mol.%.

5. A solid component of catalyst according to claim 1, characterized in that it is not extractable with succinate are compounds described by formula (I)

in which the radicals R1and R2identical or different, denote C1-C20linear or branched alkyl, alkenylphenol, cycloalkyl, aryl, arylalkyl or alcylaryl group, optionally containing heteroatoms, and the radicals R3and R4identical or different, denote C1-C20alkyl, cycloalkyl, aryl, arylalkyl or alcylaryl group, optionally containing heteroatoms, provided that at least one of them is a branched alkyl;

moreover, these compounds are in relation to the two asymmetric carbon and the Ohm, indicated in the structure of the formula (I), stereoisomers related to the type (S,R) or (R,S)that are present in pure form or as mixtures.

6. A solid component of catalyst according to claim 1, where the extracted electron-donating compound selected from esters of phthalic acid.

7. A solid component of catalyst according to claim 1, where the extracted electron-donating compound selected from alilovic esters of phthalic acid.

8. A solid component of catalyst according to claim 1, where the extracted electron-donating compound selected from (S,S), (R,R) or mesoform of succinate formula (I).

9. A solid component of catalyst according to claim 8, further containing alkalemia esters of phthalic acids in the quality of the extracted donors.

10. A solid component of catalyst according to claim 1, where extragenomic donors use a mixture of succinate according to claim 5.

11. A solid component of catalyst according to claim 1 to the size of the specific surface (according to the method of Brunauer-Emmett-teller) in the range from 20 to 500 m2/g and a total porosity (according to the method of Brunauer-Emmett-teller)exceeding 0.2 cm3/year

12. The catalyst for polymerization of olefins, containing

(i) a solid component of catalyst according to claim 1,

(ii) ORGANOMETALLIC compound and

(iii) an external electron-donor compound.

13. The catalyst according to item 12, the de ORGANOMETALLIC compound is an Al-alkyl compound.

14. The catalyst according to item 12, where the external electron-donor compound selected from silanes of the formula Ra5Rb6Si(OR7)cwhere a and b denote integers ranging from 0 to 2, p means an integer in the range from 1 to 4 and the sum (a+b+C) is 4; R5, R6and R7mean alkyl, alkylene, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.

15. The catalyst 14, where the silane is chosen from silanes with low ability stereoregularity.

16. The catalyst 14, where the silane is chosen from the compounds in which R5means methyl, R6means C1-C15linear alkyl, and R7means linear C1-C4alkyl.

17. The catalyst 14, where the silane is chosen from the compounds in which R5means triptorelin group, optionally substituted, R6means C1-C6linear alkyl or piperidinyl group, optionally substituted, and R7means linear C1-C4alkyl.

18. The catalyst 14, where the silane is chosen from silanes, which equals 3 or 4.

19. A method of obtaining a propylene polymer, wherein the polymerization is carried out in the presence of a catalyst according to any one of p-18.

20. Propylene polymer having the following characteristics: the level of content stereoblock 18% or higher as measured according to the method of TREF; the rate of polydispersity at least equal to 5, and the percentage of the pentad (mmmm), measured by NMR, less than or equal to 97.

21. The propylene polymer according to claim 20, with levels stereoblock higher than 20%.

22. The propylene polymer according to claim 20 or 21 with Index Polydispersity (P.I.) is higher than 5,3.

23. The propylene polymer according to any one of p-22 with the percentage of the pentad below 96,5.

24. The propylene polymer according to any one of p-23 that detect when analysed by the TREF technique the presence of a fraction, eluruumi at a temperature in the range from 110° to 114°S, which accounts for more than 25% of the total weight of the polymer.



 

Same patents:

FIELD: chemical technology, catalysts.

SUBSTANCE: invention relates to components of catalyst used in synthesis of ethylene (co)polymers by using methods of (co)polymerization in the gaseous phase, in suspension or in mass. The prepolymerized catalyst for polymerization of ethylene being optionally in mixtures with olefins of the formula: -CH2=CHR wherein R represents (C1-C12)-alkyl group comprises a non-stereospecific solid component of catalyst comprising Ti, Mg and halogen. A solid component of catalyst is prepolymerized with α-olefin of the formula: -CH2=CHR1 wherein R1 represents (C1-C8)-alkyl group in the presence of alkylaluminum compound in the mole ratio Al/Ti from 0.001 to 50 in such degree that the amount of α-olefin prepolymer is up to 100 g/g of solid component of catalyst. Also, invention describes a method for (co)polymerization of ethylene that is carried out in the presence of the prepolymerized catalyst and alkylaluminum compound. Invention provides preparing polymers of high bulk density and high activity, and decreasing formation of small particles also.

EFFECT: improved and valuable properties of catalyst.

18 cl, 8 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely phenyltrichloromethane PhCCl3. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 4 ex

FIELD: polymerization catalysts.

SUBSTANCE: invention, in particular, relates to preparation of Ziegler-type catalyst comprising transition metal (titanium or vanadium) compound on magnesium-containing carrier. Carrier is prepared via interaction of organomagnesium compound-containing solution depicted by formula Mg(C6H5)2·nMgCl2·mR2O, wherein n=0.37-0.7, m=2, and R2O is ether with R = i-Am or n-Bu, with chlorination agent, namely XkSiCl4-k, wherein X is OR' or R', in which R can be C1-C4-alkyl or phenyl, and k=1-2. Above named polymerization and copolymerization process are carried out with catalyst of invention in combination with cocatalyst.

EFFECT: reduced size distribution range of polymers and enabled average particle size control.

3 cl, 1 tbl, 13 ex

The invention relates to methods for macromolecular higher poly-alpha-olefins, in particular polyacene, and catalysts for carrying out the method

The invention relates to the components of the catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and at least one 1,3-W, which forms complexes with anhydrous magnesium dichloride in an amount of less than 60 mmol per 100 g of MgCl2and without substitution reactions with TiCl4or reacting in the amount less than 50 mol%, and at least one ester of mono - or polycarboxylic acid, and 1,3-diesters selected from compounds of the formula (II)

where the group RIIIidentical or different, represent hydrogen or C1-C18hydrocarbon group; groups of RIVidentical or different, have the same meaning as RIIIexcept that they cannot be hydrogen; each of the groups RIII- RIVmay contain heteroatoms selected from Halogens, N, O, S and Si, and the radicals RVidentical or different, are selected from the group consisting of hydrogen; Halogens, preferably C1 or F; C1-C20alkyl radicals with a straight or branched chain; C3-C20cycloalkyl,6e radicals Rvcan be connected to each other to form a condensed cyclic structures, saturated or unsaturated, optionally substituted, RVIradicals selected from the group consisting of halogen, preferably C1 or F; C1-C20alkyl radicals, linear or branched; C3-C20cycloalkyl, C6-C20aryl, C7-C20alkalinic and C7-C20Uralkalij radicals; the radicals RVand RVIoptionally contain one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both

The invention relates to a component of a solid catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an electron donor selected from substituted succinates formula

The invention relates to a method for producing a catalyst for polymerization of olefins and method of polymerization of olefin monomers with its use

The invention relates to a method (generowania type in a suspension of liquid monomer) obtain ethylene-propylene elastomers (EP) and ternary ethylene-propylene-diene elastomers (EPDM)

FIELD: polymerization catalysts and polymerization processes.

SUBSTANCE: high-activity ethylene (co)polymerization-appropriate supported titanium-based catalyst is composed of (A) supported catalytic component, notably titanium-containing active component on porous silica, containing at least one titanium compound, at least one magnesium compound, at least one alkylaluminum compound, at least one halide promoter, at least one electron-donor compound, and inert porous silica carrier, wherein halide promoter belongs to the class of compounds described by general formula F-R1[R2bX(3-b)], in which F represents oxygen-containing functional group reactive to organoaluminum compound, titanium compound, and hydroxyl groups; R1 bivalent C1-C6-aliphatic or aromatic grouplinked to functional group F; R2 hydrogen atom, unsubstituted or halogen-substituted C1-C6-alkyl, halogen-substituted C3-C6-cycloalkyl, or halogen-substituted C6-C10-aryl; b=0,1 or 2; and X represents fluorine, chlorine, or bromine atom; and (B) alkylaluminum cocatalyst. Invention also discloses catalyst preparation method and ethylene (co)polymerization process in presence of above-defined catalyst.

EFFECT: enabled preparation of catalyst with good morphology and flowability of particles, high catalytic activity, good sensitivity to addition of hydrogen, and ability to include comonomer; improved particle morphology of polymers.

15 cl, 2 tbl, 11 ex

The invention relates to the components of the catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and at least one 1,3-W, which forms complexes with anhydrous magnesium dichloride in an amount of less than 60 mmol per 100 g of MgCl2and without substitution reactions with TiCl4or reacting in the amount less than 50 mol%, and at least one ester of mono - or polycarboxylic acid, and 1,3-diesters selected from compounds of the formula (II)

where the group RIIIidentical or different, represent hydrogen or C1-C18hydrocarbon group; groups of RIVidentical or different, have the same meaning as RIIIexcept that they cannot be hydrogen; each of the groups RIII- RIVmay contain heteroatoms selected from Halogens, N, O, S and Si, and the radicals RVidentical or different, are selected from the group consisting of hydrogen; Halogens, preferably C1 or F; C1-C20alkyl radicals with a straight or branched chain; C3-C20cycloalkyl,6e radicals Rvcan be connected to each other to form a condensed cyclic structures, saturated or unsaturated, optionally substituted, RVIradicals selected from the group consisting of halogen, preferably C1 or F; C1-C20alkyl radicals, linear or branched; C3-C20cycloalkyl, C6-C20aryl, C7-C20alkalinic and C7-C20Uralkalij radicals; the radicals RVand RVIoptionally contain one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both

The invention relates to a component of a solid catalyst for polymerization of olefins CH2=CHR, where R is hydrogen or a hydrocarbon radical with 1-12 carbon atoms, comprising Mg, Ti, halogen and an electron donor selected from substituted succinates formula

The invention relates to a solid titanium catalyst component for use as a catalyst in the production of homopolymers or copolymers of olefins and to a method for producing a solid titanium catalyst component

FIELD: polymerization processes and catalysts.

SUBSTANCE: inventors claim organometallic catalytic system for production of elastomer stereoblock polypropylene via polymerization of propylene, which system contains octahedral hexafluorine-substituted bis-acetylacetonate complex of formula (CF3COCHCOCF3)2MCl2, where M represents Ti or Zr, and, as organoaluminum compound, AlR3, where R represents ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl, and; additionally, organomagnesium compound MgR2 or MgRX, where R is alkyl radical with 1-4 carbon atoms and X = Cl, Br, or I, M/Mg/Al molar ratio being 1.0:2.0:(100-500). Claimed is also a method for production of elastomer stereoblock polypropylene via polymerization of propylene in presence of homogenous catalyst system at transition metal complex concentration 10-3-10-5 mole/L.

EFFECT: increased catalytic activity.

2 cl, 1 tbl, 22 ex

FIELD: organic chemistry, chemistry of polymers.

SUBSTANCE: invention relates to two new compounds of the formula (1) and formula (11) that are used for destruction of polypropylene. Also, invention relates to a composition used for destruction of polypropylene in preparing polyacrylates comprising compounds of formulae (1) and (11). Invention provides preparing effective initiating agents for preparing low-molecular acrylate resins.

EFFECT: improved preparing method, valuable properties of compounds.

3 cl, 2 tbl, 8 dwg, 9 ex

The invention relates to the synthesis of polyolefins in the presence of efficient homogeneous catalytic systems based on metallocene complexes of group IVB and alyuminiiorganicheskikh connections
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