Polymer composition

 

(57) Abstract:

Composition based on olefin polymer consists of /I/ -olefin/polyene copolymerizing polymer in the amount of 0.005 to 99 wt.%, moreover, the specified-olefin/polyene copolymerize polymer includes (i) a copolymer of olefin and polyene and (ii) olefin polymer, and /II/ olefinic polymer in an amount of from 1 to 99,995% by weight. This composition based on olefin polymer consisting of olefin/polyene copolymerizing polymer /I/ and olefin polymer (II) has a high voltage melt and excellent plasticity in pneumatomachi, and it can also be molded in large containers and D. p. when using injection blow molding or the like. 5 C.p. f-crystals.

The invention relates to a composition based on olefin polymer, and in particular to olefin polymer compositions on the basis of a-olefin/polyene copolymerizing polymer high voltage melt.

Olefin polymers such as low density polyethylene, linear low density polyethylene, polypropylene have not only transparency, but also mechanical strength, e.g. the extrusion etc.

The above olefin polymers typically have low voltage melt (MT) as a result of which it is difficult to mould into containers large containers (such as bottles), for example using blowing, or it is difficult to mould housings of electrical appliances, such as vacuum forming.

As a result of these limitations in molding technology, the range of the obtained molded products is also limited. In other words, despite the many wonderful characteristics of olefinic polymers, their applications are limited.

Moreover, in the case of polypropylene, there are such problems that are associated with the emergence of the phenomenon of extraction and restriction mode molding upon receipt of the polypropylene film by the method of pneumaturia due to low pressure of the melt. To eliminate these defects, the way of doing in polypropylene polyethylene, high pressure low density or the like perform the traditional method of blow molding to increase the tension of the melt, and thereby stabilize the bubbles. However, this method sometimes leads to the decrease of the strength properties of the film and reduce its transparency.

Based on what I could molding containers of large capacity, for example bottles by the method of blowing of the melt and cover with electrical vacuum extrusion of these polymers, and therefore can greatly extend the range of applications of olefin polymers.

In addition, when forming films of olefin polymers with high voltage melt method blast can stabilize the bubbles, and the molding carried out at higher speed.

For these reasons needed was the development of olefinic polymers such as polypropylene, low density polyethylene and linear low-density polyethylene having a high voltage melt.

The authors of the present invention conducted a study on olefin polymers of high voltage melt to meet the above requirements, and as a result, they found that a-olefin/polyene copolymerize polymer high voltage melt can be obtained by way of copolymerization of a-olefins and a polyene compounds with the formation of the catalyst for polymerization of olefin, comprising a catalytic component compounds of the transition metal and ORGANOMETALLIC catalytic component, with a follow-up study on the basis of the results obtained and installed, the composition based on olefin polymer containing a-olefin/polyene copolymerize polymer and well-known olefin polymer, with a-olefin/polyene copolymerize polymer obtained by copolymerization of a-olefins and polyene in the presence of a catalyst for polymerization of olefin, followed by polymerization of the olefin to obtain the above-mentioned final product has a high rate of voltage melt, high capacity molded using molding technology, for example, blown, etc. as a result of these studies was established the present invention.

The purpose of the present invention to provide a composition based on olefin polymer having a high capacity for forming, for example films, and high voltage melt resulting from it can be molded using blowing from the melt containers of large capacity, though usually such molding elusive.

The present invention provides a composition based on olefin polymer, consisting of:

(I) a-olefin/polyene copolymerizing polymer in an amount of from 0.005 to 99 wt. moreover, the specified a-olefin/polyene copolymerizing Edinboro polymer in an amount of from 1 to 99,995 wt. Alpha-olefin/polyene copolymerize polymer (I) can be obtained by polymerization or copolymerization of olefin to education pre-polymerized catalyst to obtain the olefin polymer (ii), with the specified terpolymerization catalyst containing a copolymer of a-olefin and polyene (I) obtained by copolymerization of a-olefins and Poliana with the formation of the catalytic component, consisting of:

A/ catalytic component compounds of the transition metal and

B/ catalytic component on the basis of the ORGANOMETALLIC compound containing a metal selected from the group of metals of Groups 1-3 of the Periodic table, taken in the total amount of olefin and polyene compounds from 0.01 to 2,000 grams per gram of catalytic component of the transition metal compounds (A). This composition based on olefin polymers containing a-olefin/polyene copolymerize polymer /I/ and the olefin polymer (II), discussed earlier, has a high voltage melt and high forming ability by using the method of razuki and from it you can get containers of large capacity and other Products pneumoperitoneum etc.

sanija.

Used in this description, the term "polymerization" sometimes means not only homopolymerization", but also "copolymerization", when used herein, the term "polymer" also means "Homo-polymer" and "copolymer".

Composition based on olefin polymers of the present invention includes:

I/ a-olefin/polyene copolymerize polymer and

II/ olefinic polymer.

Consider first a-olefin/polyene copolymerize polymer /I/ used in the present invention.

Used in the present invention a-olefin/polyene copolymerize polymer contains:

(i) a-olefin/polyene copolymer and

(ii) -olefin polymer.

These a-olefin-polyene copolymerize polymer /I/ can be obtained for example by polymerization or copolymerization of olefin to the pre-polymerized catalyst to form olefin polymer (ii), with the specified pre-polymerized catalyst contains a-olefin/polyene copolymerize polymer /I/, obtained by the copolymerization of a-olefins and Poliana with the formation of a catalyst consisting of catalytics the value /B/.

Will be described below is used to obtain a-olefin/polyene copolymer /II/ a-olefin and the polyene compound.

Used in this invention a-olefins belong to C2-20alpha-olefins. As specific examples are ethylene, propylene, 2-butene, 1-penten, 1-hexene, 3-methyl-1-butene, 3-methyl-1-penten, 4-methyl-1-penten, 1-octene, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene and 1 achozen. They can be used separately, or in combination with each other.

Used in this invention a-olefins can have the same value, or different from the a-olefin used to obtain the olefin polymer (II), which will be described below.

Among the above a-olefin is preferable to use ethylene, propylene, 1-butene, 4-methyl-1-penten-3-methyl-1-butene and 1-achozen.

As specific examples of the unsaturated compounds include: aliphatic a polyene, such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,5-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadi is h, 1,13-tetradecane, 1,5,9-decatriene-butadiene and isoprene; vinylcyclohexane, vinylnorbornene, ethylidenenorbornene, Dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene;

alicyclic the polyene, such as 1,4-diphenylsiloxane, 1,3-diphenylsiloxane, 1,3-diphenylcyclopropane, 1,5-diphenylsiloxane, 1-allyl-4-vinylcyclohexane, 1,4-dialectological, 1-allyl-5-vinylcyclopentane, 1,5-dialectically, 1-allyl-4-isopropylcyclohexane, 1-Isopropenyl-4-vinylcyclohexane, and 1-Isopropenyl-3-vinylcyclopentane; and

aromatic polyene, for example, divinylbenzene and minimizepersonnel.

These polyene used separately and in combination with each other.

Among the above-mentioned unsaturated compounds preferably used compounds of the invention are polynom containing 7 or more carbon atoms and having an olefinic double bond at both ends of the chain. As the most preferred polyene compounds using aliphatic or alicyclic polyene compounds with olefinic double bond at both ends of the polymer chain.

As specific examples of these preferred polyene can lead 1,6-HepB is 1,5-diphenylsiloxane, 1-allyl-4-vinylcyclohexane, 1,4-dialectological and 1,3,4-trivinylcyclohexane.

Of these polyene as the preferred aliphatic of polyene you can specify the polyene with 8 or more carbon atoms, preferably 10 or more carbon atoms and most preferred are the aliphatic polyene having an unbranched chain with 10 or more carbon atoms.

To obtain a-olefin/polyene copolymer (I) carry out the copolymerization of a-olefins and a polyene compounds on the basis of the following combinations:

ethylene 1.7 octadiene, ethylene and 1.9-decadiene, ethylene and 1,13-tetradecane, ethylene and 1,5,9-decatriene, propylene and 1.7-octadiene, propylene and 1,9-decadiene, propylene and 1,13-tetradecane, propylene and 1,5,9-decatriene, butene and 1.9-decadiene, butene and 1,5,9-decatriene, 4-methyl-1-pentene and 1.9-decadiene, 3-methyl-1-butene and 1.9-decadiene, 1 eicosene and 1.9-decadiene, propylene and 1,4-diphenylsiloxane and butene to 1,4-diphenylsiloxane.

It is advisable that the copolymer a-olefin and polyene contained a-olefin component in an amount of usually from 99,999 to 50 mol%, preferably from 99,999 to 70 mol%, more preferably from 99,999 to 75 mol% much more preference is icesto usually from 0.001 to 50 mol%, preferably from 0.001 to 30 mol%, more preferably from 0.01 to 20 and most preferably from 0.05 to 15 mol%

In addition, the copolymer of α-olefin and polyene (i) may contain constituent units derived from other olefins, which will be described later in the description, in the quantity necessary to achieve the purposes of the present invention. In this case, the units derived from other olefins present in the a-olefin/polyene copolymer (i) in an amount of usually less than 30 mol%, preferably not more than 20 mol%, more preferably not more than 15 mol%

The ratio of the components in the above-mentioned copolymer of a-olefin and polyene possible to determine the amount consumed in the reaction prior to the polymerization of a-olefins and a polyene compounds. In particular, the ratio of the components of /P/ (mol%) can be calculated from the following formula:

< / BR>
where

/Po/ is the number of moles of the unsaturated compounds uploaded for pre-polymerization;

/Pr/ is the number of moles of unreacted unsaturated compounds;

/0// the number of moles loaded for pre-polymerization of olefin;

/r/ the number of unreacted-olefin;

the value of /r/ s /Pr/ in the above formula can be determined by neprieinama the th chromatography, etc.

Examples of the olefins used for obtaining the olefin polymer (ii) necessary for the formation of a-olefin/polyene copolymerizing polymer /I/ are the above C20- C20a-olefins.

You can also use the following connections:

aromatic vinyl compounds such as styrene, substituted styrene (such as dimethylstyrene), allylbenzene, substituted allylbenzenes (such as allitaliana), vinylnaphthalene, substituted vinylnaphthalene, alienation and substituted Allington;

alicyclic vinyl compounds such as vinylcyclohexane, substituted vinylcyclohexane, vinylcyclopentane, substituted vinylcyclopentane, vinylcyclohexane, substituted vinylcyclopropanes, and allylnormorphine;

cyclic olefins, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclinea and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4 a,5,8,8A-octahydronaphthalene;

unsaturated compounds of the type of silane, such as alliteratively, allyltrimethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-Nexen, 8-trimethylsilyl-1-octene and 10-trimethylsilyl-1-mission; and

the above polyene compounds.

the sustained fashion using ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane and alienation.

Alpha-olefin/polyene copolymerize polymer /31/ contains a copolymer of a-olefin and polyene /i/ in quantities of from 0.001 to 99 wt. preferably from 0.05 to 90 wt. and olefin polymer (ii) in an amount of from 99,999 to 1 wt. preferably 99.995 to 10 wt. and more preferably from 99,99 up to 12 wt.

Among these olefin polymers of the present invention, particularly preferred is an olefinic polymer containing a copolymer of a-olefin and polyene (i) in an amount of from 0.001 to 15 wt. preferably from 0.008 to 10 wt. and olefin polymer (ii) in an amount of from 99.999 to 85 wt. especially from 99,992 to 90 wt.

The rate of melt fluidity (MFR) of the proposed olefinic polymer defined according to the standard ASTM d 1238, is not more than 5000 g/10 min, preferably in the range from 0.01 to 3000 g/10 min, more preferably from 0.02 to 2000 g/10 min, and most preferably from 0.05 to 1000 g/10 m

The specified a-olefin/polyene copolymerize polymer /1/ has the highest voltage of the melt (MT).

In the above a-olalala (MT) and the rate of melt fluidity (MFR) satisfy the following condition.

For example, if a copolymer of alpha-olefin and polyene (i) and olefin polymer (ii) both components of the a-olefin/polyene copolymerize polymer /1/ is a copolymer of ethylene and polyene and propylene, respectively, the voltage level of the melt and the rate of melt of the specified a-olefin/polyene copolymerizing polymer /1/- satisfies the following condition:

usually log/MT/0,1 log /MFR/+0,3;

preferably, log [MT]of 0.8 log [MFR]+0,5

more preferably, log [MT]of 0.8 log[MFR]+0,7

most preferably, log [MT]of 0.8 log[MFR]+0,8

If a-olefin/polyene copolymer (i) is a copolymer of an a-olefin of 3 or more carbon atoms and Poliana, and the olefin polymer (ii) is a polymer in a-olefin/polyene copolymerization polymer /1/, the tension of the melt and the rate of melt flow a-olefin/polyene copolymerizing polymer 31/ satisfies the following condition:

usually log[MT]of 0.8 log[MFR]+0,30;

preferably log[MT]of 0.8 log[MFR]+0,35;

more preferably, log[MT]of 0.8 log[MFR]+0,40

Moreover, in the case when a-olefin/polyene copolymerize polymer /1/ consists of a copolymer of ethylene and polyene (i) and polypropylene (ii), described the wound/polyene copolymerizing polymer is not less than 2.5 g, preferably not less than 3.5 g, more preferably not less than 4.0 g, more preferable not less than 4.5 g, most preferably not less than 5.0,

Characteristic viscosity / h / olefin polymer of the present invention, measured in decaline at a temperature of 135oC is from 0.05 to 20 DL/g, preferably from 0.1 to 15 DL/g, more preferably from 0.2 to 13 DL/g

In the inventive olefinic polymer, the tension of the melt and the characteristic viscosity / h / also satisfies the following condition.

For example, if a-olefin/polyene copolymer (i) and olefin polymer (ii) comprising both olefinic polymer are copolymers of ethylene and polyene and polypropylene, respectively, the tension of the melt and the characteristic viscosity of this olefin polymer satisfy the following condition: log[MT]3,7 log[(h)]-1,5;

usually: log[MT]3,7 log[(h)]-1,3;

preferably, log[MT]3,7 log[(h)]-1,1;

more preferably, log[MT]3,7 log[(h)]-1,0;

most preferably, log[MT]3,7 log[(h)]-1,0;

If as a copolymer of olefin and polyene (i) use a copolymer of a-olefins containing 3 or more carbon atoms, and Poliana, and the olefin polymer (ii) is a poly is th viscosity of this olefin polymer satisfies the following condition:

usually, log[MT]3,7 log[(h)]-1,50;

preferably, log[MT]3,7 log[(h)]of-1.45;

more preferably log[MT]3,7 log[(h)]-1,40.

Moreover, when the olefin polymer of the present invention consists of a copolymer of ethylene and polyene (i) and polyethylene (ii) as disclosed above, and has a density of about 0,92 g/cm3and characteristic viscosity /W to 1.8 DL/g, the tension of the melt is at least 2.5 g, preferably not less than 3.5 g, more preferably not less than 4.0 g, more preferable not less than 4.5 g, and most preferably not less than 5.0,

The tension of the melt can be determined by the following method.

Using the setup for measuring MT (manufactured by Toyo Seiki Seisakusho K. K.) 7 g of the polymer is loaded into the cylinder with a hole at the base and plunger, with the specified cylinder is kept at the melting temperature of the specified polymer (polypropylene: 230oC). After 5 min, the plunger descends at a speed of 10 mm/min, squeezing the specified polymer melt in the form of strands through a hole provided in the lower part of the cylinder. Extrudable strand is extruded in the form of monofilament, and wound at a speed of 25 m/min using a detector load. This CPA.

Next, the description will be described catalytic component compounds of the transition metal /A/ to obtain the above-mentioned a-olefin/polyene copolymerizing polymer /1/.

Catalytic component of the transition metal compounds (A) used in the present invention is a compound containing a transition metal selected from metals of Groups III to VIII of the Periodic table, and preferably a compound containing at least one transition metal selected from Ti, Zr, Hf, Na, Ta, Cr, and V

Examples of the specified catalytic component /A/ based on transition metal compounds include a variety of known catalytic systems, in particular, on the basis of titanium containing titanium and halogen. More specifically, in the example of catalytic systems on the basis of solid titanium can cause the catalytic component (A-1) containing titanium, magnesium and halogen, and optionally, if necessary, electron donor (a).

Methods of obtaining a catalytic component, /A-1/ on the basis of solid titanium are described in detail in the following publications. In other words, these methods are disclosed, for example, in published patent application Japan # 46(1971) 343)-19794, lined patent publications Japan N 60(1985)-26803, No. 59(1984)-147004, No. 59(1984)-149911, No. 1(1989)-201308, No. 61(1986)-151211, No. 53(1978)-58495, No. 53(1978)-87990, No. 59(1984)-206413; N 58(1983)-206613, No. 58(1983)-125706, No. 63(1988)-68606, No. 63(1988)-69806, No. 60(1985)-81210, No. 61(1986)-40306, No. 51(1976)-281189, No. 50(1975)-126590 and No. 51(1976)-92885, published patent applications in Japan No. 57(1982)-45244, No. 57(1982)-26613, and N 61(1986)-5483 lined the patent application of Japan No. 56(1981)-811, patent publication Japan N 60(1985)-37804 and No. 59(1984)-50246 lined patents Japan N 58(1983)-83006, No. 48(1973)-16986, No. 49(1974)-65999 and No. 49(1974)-86482, patent publications Japan No. 56(1981)-39767 and 56(1981)-32322 tiled applications for Japan patent No. 55(1980)-29591, No. 53(1978)-146292, No. 57(1982)-63310, No. 57(1982)-63311, No. 57(1982)-63312, No. 62(1987)-273206, No. 63(1988)-69804, N 61(1986)-21109, 63(1988)-264607, N 60(1985)-23404, NO. 60(1985)-44507, NO. 60(1985)-158204, NO. 61(1986), 55104, N 2(1990)-28201, 58(1983)-196210, N 64(1989)-54005, NO. 59(1984)-149905, NO. 61(1986)-145206, NO. 63(1988)-302, NO. 63(1988) 225605, NO. 64(1989)-69610, NO. 1(1989)-168707, NO. 62(1987)-104810, No. 62(1987)-104811, No. 62(1987)-104812 and No. 62(1987)-104813.

The specified catalytic component, /A-1/ based on titanium can be obtained when using, for example, titanium compounds, magnesium compounds, and if desired, electron donor (a) by bringing them into contact with each other.

Examples of the titanium compounds used for obtaining a catalytic component, /A-1/ based on titanium are compounds of trivalent and chetyrehvagonnye formula:

Ti(OR)gX4-g< / BR>
where

R means a hydrocarbon group, X represents a halogen atom, a denotes a number satisfying the condition 0g4.

The following describes specific examples of these compounds.

For example, tetrachloride titanium, such as TiCl4, TiBr4and TiI4.

trechaleidae connection alkoxysilane, for example:

Ti(OCH3)Cl3,

Ti(OC2H5)Cl3,

Ti(On-C4H9)Cl3,

Ti(OC2H5)Br3and

Ti(O-ISO-C4Mg)Br3.

Dogalogue connection dialaction, such as:

Ti(OCH3)2Cl2,

Ti(OC2H5)2Cl2,

Ti(On-C4Mg)2Cl2and

Ti (OC2H5)2Br

Mongaloid of trialkylamine, such as:

Ti(OCH3)3Cl

Ti(OC2H5)3Cl

Ti(On-C4Mg)3Cl, and

Ti(OC2H5)3Br

Complexes of tetraalkoxysilane, such as:

Ti(OCH3)4,

Ti(OC2H5)4,

Ti(On-C4Mg)4,

Ti(O-ISO-C4Mg)4,

Ti(O-Z-ethylhexyl)4< / BR>
Of these compounds, preferably compounds can be used in pure form or in combination with each other. In addition, they can be used after dilution with hydrocarbon or halogen-substituted hydrocarbons.

As trivalent titanium compounds are used trichloride titanium.

Preferably used trichloride titanium obtained by bringing into contact of titanium tetrachloride with hydrogen, a metal, such as magnesium, aluminum or titanium) or ORGANOMETALLIC compound, for example, magyarkanizsa connection, alyuminiiorganicheskikh connection and incoordination connection with the possibility of its recovery.

Compounds of magnesium, is used to obtain a solid catalytic component on the basis of titanium /A-1/ may or may not have a regenerative ability.

As examples of magnesium compounds exhibiting resilience can lead compound represented by the following formula

XnMgR2-n< / BR>
where

n represents the number satisfying the condition 0n<2;1-20alkyl, aryl or cycloalkyl; in the case when n is 0, two of R may be the same or different meanings; X represents halogen.

Specific examples of magnetotherapies, dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, vexillaria, dodecylamine, activatemenu and ethylbutylamine;

mineralogically, for example, as magnicharters, manoharpur, minicomputer, magniloquence and magnicornis; alcoholate alkylamine, for example, butylamine, ethylbutane and activetextarea; and hydride butylamine;

Specific examples of magnesium compounds not shown resilience include: galoidoproizvodnykh magnesium, for example, chloride, bromide, iodide and magnesium fluoride; halide lamp alkoxyamine, for example, chloride methoxamine, chloride ethoxyline, chloride isopropoxide, chloride botoxonline and chloride octocrylene;

halide compounds ariline, for example chloride phenoxyimine and chloride methyleneimine;

alkoxysilane connection, for example ethoxyline, isopropoxide, butoxymethyl, n-octoxide and 2-ethylhexylamine;

arylacetamide compounds, such as enoximone and dimethylethanolamine; and

magnesium salts of carboxylic acids, such as magnesium laurate and magnesium stearate.

As the magnesium compounds having no is th magnesium.

As the above-mentioned magnesium compounds, not having reducing ability can be used the compounds formed from the above-mentioned magnesium compounds with healing ability or compounds formed in the process of obtaining a catalytic component. To obtain the magnesium compounds having no reducing ability of compounds of magnesium with healing ability, for example, the above magnesium compound-reducing agent is brought into contact with polysiloxane compounds, galoidsodyerzhascikh wilanowie compounds galoidsodyerzhascikh the aluminum compounds, esters, alcohols, halogenated compounds, or compounds having an OH group or an active link carbon-oxygen.

The above compounds of magnesium, possessing and not possessing healing ability can form disclosed hereinafter in the description of the ORGANOMETALLIC compound, for example, complex compounds with other metals (e.g. aluminum, zinc, boron, beryllium, sodium, potassium) and their complexes, or can be presented in the form of a mixture with another metal connection. Moreover, we offer magnesium compound can IP the claimed compounds of magnesium can be used in liquid, and solid form. When using magnesium compounds in solid form, it can be converted into liquid form using alcohols, carboxylic acids, aldehydes, amines, ORGANOMETALLIC esters, acids, etc. which will be described later in the proposed description of the invention as the electron donors (a).

Many other compounds of magnesium, in addition to the above previously, can also be used to obtain a solid catalytic component, /A-1/ titanium, but preferred, however, are compounds in the form of halogenated magnesium compounds in the target catalytic component, /A-1/ on the basis of solid magnesium. In accordance with the above, if you use the magnesium compound not containing halogen, the said connection is preferably subjected to contact with haloesters connection for implementation with him reaction in order to obtain a solid catalytic component on the basis of magnesium.

Among the above-mentioned magnesium compounds are preferred compounds of magnesium, not having resilience, and of these the most preferred magnesium chloride, alkoxysilane and aryloxyalkyl.

the electron donor (a).

Examples of the electron donors (a)include:

oxygen-containing electron donors such as alcohols, phenols; ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic and inorganic acids, ethers, diesters, acid amides, acid anhydrides and alkoxysilanes; and

nitrogen-containing electron donors, such as ammonium compounds, amines, NITRILES, pyridines and isocyanates.

In particular, you can specify, for example,

C1-18alcohols, such as methanol, ethanol, propanol, butanol, pentane alcohol, hexane alcohol, 2-ethylhexanoates alcohol, octane, octadecenoic, oleic, benzyl, phenethyl, tomilovy, isopropyl and isopropylbenzyl alcohol, halogenated alcohols with 1-18 carbon atoms, such as trichloroethanol, trichloroethanol and trichloroethanol;

C6-20phenols, which may have lower alkyl group, such as phenol, kretlow silently, ethylphenols, propylaniline Nonylphenol cumylphenol and naftolin;

C3-15ketopropane, such as acetone; methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone;

C2-15aldehydes, such as AC the organic acids, containing from 2 to 18 carbon atoms, such as methylformate, methyl acetate, ethyl acetate, vinyl acetate, propyl, octylated, cyclohexylacetate, ethylpropane, methylbutyrate, Etisalat, methylchloride, ethylsilicate, methyl methacrylate, etildronat, ethylcyclohexylamine, methylbenzoate, ethylbenzoic, propylbenzoate, butylbenzoate, octylbenzoic, cyclohexylbenzene, phenylbenzoate, benzyl benzoate, methylfolate, atilola, amitola, ethyl ester ethylbenzene acid, methyl ester anise acid, ethyl ester anise acid, ethyl ester ethoxybenzoyl acid, g-butyrolactone, d-valerolactone, coumarin, phtalic and ethylcarbonate;

galodamadruga containing from 2 to 15 carbon atoms, such as acetylchloride, benzoyl chloride, chloride toluene acid and chloride anise acid;

ethers containing from 2 to 20 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether;

amides of acids, for example, N,N-dimethylacetamide, N,N-dimethylbenzamide and N, N-diethyltoluamide;

amines, such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine;

nitri the n and dimethylpyridin;

and anhydrides of the acids, for example acetic anhydride, phthalic anhydride and the anhydride of benzoic acid.

For the preferred examples of esters of organic acids include polycarboxylate, having a structure of the following formula.

or

R3-C-OCOR5< / BR>
R4-C-OCOR6< / BR>
In the above formulas, R1means substituted or unsubstituted hydrocarbon group; each of the radicals R2, R5and R6means hydrogen or a substituted or unsubstituted hydrocarbon group; and each of the radicals R3and R4means hydrogen, or substituted or unsubstituted hydrocarbon group, preferably at least one substituted or unsubstituted hydrocarbon group. R3and R4can be connected to each other to form a cyclic structure. In the case where the hydrocarbon radicals R1-R6substituted, the substituted group contain different atoms, for example N, O, and S, and groups such as C-O-C, COOR, COOH, OH, SO3H-C-N-C - NH2.

Specific examples of polycarboxylates include:

aliphatic polycarboxylate;

alicyclic polycarboxylate;

the examples of polycarboxylates include n-butyl ester of maleic acid, diisobutenyl ether methylmaleimide acid, di-n-hexyl ether cyclohexanecarbonyl Diisobutyl ester of phthalic acid, di-n-butyl ester of phthalic acid, di-2-ethylhexylamine ester of phthalic acid and disutility ether of 3,4-furandicarboxylic acid.

Particularly preferred examples of polycarboxylates are phthalates.

As a simple diesters can be mentioned compounds represented by the following formula:

< / BR>
where

n means an integer satisfying the condition 2n10; R1-R26mean substituents containing at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon; any possible combination, selected from R1-R26but preferably R1-R2nmay form in combination a ring other than a benzene ring; and the main chain may contain another atom than the carbon atom.

For the preferred examples of these compounds include:

2.2-Diisobutyl-1,3-dimethoxypropane,

2-isopropyl-2-isopentyl-1,3-dimethoxypropane,

2,2-DICYCLOHEXYL-1,3-dimethoxypropane, and

2,2-bis-(cyclohexylmethyl)-1,3-dimethoxypropane.

Vice obtain a solid catalytic component, /A-1/ based on titanium, used in the present invention, the above compounds can be brought into contact with organic or inorganic compounds containing silicon, phosphorus, aluminum, etc. which are traditionally used as carriers and activating substances.

As carriers can be used Al2O3, SiO2B2O3, MgO, CaO, TiO2, ZnO, SnO2BaO, ThO and a polymer such as a copolymer of styrene and divinylbenzene. Of these, preferred are Al2O3, SiO2and a copolymer of styrene and divinylbenzene.

The solid catalytic component on the basis of titanium /A-1/, used in the present invention is obtained by bringing the above-mentioned titanium compounds and magnesium (and preferably also the above e-donor (a) into contact with each other.

Using these compounds in a method of producing a solid catalytic titanium component, /A-1/ there are no special restrictions. The following summarizes the examples of the methods of the present invention using compounds of tetravalent titanium.

1) the Method lies in the fact that the solution containing the magnesium compound, e is receiving after or simultaneously with the deposition of the formed solid product resulting from the contact of the specified solution with a compound of titanium.

2) the Method which consists in the fact that the complex consisting of compounds of magnesium and electron donor (a) is brought into contact with the ORGANOMETALLIC compound, and then the resulting reaction product is subjected to interaction with the compound titanium.

3) of the Method lies in the fact that the product obtained by contacting an inorganic carrier and magyarkanizsa connection lead in contact with the connection of titanium. In this case, the above product can be pre-set in contact with haloesters connection, electron donor (a) and/or ORGANOMETALLIC compound.

4) the Method lies in the fact that you get an inorganic or organic substrate, which is held magnesium compound from a mixture consisting of an inorganic or organic carrier and a solution containing the magnesium compound and the electron donor (a) (and in some cases, moreover, hydrocarbon solvent) with subsequent conversion of the obtained substrate in contact with the connection titanium.

5) the Method lies in the fact that the solution containing compound of magnesium, titanium and electron donor (a) (and in some cases also containing the catalytic component on the basis of titanium /A-1/, which serves as a substrate for the magnesium and titanium compounds.

6) the Method consists in the fact that the solution containing magyarkanizsa connection is brought into contact with haloesters connection titanium.

7) the Method lies in the fact that the solution containing magyarkanizsa connection is brought into contact with haloesters connection, followed by contacting the resulting product with a compound of titanium.

8) the Method lies in the fact that alkoxystyrene the magnesium compound is brought into contact with haloesters connection titanium.

9) the Method lies in the fact that the complex consisting of alkoxysilane compounds of magnesium and electron donor (a) is brought into contact with the connection titanium.

10) the Method lies in the fact that the complex consisting of alkoxysilanes magnesium compound and the electron donor (a) is subjected to interaction with the ORGANOMETALLIC compound, and then the resulting product is brought into contact with the connection titanium.

11) the Method lies in the fact that the magnesium compound, electron donor (a) and a compound of titanium is brought into contact with each other in p donor (a) and/or activating reagent, for example, as an ORGANOMETALLIC compound or haloesters compound of silicon.

12) the Method lies in the fact that the solution containing the magnesium compound having reducing ability, result in interaction with a solution of compounds of titanium, in the presence of, if necessary, electron donor (a) precipitation of the resulting solid complex compound of magnesium/titanium.

13) the Method lies in the fact that the reaction product obtained according to the above method (12) result in interaction with the compound titanium.

14) the Method lies in the fact that the reaction product obtained according to the above method (11) or (12) next, bring in the interaction with the electron donor (a) and a compound of titanium.

15) the Method lies in the fact that compounds of magnesium and titanium, and optionally e-donor (a)) is sprayed with obtaining a solid product, after which the solid product is treated with either halogen or haloesters compound, or an aromatic hydrocarbon. The method may include the stage of spraying only the magnesium compound, the stage of spraying complex compounds, SOS is Ethan. After spraying, the resulting solid product can then be subjected to a preliminary treatment with an activating reagent and then treated with a halogen or the like. Examples of activating reagents include ORGANOMETALLIC compound and haloesters compound of silicon.

16) the Method lies in the fact that the magnesium compound is sprayed on the substrate, and then sprayed the magnesium compound is brought into contact with a compound of titanium. At the stage of spraying and/or stage of contact, you can use e-donor (a) and reagent contributing to the course of the reaction.

17) the Method lies in the fact that the compound obtained by any of the above methods (11) (16) is treated with a halogen, haloesters compound or an aromatic hydrocarbon.

18) the Method lies in the fact that the reaction product obtained by the interaction with the metal oxide, magnetogenesis connection and haloesters connection lead in contact with the connection of titanium, and optionally with electronic donor (a).

19) the Method lies in the fact that the connection of magnesium, such as magnesium salt of organic acid, Alcock the ri needed with the electron donor (a).

20) the Method lies in the fact that the solution of a hydrocarbon containing at least a magnesium compound and alkoxylated lead in the interaction with the compound of titanium and/or electron donor (a). However, haloesters connection, for example, haloesters compound of silicon, if necessary, can continue to lead in the interaction with the product obtained above.

21) the Method lies in the fact that the liquid magnesium compound not having a healing ability, lead in the interaction with the ORGANOMETALLIC compound with the precipitation of the solid complex compound of magnesium/metal (aluminum), and then the obtained solid bimetallic compound is brought into contact with a compound of titanium and, if necessary, with e-donor (a).

Preparation of solid catalyst component based on titanium /A-1/ is usually carried out at a temperature of from 70oC to 200oC, preferably in the range from -50 to 150oC.

The solid catalytic component on the basis of titanium /A-1/, thus obtained contains titanium, magnesium and halogen, and in the preferred embodiment, further comprises electron donor (a).

The ratio of electron donor (a)/titanium (molar ratio) e-donor (a) usually contains from 0.01 to 100 mol, preferably from 0.05 to 50 mol.

As for the solid catalytic component on the basis of titanium /A-1/, in the description of the invention describes examples of using compounds of titanium, but titanium is used in the above compounds can be replaced by zirconium, hafnium, vanadium, niobium, tantalum or chromium.

In the present invention, well-known catalytic component on the basis of trichloride titanium (A2) can also be used as another example of the solid catalytic component on the basis of titanium, is listed as a catalytic component compounds of the transition metal /A/.

Methods of obtaining a catalytic component on the basis of trichloride titanium is described, for example in laid the patent application of Japan No. 63(1988)-17274, No. 64(1989)-38409, No. 56(1981)-34711, No. 61(1986)-287904, No. 63(1988)-75007, No. 63(1988)-83106, No. 59(1984)-13630, N 63(1988)-108008, 1 (63)(1988)-27508, No. 57(1982)-70110, No. 58(1983)-219207, N 1(1989)-144405 and N 1(1988)-292011.

For example the catalyst A-2/ based on trichloronate electron donor (a) and/or a compound of tetravalent titanium, or you can use it after bringing it in contact with each other of these components.

In addition, the connection metallocene /A-3/ can also be used as a catalytic component based on the compound of the transition metal /A/.

Methods for obtaining compounds of metallocene /A-3/ described in detail, for example in tiled applications for Japan patent No. 63(1988)-61010, note # 63(1988)-152608, No. 63(1988)-264606, No. 63(1988)-280703, No. 64(1989)-6003, No. 1(1989)-95110, N 3(1991)-62806, 1(1989)-259004, N 64(1989)-45406, No. 60(1985)-106808, N 60-1985)-137911, No. 58(1983)-19309, N 60 (1985)-35006, NO. 60(1985)-35007, NO. 61(1986)-296008, NO. 63(1988)-501369, NO. 61(1986)-221207, NO. 62(1987)-121707, NO. 61(1986)-66206, NO. 2(1990)-22307, NO. 2(1990)-173110, NO. 2(1990)-302410, NO. 1(1989)-129003, NO. 1(1989)-210404, NO. 3(1991)-66710, NO. 3(1991)-70710, N 1(1989)-207248, NO. 63(1988)-222177, NO. 63(1988)-222178, NO. 63(1988)-222179, NO. 1(1989)-12407, NO. 1(1989)-301704, NO. 1(1989)-319489, NO. 3(1991)-74412, NO. 61(1986)-264010, NO. 1(1989)-275609, NO. 63(1988)-251405, NO. 64(1989)-74202, NO. 2(1990)-41303, NO. 2(1990)-131488, N 3(1991)-56508, No. 3(1991)-70708 and N 3(1991)-70709.

Connection metallocene /A-3/ is a compound represented by formula

MIz< / BR>
where

M indicates a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta, Cr, L is a ligand forming a coordination bond relative to the transition metal, and at least one L is a ligand with cyclopentadienyls skeleton, and the other is L except l is oxygraph, trialkylsilyl group, SO3R (where R is C1-8hydrocarbon group, possibly substituted by halogen), halogen atom or hydrogen, and x is the valence of the transition metal).

For ligands with cyclopentadienyls skeleton include, for example, cyclopentadienyls, alkyl substituted cyclopentadienyls groups, such as methylcyclopentadienyl, dimethylcyclopentane, trimethylcyclopentanone, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, ethylcyclopentadienyl, methylethylenediamine, propylcyclopentanol, methylpropylketone, butylcyclopentadienyl, methylbutyraldehyde and hexyltrichlorosilane, and angenlina group, 4,5,6,7-tetrahydroindole group and fluoroaniline group. These groups may be substituted by a halogen atom or trialkylsilyl.

Of these ligands with the coordination relationship relative to the transition metal is most preferred alkyl-substituted cyclopentadienyls group.

In the case where the compound represented by the above formula contains two or more ligands with cyclopentadienyls skeleton, two of the ligand with the specified skeleton may be linked pax is, illinova group or substituted similarbuy a group, such as dimethylsilane, diphenylsilane and methylpenicillin.

The following ligands may serve as a ligand, other than those of cyclopentadienyls skeleton.

TO C1-12the hydrocarbon group includes, for example, alkyl, cycloalkyl, aryl and aralkyl.

In the alkyl group includes methyl, ethyl, propyl, isopropyl and butyl;

in cycloalkyl group includes, for example, cyclopentyl and cyclohexyl;

to the aryl group includes, for example, phenyl and tolyl; and

to Uralkaliy group includes, for example, benzyl and neophyl.

To alkoxygroup include, for example, methoxy, ethoxy, butoxy;

to alloctype include, for example, fenoxaprop and the group of halogen includes, for example, fluorine, chlorine, bromine and iodine.

The ligands represented by the formula SO3R include, for example, para-toluensulfonate, methanesulfonate and triftorbyenzola.

If the transition metal has a valency of 4, the connection metallocene /A-3/ containing a ligand with cyclopentadienyls skeleton may be represented in particular by the formula

R2kR31R4mR53, R4and R5each stands for a group with cyclopentadienyls skeleton, alkyl, cycloalkyl, aryl, aracelio group, alkoxygroup, alloctype, trialkylsilyl group, a group of the formula SO3R, halogen atom or hydrogen, k is an integer at least equal to 1, and the sum of k+1+m+n 4.

In the transition metal compounds of the above formula, R2kR31R4mR5mM at least two of R2, R3, R4and R5preferably have cyclopentadienyls group, that is, R2and R3mean of each group with cyclopentadienyls skeleton. These groups cyclopentadienyls skeleton can be connected to each other through alkylenes a group, such as ethylene and propylene, substituted alkylene, for example isopropylidene, diphenylmethylene, similarbuy group or substituted similarbuy group, for example dimethylsilane diphenylsilane and methylpenicillin. In addition, R4and R5can each be a group with cyclopentadienyls skeleton, alkyl, cycloalkyl, the aryl aralkyl, alkoxygroup, alloctype, trialkylsilyl, a group of the formula SO3R, halogen or hydrogen.

No"ptx2">

dichloride, bis(indenyl)zirconium,

dibromide bis(indenyl)zirconium,

bis(para-toluensulfonate)bis(indenyl) zirconium,

dichloride, bis (4,5,6,7-tetrahydroindene) zirconium,

dichloride, bis (Florisil)zirconium,

dichloride ethylenebis(indenyl)zirconium,

dichloride ethylenebis(indenyl)zirconium,

dibromide ethylenebis(indenyl)zirconium,

ethylenebis(indenyl)dimethylzirconium,

ethylenebis(indenyl)diphenylsilane,

monochloride ethylenebis(indenyl)methylsilane,

bis(methanesulfonate) ethylenebis(indenyl)zirconium,

bis(para-toluensulfonate) ethylenebis(indenyl)zirconium,

bis(triftorbyenzola) ethylenebis(indenyl)zirconium,

dichloride ethylenebis (4,5,6,7-tetrahydroindene)zirconium,

dichloride, isopropylidene (cyclopentadienylmagnesium)zirconium,

dichloride, isopropylidene (cyclopentadienylzirconium)-zirconium,

dichloride dimethylsilicone(cyclopentadienyl)zirconium,

dichloride dimethylsilicone (methylcyclopentadienyl)zirconium,

dichloride dimethylsilicone (dimethylcyclopentane)zirconium,

dichloride dimethylsilicone (dimethylcyclopentane)zirconium,

dichloride dimethylsilicone (trimethylcyclopentanone lenses(indenyl)zirconium,

dichloride dimethylsilicone (4,5,6,7-tetrahydroindene)zirconium,

dichloride dimethylsilane (cyclopentadienylmagnesium)zirconium,

dichloride diphenylsilane(indenyl)zirconium,

dichloride methylphenylsiloxanes(indenyl)zirconium,

dibromide bis(cyclopentadienyl)zirconium,

monochloride bis(cyclopentadienyl)methylsilane,

monochloride bis(cyclopentadienyl)Emilceramica,

monochloride bis (cyclopentadienyl)cyclohexylcarbonyl,

monochloride bis (cyclopentadienyl)phenylsilane,

monochloride bis (cyclopentadienyl)benzylcyanide, Monohydric

monochloride bis (cyclopentadienyl)zirconium,

Monohydric bis(cyclopentadienyl)methylsilane,

bis(cyclopentadienyl)dimethylzirconium,

bis(cyclopentadienyl)diphenylsilane,

bis(cyclopentadienyl)dibenzalacetone,

methoxsalen chloride bis(cyclopentadienyl)zirconium,

ethoxysilanes chloride bis(cyclopentadienyl)zirconium,

bis(methanesulfonate) bis(cyclopentadienyl)zirconium,

bis(para-toluensulfonate) bis(cyclopentadienyl)zirconium,

bis(triftorbyenzola)bis(cyclopentadienyl)CID-Konya,

dichloride, bis(methylcyclopentadienyl)zirconium,

diakonia,

bis(triftorbyenzola) bis)dimethylcyclopentane)zirconium,

dichloride, bis(ethylcyclopentadienyl)zirconium,

dichloride, bis(ethylcyclopentadienyl)zirconium,

dichloride, bis(methylethylenediamine)zirconium,

dichloride, bis(propylcyclopentanol)zirconium,

dichloride, bis (methylpropionamidine)zirconium,

dichloride, bis(butylcyclopentadienyl)zirconium,

dichloride, bis(methylbutyronitrile)zirconium,

bis(methylsulfonyl)bis(methylbutyronitrile)zirconium,

dichloride, bis(trimethylcyclopentanone)zirconium,

dichloride, bis(hexyltrichlorosilane)zirconium,

dichloride, bis(trimethylsilylethynyl)zirconium.

In the above metallocene compound, (disubstituted) cyclopentadienyls group refer to 1,2 - and 1,3-substituted groups, and to trehzameshchenny cyclopentadienyls groups include 1,2,3 - and 1,2,4-substituted group. In addition, alkyl groups such as propyl and butyl includes n-, Isover - and tert-isomers.

In addition it is possible to use transition metal compounds, where the zirconium in the above zirconium compounds given as examples, replaced by titanium, hafinaly of two or more compounds.

In addition, these compounds can be used after dissolving in a hydrocarbon or Alojamientos hydrocarbon.

In the present invention, zirconocene compound containing zirconium as its Central metal atom and a ligand containing at least two cyclopentadienyls group is preferably used as the metallocene compounds /A-3/.

This connection metallocene, mentioned above, can be used on the substrate by bringing into contact with a specific connection carrier.

Examples of compounds used in the present invention as a substrate, includes connection carriers, for example: SiO2, Al2O3B2O3, MgO, ZrO2, CaO, TiO2, ZnO, SnO2, BaO and ThO; and resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-Peten and a copolymer of styrene and divinylbenzene.

These connections media may be used in combination of two or more types of compounds.

Among the above compounds preferably using SiO2, Al2O3and MgO.

Next, the description will be disclosed catalytic component is practical tables used to obtain the alpha-olefin/polyene copolymerizing polymer /1/.

As the catalytic component of /B/ on the basis of the ORGANOMETALLIC compound can be used, for example, alyuminiiorganicheskikh connection /B-1/, alkylesters complex compound consisting of a metal of Group I of the Periodic table and aluminum ORGANOMETALLIC compound of a metal of Group II of the Periodic table.

Alyuminiiorganicheskikh connection /B-1/ is, for example, alyuminiiorganicheskikh connection formulas

RanAIX3-n< / BR>
where

Rameans C1-12hydrocarbon, X is halogen or hydrogen, and n takes the values 1-3.

In the above formula, Rameans C1-12hydrocarbon group such as alkyl, cycloalkyl or aryl, in particular methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl, etc.

To alyuminiiorganicheskikh compounds include, in particular, such compounds, which are described below.

Trialkylaluminium, for example trimethylaluminum, triethylaluminum, triisopropanolamine, triisobutylaluminum, trioctylamine, tulkintalinjojen, for example, dimethylammoniumchloride, diethylaluminium, diisopropylaminoethanol, diisobutylaluminium, dimethylaminopropyl etc.

polutorapolnye connection alkylamine, such as protragonist connection methylalanine, politologist connection ethylamine, politologist connection Isopropylamine, politologist connection bucillamine, polycarbonate connection ethylaluminum etc.

dihalogenide alkylamine, such as methylaluminoxane, ethylaminoethanol, isopropylaminocarbonyl, ethylaluminum dibromide, etc., and

alkylhalogenide, such as diethylaluminium and diisobutylaluminium.

As alyuminiiorganicheskikh connection can also be used a compound represented by the following formula:

RanAIY3-n< / BR>
where

Rahave the above values, Y represents-ORb, -OSiRc3-OAIR2,-NRe2,-SiRf3or N(Rg)AIRh2n denotes 1 or 2, and Rb, Rc, Rdand Rhevery means methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, etc.

Remeans bodoro>Alyuminiiorganicheskikh connection /B-1/ include, in particular, the following compounds.

(i) Compounds of the formula RanAl(ORb)3-nfor example dimethylaminomethyl, diethylaminoethyl, diisobutylaluminium etc.

(ii) the compounds of formula RanAl(OSiRen)3-nsuch as Et2Al(OSiMe3), (ISO-Bu)2Al(OSiMe3), (ISO-Bu)2Al(OSiEt3and so on

(iii) the compounds of formula RanAl(OAIR2)3-nfor example, Et2AIOAIEt2, (ISO-Bu)2AIOAI(ISO-Bu)2and so on

(iv) Compounds of the formula RanAl(NRe2)3-nsuch as Me2AI-net2Et2AINHMe, Me2AINHEt; Et2AIN(Me3Si)2, (ISO-Bu)2AIN-(Me3Si)2and so on

(v) the compounds of formula RanAl(SiRf3)3-nsuch as (ISO-Bu)2AISiMe3and so on, and

(vii) Compounds of the formula RanAl/N(Rg)-AIRh2)3-nfor example, Et2AIN(Me)-AIEt2, (ISO-Bu)2Al(Et)Al(ISO-Bu)2and so on

From alyuminiiorganicheskikh connections /B-1/, shown as the above examples, preferred are Ra3Al,R

Alkyl complex compound composed of any metal of Group I of the Periodic table and aluminum can be presented as an example of a compound of the following formula:

MIAIRj4/< / BR>
where

M1means Li, Na or K, and Rjmeans C1-15hydrocarbon group.

As specific examples of the alkyl complex compounds can lead LiAL(C2H5)4and LiAl(C7H15)4.

ORGANOMETALLIC compound of a metal selected in the group II of the Periodic table can be presented as an example of a compound of the following formula:

R1R2M2< / BR>
where each of the radicals

R1and R2means C1-15hydrocarbon group or halogen, R1and R2can have identical or different meanings, unless both of them mean a halogen, and M2means Mg, Zn or Cd.

To their specific examples include diethylzinc, determine, butylethylamine, ethylaniline and butylaniline.

These compounds can be used individually or in combination of two or more kinds.

For a concrete example is (2).

< / BR>
In the above formulas (1) and (2), R denotes a hydrocarbon group, such as methyl, ethyl, propyl or butyl, preferably methyl, ethyl, more preferably methyl: and m means an integer of 2 or more, preferably from 5 to 40.

Used in the present invention iluminacin can be obtained from mixtures alkylenediamine consisting of alkylenediamines derivative of the formula (OAl(R1)) and alkyloxyalkyl derivative of the formula (OAl(R2)), where each of R1and R2submitted by hydrocarbons, similar to the above-mentioned radicals R and R1and R2means of groups different from each other. In the preferred embodiment, iluminacin get mixed alkylenediamine derivatives containing methylacetylene of the formula (OAl(CH3) is usually not less than 30 mol%, preferably not less than 50 mol%, especially preferably at least 70 mol%

Used in the present invention alyuminiiorganicheskikh oxycoedone /B-2/ can be represented by a known alumination, or as defined by authors of the present invention, benzonitrile aluminium-containing oxycontinonline.

Iluminacin can get the adsorption of water or salt, containing water of crystallization, such as minikleid hydrate, hydrate of copper sulfate (2), hydrate of copper sulfate, hydrate sulfate and Nickel hydride cerium chloride (1) in hydrocarbon solvents are subjected to interaction with alyuminiiorganicheskikh connection, for example, trialkylaluminium, and target iluminacin extract in the form of a hydrocarbon solution containing the specified product.

(2) the Method lies in the fact that alyuminiiorganicheskikh compound is treated with water, ice and steam in a solvent such as benzene, toluene, ethyl ether or tetrahydrofuran, and the target iluminacin extract in the form of a hydrocarbon solution containing the specified product.

(3) the Method lies in the fact that alyuminiiorganicheskikh connection, for example trialkylaluminium subjected to interaction with the ORGANOTIN oxide in a solvent such as decane, benzene or toluene.

Of these methods, the preferred method (1). The above iluminacin may contain small quantities of other ORGANOMETALLIC components except aluminum. Of the above solution containing the extracted iluminacin, the solvent or unreacted ASS="ptx2">

To obtain iluminacin as alyuminiiorganicheskikh compounds can be used, in particular, trialkylaluminium, for example trimethylaluminum, triethylaluminum, Tripropylamine, triisopropanolamine, tri-n-butylamine, triisobutylaluminum, Trevor-butylamine, three tre-butylamine, trimethylamine, trioctylamine, tridecylamine, tricyclohexylphosphine, for example tricyclohexylphosphine or tricyclopentadiene;

dialkylaminoalkyl, such as dimethylaluminum chloride, diethylaluminium, diethylaluminium or diisobutylaluminium;

dialkylaminoalkyl, such as diethylaluminium or diisobutylaluminium;

dialkylamide the alcoholate, such as dimethylaminomethyl or diethylaminoethyl; and

dialkylaminoalkyl, for example, diethylaminoethoxy.

In addition, you can also use isopropanolamine General formula

(i-C4H9)xAly(C5H10)z< / BR>
where

x, y and z each denotes a positive number, and z has a value of 2x.

Of these compounds, particularly preferable to use trialkylaluminium.

To rectorial, xylene, cumene, cimal; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and Methylcyclopentane; petroleum fractions such as gasoline, kerosene and gas oil; or golozhabernyi hydrocarbons, for example the halides, especially the chlorides and bromides of the above aromatic and alicyclic hydrocarbons. Moreover, you can also use the addition of ethyl ether and tetrahydrofuran other ethers. From the above as examples of the above solvents are preferably used aromatic hydrocarbons.

In case the code above catalytic component on the basis of the connection of the transition metal valency of /A/ is a catalytic solid component titanium /A-1/ or the catalytic component on the basis of trichloride titanium /A-2/, as the catalytic component of /B/ on the basis of the ORGANOMETALLIC compound preferably the use of aluminium-containing organic compounds /B-1/. If the catalytic component to /A/ on the basis of the transition metal valency is a compound of metallic the use alyuminiiorganicheskikh oxycoedone /B-2/.

In the pre-polymerization-olefin and the polyene compound to obtain a catalyst containing catalytic component based on the compound of the transition metal /A/ and the catalytic component on the basis of the ORGANOMETALLIC compound /B/, you can use the above electron donor (a) or, if necessary, disclose the following e-donor (b).

As the electron donor (b) it is possible to use silicon-containing organic compound represented by the following formula:

RnSi(OR')4-n< / BR>
where

each of R and R' independently denotes a hydrocarbon group, and n has a value satisfying the condition of 0<n<4.
trimethyloxonium, trimethylaluminium, dimethyldiethoxysilane, dimethyldiethoxysilane, diisobutyldimethoxysilane, tert-butylmethylether, tert-butylmethylether, tert-amiloridesensitive, diphenylmethylsilane, FemaleCircumcision, diphenyldichlorosilane, bis-ortho-tridimensional, bis-meta-tridimensional, bis-para-tridimensional, bis-parton, cyclohexyltrichlorosilane, ethyltrimethoxysilane, methyltriethoxysilane, n-propyltriethoxysilane, decyltriethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, g-chloropropionitrile, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, tert-butyltrichlorosilane, n-butyltrichlorosilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, g-aminopropyltriethoxysilane, chlorotriethylsilane, ethyltriethoxysilane, VINYLTRIMETHOXYSILANE, cyclohexyltrichlorosilane, cyclohexyltrichlorosilane, 2-norbornenedicarboxylic, 2-norbornenedicarboxylic, 2-norbornenedicarboxylic, ethyl silicate, butylsilane, tributyltinoxide, methyltriethoxysilane, vinyltris ( b-methoxyethoxide), vinyltriethoxysilane, dimethyldiethoxysilane,

Cyclopentasiloxane, 2-methylcyclopentadienyl, 2,3-dimethylcyclopropanecarboxylate, Cyclopentasiloxane,

dicyclopentadienyliron, bis(2-methylcyclopentene)dimethoxysilane, bis(2,3-dimethylcyclobutyl)dimethoxysilane, dicyclopentadienyliron, tricyclopentadiene, tricyclopentadiene, dicyclopentadienyltitanium, dicyclopentadienyltitanium, dicyclopentadienyltitanium and cyclopentadienylmagnesium.

Of these compounds, preferably used ethyltriethoxysilane, n-propyltriethoxysilane, tert-butyltrichlorosilane, vinyltriethoxysilane, phenyltriethoxysilane, VINYLTRIMETHOXYSILANE, diphenylmethylsilane, FemaleCircumcision, bis-para-tridimensional, para-trimethylchlorosilane, dicyclohexylammonium, cyclohexanedimethanol, 2-norbornenedicarboxylic, 2-norbornenedicarboxylic, phenyltriethoxysilane, dicyclopentadienyliron, hexyltrimethoxysilane, Cyclopentasiloxane, tricyclopentadiene and cyclopentadienylmagnesium.

The above organosilicon compounds can be used in pure form or in combination of two or more compounds.

More as e-donor (b) in the present invention can also be used:

2,6-substituted piperidine, 2,5-substituted piperidine;

substituted methylvaline, such as N,N,N',N'-tetramethylenebis and N, N,N',N'-tetraethylethylenediamine;

nitrogen-containing electron donors, for example, substituted methylenediamine (for example, 1,3-bibenzimidazole and 1,3-dibenzyl-2-phenylimidazole);

phosphate electronic donaries); and oxygen-containing electron donors, for example, 2,6 - substituted tetrahydropyran and 2.5 substituted tetrahydropyranyl.

The above-mentioned electron donor (b) can be used in combination of two or more types.

To obtain a-olefin/polyene copolymerizing polymer /1/ of the present invention, in the first stage above a-olefin and the polyene compound will copolymerized relative to the catalytic component on the basis of the connection of the transition metal valency of /A/ and the catalytic component of /B/ on the basis of the ORGANOMETALLIC compound with the formation of terpolymerization catalyst containing a copolymer of a-olefin and polyene (i).

When carry out a preliminary polymerization of a-olefins and a polyene compound with a catalytic component of the transition metal compounds (A) and the catalytic component of /B/ on the basis of the ORGANOMETALLIC compound, while the polyene compound is usually used in amounts of from 0.0001 to 10 mol, preferably 0.005 to 5 mol, and particularly preferably from 0.001 to 2 mol per 1 mol of a-olefin.

The copolymerization of α-olefin and polyene compounds can Khujand what liberizatsii. When the polymerization is carried out in the liquid phase, it can be done in the presence of an inert solvent disclosed hereinafter in the description. Additionally, the polymerization reaction can be carried out if the use of these olefins in the liquid state and/or polyene compounds as the solvent or without using any solvent.

In the present invention the pre-polymerization (pressuremedical) can be carried out in the presence of an inert solvent which will be described later. In this case, the above-mentioned monomers and catalyst components are introduced into an inert solvent, and pre-copolymerization in a preferred embodiment, carried out under relatively mild conditions. The preliminary polymerization can be conducted under such conditions that formed the prepolymer is either dissolved or undissolved state in the medium for polymerization, but preferably takes place under such conditions, when a prepolymer formed is not dissolved in the polymerization medium.

More specifically, the pre-polymerized catalyst can be obtained following the methods of the invention.

(ii) the Method lies in the fact that the catalytic component on the basis of transition metal compounds (A) and the catalytic component on the basis of the ORGANOMETALLIC compound, and if necessary, the electronic lead donor in interaction with each other in a mixture of alpha-olefin and the polyene compound with the formation of the catalyst and subsequent copolymerization of a-olefins and a polyene compounds obtained with the catalyst with the formation of terpolymerization catalyst.

Specific examples of the above-mentioned inert solvents include:

aliphatic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene;

alicyclic hydrocarbons such as cyclopentane, cyclohexane and Methylcyclopentane;

aromatic hydrocarbons such as benzene, toluene and xylene;

golozhabernyi hydrocarbons, for example predpochtitelno the use of aliphatic hydrocarbons.

The preliminary polymerization can be accomplished in any way periodic, continuous and semi-continuous process.

The concentration of the catalytic components when carrying out the preliminary polymerization varies depending on the catalyst components. The catalytic component on the basis of the connection of the transition metal valency use in quantity (per 1 liter of the polymerization mass) is usually from about 0.001 to 5,000 mol, preferably from about 0.01 to 1,000 mmol, more preferably from 0.1 to 500 mmol per transition metal atom.

The catalytic component on the basis of the ORGANOMETALLIC compound is used in an amount such that the content of the obtained polymer ranged from 0.01 to 2,000 g, preferably from 0.03 to 1,000 g, more preferably from 0.05 to 200 g per 1 g of the catalytic component compounds of the transition metal, i.e. the catalytic component on the basis of the ORGANOMETALLIC compound is used in an amount usually from about 0.1 to 1,000 mol, preferably about 0.5 to 500 mol, more preferably from 1 to 100 mol per 1 mol of the transition metal atom contained in the catalytic component is CE pre-polymerization, the number of electronic donor varies in the range from 0.01 to 50 mol, preferably from 0.05 to 30 mol, more preferably from 0.1 to 10 mol per 1 mol of the transition metal atom contained in the catalytic component on the basis of transition metal compounds.

The reaction temperature in the preliminary polymerization should be usually from about -20 to + 100oC, preferably from approximately -20 to + 80oC, more preferably in the range from -10 to + 80oC.

The molecular weight regulator such as hydrogen, can be used in the preliminary polymerization.

Used in the present invention terpolymerization the catalyst can be obtained by copolymerization of the above a-olefin and the polyene compound with a catalytic component based on the compound of the transition metal /A/ and the catalytic component on the basis of the ORGANOMETALLIC compound /B/ total number of a-olefin and polyene from 0.01 to 2,000 g, preferably from 0.03 to 1,000 g, more preferably from 0.05 to 200 g per 1 g of the catalytic component compounds of the transition metal.

Pre-polymerized catalyst containing copolyme the congestion in suspension can be used directly in subsequent reactions of polymerization, or pre-polymerized catalyst, selected from the suspension can also be used at a later stage of polymerization.

When the pre-polymerized catalyst in suspension directly used in subsequent polymerization reactions, it can be used individually without the connection with the catalytic component on the basis of the ORGANOMETALLIC compound (II) and electron donor /III/.

In the present invention before the pre-copolymerization can be pre-polymerization of the olefin with the catalyst component compound of the transition metal /A/ and the catalytic component on the basis of the ORGANOMETALLIC compound /B/.

As used in this invention, the olefin you can use the above olefins. Of these olefins, preferably using a-olefins, and more preferably propylene.

If carried out in advance of the preliminary polymerization of the olefin with a catalyst for olefin polymerization before pre-copolymerization, the result can be obtained for example, the following effect. That is, at about the polymerized catalyst, possessing excellent properties of its particles, such as the distribution of particle diameter and particle size distribution.

At the next stage, the above-mentioned olefin will polimerizuet or copolymerized with terpolymerization catalyst obtained by the above method with the formation of the olefin polymer (ii).

To obtain the olefin polymer (ii) terpolymerization the catalyst is used in amount (per 1 liter of the polymerization mass) is usually from about 0.001 to 100 mmol, preferably about 0.005 to 20 mmol per based on the transition metal atom.

In the process of formation of the olefin polymer (ii), can optionally be used catalytic component on the basis of the ORGANOMETALLIC compound /B/ or electron donor in addition to the catalyst terpolymerization.

When using the catalytic component on the basis of the ORGANOMETALLIC compound /B/, its content is such that the quantity of contained metal atoms in the specified catalytic component of /B/ is usually about 1 to 2,000 mol, preferably about 2 to 500 mol per 1 mol of the transition metal atom contained in prepolymerisation catalysts of the et from about 0.001 to 10 mol, preferably from 0.01 to 5 mol per 1 mol of the metal atom contained in the catalytic component on the basis of the ORGANOMETALLIC compound /B/.

If the polymerization process using hydrogen, it is possible so to regulate the molecular weight of the obtained polymer, the obtained polymer has a high rate of speed melt.

In accordance with the invention, the polymerization of the olefin can be performed either by the method of liquid-phase polymerization, for example by polymerization in solution or suspension or gas-phase polymerization. Moreover, the polymerization of the olefin can be conducted as batch, semi-continuous, continuous process.

When the polymerization reaction carried out as suspension polymerization, can be used as the reaction solvent of the aforementioned inert organic solvents, or as a solvent, you can use the olefins in the liquid state at the temperature of polymerization. The conditions of polymerization depends on olefins, however, the polymerization temperature is usually in the range of from about -20 to 300oC, preferably from -20 the t in the range of from normal pressure to a pressure of 100 kg/cm2preferably from about 2 to 50 kg/cm2.

In addition to the above, the polymerization reaction can be carried out in two or more stages with the reaction conditions, which differ from each other.

Thus obtained olefin polymer (ii) may be a homopolymer of the olefin. In other words, it can represent a statistical copolymer or a block copolymer consisting of olefins of two or more types.

Below are examples of the olefin polymer (II) contained the proposed composition based on olefin polymer /II/.

As the olefin polymer (II) used in the present invention, one can cite many well-known C1-20a-olefin polymers and copolymers. As specific examples of the olefin polymer (II) can lead to a-olefins of high and low pressure, linear a-olefin high pressure, polypropylene, polybutene, poly(4-methyl-1-penten), polypenco, copolymer of α-olefin and propylene, a copolymer of olefin and butene, a copolymer of propylene and butene, a copolymer of α-olefin propylene and butene, a copolymer of 4-methyl-1-pentene and olefin, a copolymer of olefin and cycloolefin, the copolymer a-Olivieri propylene type as well as mixtures thereof.

From the above examples preferably used as the olefin polymer (II) polymers of olefins, similar to those used for the formation of olefin polymer (ii) contained in a-olefin/polyene copolymerization the polymer (I).

The proposed composition based on olefin polymer contains a-olefin/polyene copolymerize polymer (I) in an amount of 0.005 to 99 wt. preferably from 0.01 to 90 wt. more preferably from 0.03 to 85 most preferably in the range from 0.05 to 80 wt. and olefin polymer (II) in an amount of from 99,995 up to 1 wt. preferably from 99.99 to 10 wt. more preferably from 99,97 to 15 wt. and most preferably from 99.95 to 20 wt.

The proposed composition based on olefin polymer is produced by mixing a-olefin/polyene copolymerizing polymer /I/ and olefin polymer (II) in the above amounts. In particular containing a copolymer of a-olefin and polyene polymer /II/ mixed at a temperature of from 100 to 350oC, preferably from 150 to 300oC using various kneading machines, which are traditionally used for mixing polymers.

In the proposed composition based on olefin polymer voltage of the melt and the rate of melt flow satisfy the following condition.

When used as the olefin polymer (II) polypropylene tension of the melt and the rate of its turnover in the composition based on olefin polymer satisfy the following condition:

usually log[MT]of 0.8 log[MFR]+0,28

preferably log[MT]of 0.8 log[MFR]+0,30

more preferably log[MT]of 0.8 log[MFR]+0,33.

In contrast to this, in the case of using only the above-mentioned polypropylene (olefin polymer (II), the tension of the melt and the rate of melt flow in the specified olefin polymer satisfies the following condition:

usually log[MT]of 0.8 log[MFR]+0,24.

In accordance with the above, the composition based on olefin polymer has a higher voltage melt compared to conventional olefin polymers.

The specified composition based on olefin polymer can be applied on various assignments because of the high tension of the melt, and accordingly, it is possible to expand the range of its application.

Naproject etc. can be obtained with a high degree of formemost and high yield of the composition based on olefin copolymer.

Composition based on olefin polymer used as a material for vacuum forming or material for pneumaturia, while at the stage of molding can assure her deep drawing. Moreover, the composition based on olefin polymer of the present invention can be molded in large product by vacuum pressing, or large product obtained by the method of pneumaturia.

The addition of the proposed composition based on olefin polymer can produce any container (e.g. bottle) with high strength and large size when using injection blow molding.

Moreover, the proposed composition based on olefin polymer can be produced by calandrinia any sheet or rolled product in the form of a nearly uniform film thickness with a high degree of gloss.

In addition, the proposed composition based on olefin polymer can be obtained porous material (foam) with high porosity and containing ognia can be formed by various forming methods, for example by extrusion or by molding with a hood.

Among the compositions based on the olefin polymer proposed by the present invention can be effectively used in large quantities as masterbatches composition based on olefin polymer containing a-olefin/polyene copolymerize polymer /I/ concrete composition and the characteristic voltage of the melt.

When implementing the proposed composition based on olefin polymer as masterbatches, use a-olefin/polyene copolymerize polymer /I/, which contains a large number of copolymers of a-olefins and Poliana. In particular, a-olefin/polyene copolymerization polymer /I/ copolymer of α-olefin and polyene (i) is contained in an amount of from 15 to 99 wt. preferably from 20 to 90 wt. more preferably from 22 to 88 wt. and the olefin polymer (ii) is contained in an amount of from 85 to 1 wt. preferably from 80 to 10 wt. and more preferably from 78 to 12 wt.

The tension of the melt used a -/polyene copolymerizing polymer /I/ is usually not less than 20 g, preferably not less than 25 g, more preferably not less than 30 g, while the MFR copolyme kotoryj cases cannot be determined due to the inability to obtain a monofilament from a bundle of fibers.

Used as masterbatches offer composition based on olefin polymer contains a/polyene copolymerize polymer /I/ in the amount of 0.005 to 99 wt. preferably from 0.01 to 95 wt. and more preferably from 0.02 to 90 wt. as well as olefin polymer (II) in an amount of from 99,995 up to 1 wt. preferably from 99,99 up to 5 wt. and more preferably of 99.98 up to 10 wt.

When using such masterbatches, its also mixed with the olefin polymer. As the olefin polymer in the mixture in combination with the specified fallopian mix is used effectively olefinic polymer, similar olefinic polymer /II/. The subsequent mixing of masterbatches containing olefin polymer (II), with the olefin polymer, which can be used olefinic polymer /II/, you can easily obtain a composition based on olefin polymer with a ratio of components in the specified composition, preferred for their formation as a result of their compatibility with each other.

The proposed composition based on olefin polymers may also contain various stabilizers, any antistatic agent, antiAmerican, sizing, initiate the ptx2">

With the introduction of the composition based on olefin polymer of the present invention, the phenolic stabilizer type, it is possible to obtain a molded product with improved thermal stability and transparency, it is preferable introduction phenolic stabilizer type. In the case of the introduction of both phenolic stabilizers of the type and on the basis of organic phosphite in the proposed composition based on olefin polymer, obtaining a molded product with significantly improved thermal stability and transparency, and therefore, their introduction is preferred.

Moreover, in the case of the introduction of the proposed composition based on olefin polymer metal salt of higher aliphatic acid in the resulting resin may increase thermal stability at the stage of molding, and it is possible to eliminate the difficulties associated with rust and corrosion molding machine due to the release of the catalyst halide gas. Especially preferably the use of a combination comprising a phenolic stabilizer type and/or the regulator on the basis of organic phosphite and a metal salt of higher aliphatic acid.

Specific examples of phenolic stabilizers of the relative,

2,6-aminobutiramida 4-ethylphenol,

2,6-di-tert-amyl-4-METHYLPHENOL,

2,6-di-tert-octyl-4-n-propylene,

2,6-DICYCLOHEXYL-4-n-op,

2-isopropyl-4-methyl-6-tert-butylphenol,

2-tert-butyl-2-ethyl-6-tert-op,

2-isobutyl-4-ethyl-5-tert-hexylphenyl,

2-cyclohexyl-4-n-butyl-6-isopropylphenol,

crenoline mixture modified with styrene,

di-a-tocopherol,

tert-butylhydroquinone,

2,2'-Methylenebis(4-methyl-6-tert-butylphenol),

4,4'-butylidene(3-methyl-6-tert-butylphenol),

4,4'-THIOBIS (3-methyl-6-tert-butylphenol),

2,2'-THIOBIS(4-methyl-6-tert-butylphenol),

4,4'-Methylenebis(2,6-di-tert-butylphenol),

2,2'-Methylenebis[6-(1-methylcyclohexyl)-para-cresol]

2,2'-ethylidene(4,6-di-tert-butylphenol),

1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,

triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)-propionate]

1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-thiodiethanol/3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 3,5-di-tert-butyl-4-hydroxymethylphosphonate diethyl ether, 1,3,5-Tris(2,6-dimethyl-3-hydroxy-4-tertbutylphenyl)isocyanurate, 1,3,5-Tris/(3,5-di-tert-butyl-4-HYDR/BR>2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butyl-aniline)-1,3,5-triazine,

tetrakis/methylene-3-(3,5-ditretbutyl-4-hydroxyphenyl)propionate/methane/,

bis/3,5-di-tert-butyl-4-hydroxymethylphosphonate ester)calcium,

bis(3,5-di-tert-butyl-4-hydroxybenzophenone acid ethyl ester)Nickel complex,

bis/3,3-bis(3-tert-4-hydroxyphenyl)butyric acid glycol ester,

N,N'-bis/3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl/-hydrazine,

2,2'-oxalidales/ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

bis/2-tert-butyl-4-methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl] terephthalate,

1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene,

3-9-bis/1,1-dimethyl-2-{b-(3-tert-butyl-4-hydroxy-5-were)-propionyloxy} ethyl]-2,4,8,10--tetraoxaspiro/5,5/undecane,

2,2,-bis/4-(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))- ethoxyphenyl]propane, and

complex alkalemia esters of b-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid.

Especially preferred alilovic esters of b-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, mentioned above, are alkalemia esters containing alkyl group of not more than 18 carbon atoms.

R>
< / BR>
where

R means a hydrogen atom, or a C1-6alkyl, R1and R2accordingly, mean C1-6alkyl, R3means C1-6alkyl or C1-6alkoxygroup, R4means C1-22alkyl or a group of any of the following patterns:

< / BR>
< / BR>
Of these preferred compounds

2,6-di-tert-butyl-4-METHYLPHENOL,

stearyl ester b-(4-hydroxy-3,5-di-tert-bitolterol)-propionic acid,

2,2'-ethylidene bis(4,6-di-tert-butylphenol),

tetrakis/methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate/-methane.

We offer phenolic stabilizers are used both in pure form and in combination with each other.

Specific examples of stabilizers on the basis of organic phosphites include:

Tichilesti,

Triarylphosphite,

Christadelphia,

Transtelephonic,

phenoldisulfonic,

phenoldisulfonic,

phenyldi(tridecyl)FOSFA,

diphenyldiisocyanate,

diphenylisobenzofuran,

diphenylacetylene,

Triphenylphosphite,

Three(nonylphenyl)FOSFA,

Tris(2,4-di-tert-butylphenyl)FOSFA,

Tris(butoxyethyl)FOSFA,

Tetra(tridecyl)-4,4'-butylic from about 12 to 15 carbon atoms),

4,4'-isopropylidenebis (2-tert-butylphenol)di(nonylphenyl)FOSFA, Tris(biphenyl)FOSFA,

Tetra(tridecyl)-1,1,3-Tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butandiol,

Tris(3,5-di-tert-butyl-4-hydroxyphenyl)FOSFA,

hydrogenated 4,4'-isopropylidenediphenol,

bis(octylphenyl)bis/4,4'-butylidene(3-methyl-6-tert-butylphenol)/1,6 - hexanedioic,

hexa(tridecyl)-1,1,3-three(2-methyl-4-hydroxy-5-tert-butylphenol) diphosphite,

Tris/4,4'-isopropylidenebis(2-tert-butylphenol)/postit,

Tris(1,3-distearyldimethyl)FOSFA,

9,10-dihydro-9-phosphatisation-10-oxide, and

tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyldiol.

Of these compounds, preferably using Tris(2,4-di-tert-butylphenyl)phosphite, Tris(nonylphenyl)phosphite and tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenylacetic.

Moreover, the most preferred are Tris(2,4-di-tert-butylphenyl)FOSFA.

As stabilizers based on phosphites have also been formed from pentaerythritol, illustrated below by the following formula:

< / BR>
< / BR>
In the above formula (1) and (2), R1and R2mean respectively an alkyl group.

Examples of metal salts of higher aliphatic acids include salts of alkali metals, salts of alkaline earth metals and salts of other metals of saturated or unsaturated carboxylic acids containing from 12 to 40 carbon atoms. C12-40saturated or unsaturated carboxylic acids mentioned above may contain substituents, for example hydroxyl groups.

Examples of C12-40saturated or unsaturated carboxylic acids include stearic, oleic, lauric, kuprianova, arachidonic, Kalitina, Bekenova, 12-hydroxystearate and montanoa acid, and examples of metals which can form a salt when interacting with these higher aliphatic acids include alkaline earth metals such as magnesium, calcium and barium; alkali metals such as sodium, potassium and lithium and other metals, such as cadmium, zinc and lead.

Specific examples of metal salts of higher aliphatic acids include: magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium salt arachidonic acid, barium salt beganovi acid, zinc stearate, realia, 12-hydroxystearate calcium, sodium salt montenovo acid, calcium salt montenovo acid and Montana zinc.

Of these metal salts of higher aliphatic acids are particularly preferably used zinc salts of saturated aliphatic acids containing from 12 to 35 carbon atoms.

These metal salts of higher aliphatic acids can be used in pure form or in combination with each other.

In the case of the above-mentioned stabilizers in the proposed composition based on olefin polymer of phenolic stabilizers are contained in amounts of usually from 0.01 to 1.0 wt. preferably from 0.02 to 0.5 wt. more preferably from 0.03 to 0.2 wt.

The stabilizers on the basis of organic phosphites are used in amounts of generally from 0.01 to 1.0 wt. preferably from 0.02 to 0.5 wt. more preferably from 0.03 to 0.2 wt. in the proposed composition of the olefin polymer.

Metal salt of higher aliphatic acids are used in amounts of generally from 0.01 to 1.0 wt. preferably from 0.02 to 0.5 wt. and more preferably from 0.03 to 0.2 wt. in the proposed composition based on olefin polymer.

The proposed composition on snowarama. The proposed composition based on olefin polymer has excellent formability in forming the filler, and from it you can get any film with high yield and at high speed. Moreover, for moulding articles of the proposed composition based on olefin polymer can be used in various ways, for example as pneumotropica, vacuum forming, cylindromyia, the formation of an extrudable blanks and forming with the hood, so you can extend the scope of the specified composition based on olefin polymer.

The present invention is illustrated further by the following Examples, which in no way limit the scope of the invention.

Example 1. Obtaining a catalytic component on the basis of solid titanium /A/.

for 95.2 g of anhydrous minikleid, 442 ml of decane and 390,6 g 2-etylhexyl alcohol is stirred and heated at 130oC for 2 h to obtain a homogeneous solution. To the resulting solution was then added phthalic anhydride, and the mixture was stirred at 130oC for 1 h to dissolve the phthalic anhydride in the specified solution. The resulting gamut dropwise to 200 ml of titanium tetrachloride, aged at a temperature of 20oC for 1 h After completion of the injection mortar the temperature of the obtained liquid mixture was raised to 110oC for 4 h, after which to this liquid mixture was added with 5.22 g diisobutylphthalate(DIBP), and then the resulting mixture was stirred at the same temperature for 2 hours

After completion of the reaction from the reaction liquid to separate the solids by the method of filtration in the hot condition. The obtained solid product re-suspended in 275 ml of titanium tetrachloride, and the resulting suspension is then heated at 110oC within 2 hours After completion of the reaction, the solid residue is again separated from the reaction solution by hot filtration. The obtained solid product is thoroughly washed with decane and hexane at 110oC up until in solution will not be found no presence of the titanium compound.

The catalytic component on the basis of solid titanium /A/, obtained above, is kept in suspension in the Dean. A portion of the specified decanoas suspension is dried to analyze the catalytic composition. As a result of analysis obtained above catalytic component on the basis of solid titanium /A/ has a composition containing 2,4 data catalyst /B/-1.

400 ml-St 4-Karlovy glass reactor equipped with a stirrer, was loaded with 200 ml of purified hexane, 6 mmol of triethylaluminum and 2 mmol (calculated as titanium atom) of the above solid catalyst component based on titanium /A/, in nitrogen atmosphere. Then the reactor additionally served propylene with download speeds of 6.4 l/h at 20oC for 1 h

After loading of propylene, the reactor is rinsed with nitrogen, the reaction mixture is washed to remove the supernatant and add twice purified hexane. Thereafter, the resulting reaction solution was re-suspended purified hexane, and the whole amount of the resulting suspension is transferred into a flask with a catalyst to obtain terpolymerization catalyst (B)-1).

Obtaining the ethylene/polyene copolymerizing polymer (1)-1.

The copolymerization of ethylene and polyene.

400 ml-th chetyrehraundovy glass reactor equipped with a stirrer, was loaded in a nitrogen atmosphere 334 ml of purified hexane, 1,9-decadiene, 10 mmol of diethylaluminium and 1.0 mmol (based on titanium atom) obtained above terpolymerization catalyst (B)-1. After that, the reactor further added ethylene at 0oC, and the hearth is edenia ethylene, the reactor was rinsed with nitrogen, and double rinse, including the removal of the supernatant and the introduction of purified hexane. After that, the obtained reaction liquid is re-suspended with the use of purified hexane, and the whole amount of the resulting suspension was poured into the flask with getting terpolymerization catalyst (C)-1, containing a copolymer of ethylene and polyene (i).

In the thus obtained terpolymerization catalyst (C)-1 is a copolymer of ethylene and 1.9-decadiene is formed in the amount of 15.3 g per 1 g of the catalytic component on the basis of transition metal compounds.

Polymerization of olefin.

In a 1-liter pathology glass reactor equipped with a stirrer in a nitrogen atmosphere download 600 ml of purified heptane, and the temperature in the reactor was adjusted to 60oC. then charged to the reactor 30 mmol of triethylaluminum, 3 mmol of cyclohexyltrichlorosilane (CMMS) and 0.6 mmol (based on titanium atom) obtained above terpolymerization catalyst (C)-1 followed by the introduction of propylene and hydrogen at a feed rate of 150 l/h and 0.2 l/h, respectively, and conducting the polymerization for 60 minutes the Temperature in the polymerization process support at 70ooC with removal of residual catalyst.

After stopping stirring, the slurry containing the resulting solid product was filtered, separating the polymer from the suspension. The obtained polymer was dried at 70oC under reduced pressure to yield 195,2 g of the ethylene/polyene copolymerizing polymer (1)-1. The rate of melt fluidity (MFR) of the obtained ethylene/polyene copolymerizing polymer (1)-1 is 11,2 DG/min.

Obtained above containing a copolymer of ethylene and polyene polymer (1)-1 has a composition that includes a copolymer of ethylene and polyene in the amount of 13.2 wt. and olefin polymer in the amount of 86.8 wt.

Obtaining a polypropylene composition.

21.8 wt.h. the above ethylene/polyene copolymerizing polymer /1/-1,1 wt.h. calcium stearate, 1 wt.h. 3,5-di-tert-butyl-4-hydroxytoluene, 1 wt.h. tetrakis/methylene-(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate/methane and 1.000 wt.h. Propylene homopolymer /11/ (MFR of 1.5 DG/m, the residue from the extraction using boiling heptane: 98.0%ametre.

The tension of the melt (MT) of the resulting polypropylene composition is 1.7 g, and the rate of melt fluidity (MFR) of 1.8 DG/min

Example 2. Copolymerization of propylene and 1,9-decadiene.

400 ml-th chetyrehraundovy glass reactor equipped with a stirrer, was loaded in a nitrogen atmosphere 334 ml of purified hexane, 2 ml of 1,9-decadiene, 10 mmol of triethylaluminum, 2 mmol of cyclohexyltrichlorosilane (SMS) and 1.0 mmol (calculated as titanium atom) of the solid catalytic component on the basis of titanium /A/, obtained by the method of Example 1. After that, the reactor is additionally loaded propylene at a temperature of 20oC, and the supply of propylene cease when the amount entered in the reaction of propylene, comprising 16 HP After the introduction of propylene reactor rinsed with nitrogen and rinse twice, which involves removal of the supernatant liquid and addition of purified hexane. After that, the obtained reaction liquid is re-suspended with the use of purified hexane, and the entire amount of the resulting suspension is transferred into a flask with a catalyst resulting in a gain terpolymerization catalyst (C)-2.

In terpolymerization catalyst (C)-2, recip what about the component compounds of the transition metal.

Polymerization of olefin.

In a 1-liter pathology glass reactor equipped with a stirrer, was loaded in a nitrogen atmosphere of 600 ml of purified heptane, and then bring the temperature in the reactor to 60oC. Then the reactor impose additional propylene and hydrogen at the speed of their supply 150 l/h and 0.2 l/h, respectively, and carry out the polymerization reaction for 60 minutes At the polymerization temperature was kept at 70oC.

The polymerization reaction stopped by adding a large amount of Isobutanol containing a small amount of hydrochloric acid, and the replacement gas supplied into the reactor by nitrogen. The resulting mixture was stirred for 30 min to remove residual catalyst.

After stirring the suspension containing the solid precipitate was filtered to separate the polymer from the specified suspension. The obtained polymer was dried at 70oC under reduced pressure to yield 182,3 g propylene/1,9-decadienamide copolymerizing polymer (1)-2. MFR obtained containing copolymer of propylene and 1,9-decadiene (1)-2 is 9.9 DG/min.

Propylene/1,9-decadiene copolymerize polymer(1)-2 has a composition which includes a copolymer of propylene is Elenovo composition.

14 wt. h obtained above propylene/1,9-decadienamide copolymerizing polymer (1)-2, 1 wt.h. calcium stearate, 1 wt.h. 3,5-di-tert-butyl-4-hydroxytoluene, 1 wt.h. Tetrakis/methylene (3,5-di-tert-butyl-4-hydroxy)hydrocinnamate/methane and 1000 wt.h. polypropylene (11) (homopolymer) (MFR of 1.5 DG/min residue from extraction using boiling heptane: 98,0%) are mixed with each other. The resulting mixture was crushed and granularit when using the extruder of 20 mm in diameter.

The tension of the melt (MT) thus obtained polypropylene composition is 1.6 g, and the rate of melt fluidity (MFR) is 1.9 DG/min

Example 3. Polymerization of olefin.

In a 1-liter pathology glass reactor equipped with a stirrer, was loaded in a nitrogen atmosphere of 600 ml of purified heptane, after which the temperature in the reactor was raised to 60oC. and Then injected into the reactor 30 mmol of triethylaluminum, 3 mmol of cyclohexyltrichlorosilane (CMMS) and 0.6 mmol (based on titanium atom) terpolymerization catalyst (C)-1, obtained by the method of Example 1, followed by the introduction of propylene and hydrogen at the speed of their supply 150 l/h and 0.2 l/h, respectively, and conducting the polymerization reaction in aceshot by introducing large amounts of Isobutanol, containing a small amount of hydrochloric acid, and replacement fed to the reactor gas to nitrogen. The resulting mixture was stirred for 30 min at 60oC with removal of residual catalyst.

After stirring the slurry containing the solid product is filtered with the aim of separating from the specified suspension of the polymer. The obtained polymer is dried at a temperature of 70oC under reduced pressure to yield of 98.3 g of the ethylene/polyene copolymerizing polymer (1)-3. The rate of melt flow ethyltoluene copolymerizing polymer (1)-3 8.0 DG/min

The ethylene/polyene copolymerize polymer (1)-3, obtained above, has a composition containing a copolymer of ethylene and polyene in the number of 25.7 wt. and olefin polymer in the amount of 74.3 wt.

Obtaining a polypropylene composition as masterbatches 50 wt. including the above-mentioned polymer containing a copolymer of ethylene and polyene (1)-3, 1 wt. including calcium stearate, 1 wt.h. 3,5-di-tert-butyl-4-hydroxytoluene, 1 wt. including Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxy)hydrocinnamate)methane and 50 wt. including Propylene homopolymer (P)-2 (MFR of 7.0 DG/min residue from extraction using boiling heptane: 98,0%) mix is icii based on the olefin polymer (M-1) as masterbatches.

Obtaining propylene composition.

25 wt. including the above composition /M-1/ as masterbatches, 1 wt. including calcium stearate, 1 wt.h. 3,5-di-tert-butyl-4-hydroxytoluene, 1 wt.h. Tetrakis/methylene (3,5-di-tert-butyl-4-hydroxy)hydrocinnamate/methane and 1000 propylene homopolymer /II/ (MFR of 1.5 DG/min, the residue from the extraction using boiling heptane 98,0%) are mixed with each other. The resulting mixture granularit using the extruder of 20 mm in diameter.

The tension of the melt /MT/ polypropylene composition obtained is 1.8 g, and the speed of the melt /MFR/ 1.8 DG/min

Example 4. Polymerization of olefin.

In a 1-liter pathology glass reactor equipped with a stirrer, was loaded in a nitrogen atmosphere of 600 ml of purified hexane, after which the temperature in the reactor was raised to 60oC. and Then charged to the reactor 3 mmol of cyclohexyltrichlorosilane (CMMS) and 0.6 mmol (based on titanium atom) terpolymerization catalyst /C/-2 obtained in Example 2 and then injected propylene and hydrogen at a feed rate of 150 l/h and 0.2 l/h, respectively, and conducting the polymerization for 25 minutes the Temperature in the polymerization of podderjivaya, containing a small amount of hydrochloric acid, and replacement fed to the reactor gas to nitrogen. The resulting mixture was stirred for 30 min at a temperature of 60oC with removal of residual catalyst.

After stirring the suspension containing the obtained solid product was filtered to separate the formed polymer to the suspension. The obtained polymer was dried at 70oC under reduced pressure to yield 90,5 g propylene/polyene copolymerizing polymer /1/-4. The rate of melt fluidity (MFR)of the polymer containing a copolymer of propylene and Poliana /1/-4 is 7.6 DG/min.

The result of the above propylene/polyene copolymerize polymer /1/-4 has a composition containing 28,2 wt. copolymer of propylene and Poliana and 71,8 wt. olefin polymer.

Obtaining a polypropylene composition as masterbatches.

50 wt.h. the result of the above propylene-polyene copolymerizing polymer /1/-4, 1 wt.h.calcium stearate, 1 wt.h. 3,5-di-tert-butyl-4-hydroxytoluene, 1 wt. including tetrakis/methylene(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate/methane and 50 wt.h. Propylene homopolymer /11/-2 (MFR of 7.0 DG/min, the residue from the extraction of ispolzovanie 20 mm in diameter with obtaining a composition based on olefin polymer /M-2/ as masterbatches.

Obtaining a polypropylene composition.

21.8 wt.h. viseporodicnog song /M-2/ as masterbatches, 1 wt. including calcium stearate, 1 wt.h. 3,5-di-tert-butyl-4-hydroxytoluene, 1 wt. including tetrakis/methylene (3,5-decret-butyl-4-hydroxy)hydrocinnamate/methane and 1000 wt.h. Propylene homopolymer /11/ (MFR of 1.5 DG/min residue from extraction using boiling heptane 98,0%) are mixed with each other. The resulting mixture granularit when using the extruder of 20 mm in diameter.

The tension of the melt (MT) of the resulting polypropylene composition is 1.7 g, and the rate of melt flow (MFR) is 1.8 DG/min

Comparative Example 1.

The tension of the melt (MT) polypropylene /11/ used in Example 1 and 2 is 1.4,

1. Polymer composition comprising a polymer containing a copolymer of alpha-olefin and polyene with non-conjugate double bonds, and special additive, characterized in that it further includes a polyolefin, and a copolymer of alpha-olefin and diene with non-conjugate double bonds contains the product obtained by successively carrying out terpolymerization diene with non-conjugate double bonds, sod is the presence of a catalyst, containing catalytic component based on transition metal compounds containing at least one transition metal selected from titanium and zirconium, and alyuminiiorganicheskikh connection and/or alyuminiiorganicheskikh oxycoedone, and polymerization of alpha-olefin in the presence of the obtained prepolymer, alyuminiiorganicheskikh compounds and silicon-organic compounds and/or alyuminiiorganicheskikh oxycoedone to content in the final product 0,01 2000,0 g of a copolymer of alpha-olefin and polyene with non-conjugate double bonds per 1 g of the catalytic component on the basis of the transition metal content in the copolymer 99,999 70,0 mol. links of alpha-olefin and 0.001 30,0 mol. links diene compounds having 7 or more carbon atoms, having at both ends olefinic double bond and the content of polymer of olefin 85,0 to 99.999 wt. on 100 wt. the entire product of polymerization in the following ratio, wt.

The polymer containing a copolymer of alpha-olefin and diene with non-conjugate double bonds of 0.005 99,0

The polyolefin 1,0 99,995

The target additive and the Rest

2. The composition according to p. 1, characterized in that the polymer containing a copolymer of alpha-olefin and diene with navalnogo alpha-olefin in the presence of titanium-magnesium solid component of catalyst and trialkylamine when the content of the prepolymer alpha-olefin 85,5 to 99.999 wt. on 100 wt. just the final product.

3. The composition according to p. 1, characterized in that it contains a polymer containing a copolymer of alpha-olefin and diene with application at the stage of terpolymerization diene catalyst, optionally containing organosilicon compound.

4. The composition according to p. 1, characterized in that the metal component of the transition metal compounds is a solid titanium catalyst component containing titanium and halogen.

5. The composition according to p. 1, characterized in that the catalytic component compounds of the transition metal is zirconocene compound containing a ligand having cyclopentadienyls structure.

6. The composition according to PP.1 3 or 4, characterized in that it includes polyolefin copolymer selected from the group including high density polyolefin, the polyolefin is a low density, linear low density polyolefin, polypropylene, polybutene, poly(4-methyl-1-penten), polypenco, a copolymer of alpha-olefin and propylene, a copolymer of alpha-olefin and butene, a copolymer of propylene and butene, a copolymer of alpha-olefin, propylene and butene, a copolymer of 4-methyl-1-pentene and olefin, a copolymer of alpha-OLE ropranolol type, statistical copolymer of propylene and their mixtures.

 

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FIELD: polymer production.

SUBSTANCE: invention provides homogenous catalytic system for synthesis of copolymers and terpolymers of olefinic monomers, which system contains dialkyl bridge-type bis(indenyl)metallocene complexes with group IVB metals and trialkylaluminum at Al-to-metal ratio between 50 and 500. Catalytic system enables carrying out polymerization process at rates significantly exceeding ethylene or propylene homopolymerization rate.

EFFECT: significantly accelerated copolymerization process and achieved fractional and compositional homogeneity of ethylene/α-olefin and propylene/α-olefin copolymers.

1 tbl, 16 ex

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 processes.

SUBSTANCE: invention provides ethylene polymerization process at pressure between 1000 and 4000 bar and temperature from 140 to 320°C, which is characterized by that water is continuously or stepwise is fed into reactor so that reaction proceeds at such pressure and temperature, at which water is in supercritical state.

EFFECT: improved heat extraction and thereby increased degree of ethylene conversion.

9 cl, 2 tbl, 7 ex

FIELD: organic chemistry, chemistry of polymers.

SUBSTANCE: invention relates to olefin- and alkenylalkylate-base polymers, methods for their synthesis, their using and a composition containing these polymers. Polymer shows molecular mass from 500 to 2500 g/mole and comprises at least one link of the formula (I): wherein R1, R'1 and R''1 are similar or different and chosen from hydrogen atom and alkyl radicals comprising from 1 to 10 carbon atoms; R2 is chosen from hydrogen atom, alkyl radical comprising from 1 to 20 carbon atoms, aromatic radical comprising from 6 to 10 carbon atoms, or group -OR'2 wherein R'2 is hydrogen atom or alkyl group comprising from 1 to 6 carbon atoms and wherein R1 and R can't mean hydrogen atom simultaneously, and wherein G and G' are similar or different and chosen from the following carbonyl groups: -O-C(O)-, -C(O)-O- and -C(O)-; R3 is chosen from alkyl radicals comprising from 1 to 13 carbon atoms; R5 and R are similar or different and chosen from hydrogen atom, alkyl radicals comprising from 1 to 13 carbon atoms, or in common they form a double bond with two carbon atoms with which they are bound, or in common they form saturated or unsaturated cycle or aromatic cycle comprising from 6 to 10 carbon atoms and wherein this cycle is substituted if necessary with 1-3 groups with the same determinants as Z but with exception for hydrogen atom; Z means hydrogen atom, -NO2, -NR2, -CONR2, -COO-+NH2R2 wherein each R means independently alkyl radical comprising from 1 to 24 carbon atoms; -COOR wherein R means the abovementioned value, and if Z means hydrogen atom then R5 and R6 form in common saturated or unsaturated, or aromatic cycle that can be substituted; x, y, z and t correspond to the such mole ratios that the sum x + y = 0.60-0.98 wherein x or y can mean 0; z = 0.004-0.38; t = 0.02 <t/z<4. The above said polymer can be synthesized by two methods. The first method involves radical polymerization of the parent monomers chosen in the suitable mole ratios in the presence of an initiating agent, under pressure 50-700 MPa, at temperature 100-350°C. The second method involves two steps. On the first step a functionalized polymer is synthesized by either the direct synthesis by the polymerization reaction of at least a single olefin and at least a single unsaturated monomer comprising at least one primary alcoholic or hydroxyl functional group or by indirect synthesis comprising the polymerization reaction of at least a single olefin and at least a single unsaturated hydrolyzing ester followed by incomplete hydrolysis of indicated ester functional groups for releasing an alcoholic or hydroxyl functional groups. On the second step method involves the esterification reaction of primary alcoholic or hydroxyl functional groups of a functionalized polymer by using an acid halide or anhydride acid. Synthesized polymers are used as a multifunctional hydrocarbon cold-resistant and anti-sedimentation additive to a fuel that provides working capacity at low temperatures. The proposed composition used as a fuel comprises the following components: at least one hydrocarbon fraction as the main fraction chosen from group formed by middle distillates, biofuel, synthetic gas oil, water-emulsified fuel or fuel emulsified in a mixture water/alcohols or polyols, and their mixtures, and, in lesser amounts, part of at least 25 ppm containing at least one polymer. Invention provides preparing additive that improved low-temperature properties, i. e. the limit filtering capacity temperature value and fluidity value, and anti-sedimentation properties of fuel also.

EFFECT: valuable properties of polymers.

25 cl, 6 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to copolymers of ethylene and butadiene. Invention describes a copolymer of ethylene and butadiene showing the mole content of butadiene derivative links as 8% or above wherein these links comprise bond as trans-1,2-cyclohexane and having the mean molecular mass Mn 40000 g/mole or above. Also, invention describes a catalytic system used for synthesis of copolymer of ethylene and butadiene that comprises the following components: (i) metalloorganic complex; (ii) co-catalyst belonging to group consisting of alkylmagnesium, alkyllithium, alkylaluminum, Grignard reagent, or consisting of a mixture of indicated components and wherein the mole ratio co-catalyst/metalloorganic complex is in the range from 1 to 8, and a method for synthesis of copolymer of ethylene and butadiene. Invention provides preparing copolymer of ethylene and butadiene showing the mole content of butadiene derivative links as 8% or above wherein indicated links comprise bonds as trans-1,2-cyclohexane and having high mean molecular mass.

EFFECT: improved method of synthesis.

20 cl, 5 tbl, 12 ex

FIELD: polymer production and catalysts.

SUBSTANCE: proposed method comprises contacting monomers with deposited bimetallic catalytic composition over a period of time long enough to obtain bimodal polyolefin composition, which includes high-molecular weight polyolefin component and low-molecular weight polyolefin component, wherein deposited bimetallic catalyst includes first catalyst component, which is preferably non-metallocene, and second catalyst component, which includes metallocene catalytically active substance containing at least one fluoride or fluorine-containing leaving group, wherein bimetallic catalyst is supported by improved silica dehydrated at temperature above 800°C.

EFFECT: increased activity and productivity of catalyst.

16 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: polymer composition contains low- and high-molecular polyethylene components, the composition basically having a single peak of lamella width percentile curve and PENT greater than 1000 hours at 80°C and 2.4 MPa according to ASTM F1473. The process has several variants allowing production of tubes with enough viscosity to resist shock during laying or afterward; and with extra long working life under gas or water pressure, especially resistant to environmental stress cracking and to creep under internal pressure.

EFFECT: higher impact elasticity and longer working life of tubes.

37 cl, 5 dwg, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: described is the method of synthesising copolymers from fluorated olefin and hydrocarbon olefin, selected from ethane, propylene and mixtures of these substances, containing in essence water-emulsion polymerisation, not containing emulsifiers, fluorated olefin and hydrocarbon olefin, then copolymerisation of fluorated olefin and hydrocarbon olefin in the presence of fluoropolymer particles and/or in the presence of fluorinated liquid with a boiling point of at least 50°C at atmospheric pressure in a form, meant for improving the process of copolymerisation of fluorated olefin and hydrocarbon olefin, in this case fluoropolymer particles are formed In Situ due to polymerisation of parts of fluoropolymer olefin without substantial copolymerisation of hydrocarbon olefin or assuming that fluoropolymer particles are added at the beginning of polymerisation, and polymerisation is thermally initiated in case polymerisation is carried out in the presence of fluoropolymer particles, at that water-emulsion polymerisation, in essence free of emulsifier, means that a fluorinated surface-active substance is not available or its content is less than 500 ppm in relation to the amount of water in the system of polymerisation during its addition to the water-phase.

EFFECT: creating an effective mode of synthesizing copolymers from fluorated olefin and hydrocarbon olefin.

9 cl, 5 ex

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