The method of producing catalyst type ziegler-natta

 

(57) Abstract:

The invention relates to a method of producing catalyst type catalyst of the Ziegler-Natta with granular media. The method involves contacting a granular media with (a) organosilicon compound, (b) dialkylamines and under certain conditions trialkylaluminium, (C) monochlorobenzene compound and (d) at least one compound of tetravalent titanium. According izobreteniya organosilicon compound can be represented by a silane, such as diethoxydimethylsilane, methyltrimethoxysilane, methyltriethoxysilane or tetraethoxysilane. The organosilicon compound can be represented by diseasenon, such as hexamethyldisilazane. The proposed method allows to obtain a linear low density polyethylene with a relatively narrow distribution of molecular weight and high bulk weight. 8 C.p. f-crystals.

The invention relates to a method for producing a catalyst type catalyst of Ziegler-Natta-based granular media. The catalyst suitable for the polymerization of olefins, for example ethylene, in particular, in the gas phase.

In EP-A 453088 describes how poluchennogo oxide. The method of preparation of the catalyst involves three stages, carried out in a liquid hydrocarbon medium, namely: a) the first stage contacting of granular media dialkylamines and under certain conditions trialkylaluminium, (b) a second stage contacting of the product of the first stage with monochlorobenzene compound and (C) the third stage of the contact product of the second stage with at least one compound of tetravalent titanium. The catalyst suitable for the production of polyolefins, such as polyethylene. However, the disadvantages of the catalyst is that the catalyst is not suitable for any of polyethylene, in particular not suitable for the production of ethylene copolymers such as linear low density polyethylene with a narrow distribution of molecular weight and high bulk weight. In addition, the homogeneity of the obtained copolymer is not high enough.

In accordance with the invention features a method of obtaining a catalyst of Ziegler-Natta, which can be used to obtain polyethylene, in particular linear low density polyethylenes with a relatively narrow distribution of molecular weight and high bulk weight. This uniformity utilizator type Ziegler-Natta-based granulated oxide and catalyst type Ziegler-Natta, obtained by this method.

The proposed method includes a stage of contacting granular media:

(a) organosilicon compound,

b) dialkylamines or, under certain conditions, dialkylamines mixed with trialkylaluminium,

C) monochlorobenzene connection and d) at least one compound of tetravalent titanium.

The difference of the proposed method from the known is an additional processing stage organosilicon compound.

Usually processing stage granular media organosilicon compound is the first stage of preparation of the catalyst, and the processing stage by dialkylamines or, under certain conditions, dialkylamines mixed with trialkylaluminium second stage.

Perhaps the realization of the processing stages granular media organosilicon compound, dialkylamines or, under certain conditions, dialkylamines mixed with triethylaluminium, monochlorobenzene compound and compound of tetravalent titanium.

Preferred organosilicon compound is a compound selected from the group deoxygenation may include the additional step of processing electron carrier, as the selected electron-donating compound from the group comprising tetrahydrofuran, dimethylformamide, triethylorthoformate and tetraethoxysilane, and additional processing stage ORGANOMETALLIC compound, in particular alyuminiiorganicheskikh connection.

As alyuminiiorganicheskikh connection preferably trimethylaluminum or dimethylammoniumchloride.

In the present invention is applied granular media based on a refractory oxide. The carrier may contain a hydroxyl functional group. Granular media can have a specific surface area (BET) 50 - 1000 m2/g, for example, 100 - 600 m2/g and pore volume of 0.5 - 5 ml/g, for example, 1 to 3 ml/year Number in the media hydroxyl groups depends on the used media, from its specific surface area, from physico-chemical treatment and drying, which the media could be previously subjected. Ready-to-use granular media, typically contains 0.1 to 5, preferably 0.5 to 3 mmol of hydroxyl groups per gram. It is recommended that granular media at the moment of its use for the preparation of the catalyst was betwedn is rule 100 - 950oC, for example 150 - 800oC. Media can be selected, in particular, of silicon dioxide, aluminium oxide, aluminosilicate, or a mixture of these oxides. The carrier may consist of particles with a mass-average diameter in the range of 20 to 250 μm, preferably 30 to 200 μm, particularly 50 to 150 μm. Preferably, the carrier particles used have a spherical or spheroidal shape.

It is preferable to use silica, especially silica company Crosfield Company (UK) with the company designation "SD 490" and "ES70 or company WR Grace Company (Germany) with the brand names of "SG 332" and "SD 3217".

According to the invention the granular media is in contact with the organosilicon compound. The organosilicon compound can correspond to the General formula SiRmX4-min which R is alkyl with, for example, 1 to 6 carbon atoms; X represents a halogen atom such as chlorine or bromine, or alkoxygroup having, for example, 1 to 6 carbon atoms; and m = 1 to 4, preferably 1 to 3. Can be used silanes, such as diethoxydimethylsilane (DATMS), methyltrimethoxysilane, methyltriethoxysilane and tetraethoxysilane. The organosilicon compound can also betakey as hexamethyldisilazane (HMDS) of the formula (CH3)3Si-NH-Si(CH3)3.

We recommend contacting the media with the organosilicon compound to carry out the first stage of preparation of the catalyst. This allows you to use successfully organosilicon compound to reduce the content of hydroxyl functional groups in the carrier due to the reaction with these groups. The contacting can be carried out, for example, in a liquid hydrocarbon with 0.1 - 10 mol, preferably 0.5 to 5 mol, of organosilicon compound per gram of granular media in the temperature range 20 - 120oC, preferably 50 - 100oC. the reaction Time from 10 minutes to 10 hours At the end of this stage contact the obtained granular media can be washed one or more times with a liquid hydrocarbon.

Used dialkylamino preferably corresponds to the General formula MgR1R2and under certain conditions is a mixture or in combination with trialkylaluminium General formula AlR3R4R5where R1, R2, R3, R4and R5denote identical or different alkyl groups containing 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms. To alkaline. In particular, the use of molar ratio in the range from 0.01: 1 to 1: 1, such as 0.1:1 to 0.5:1. It is recommended to use dibutylamine, directimage, butylethylamine, ethylhexylamine or butylaniline. The preferred trialkylaluminium is triethylaluminium. Stage contacting media dialkylamines recommended stage after contacting the carrier with the organosilicon compound. The contacting may be, for example, carried out according to the method described in EP-A 453088. Usually in grams of granular media using 0.1 to 8, preferably 0.5 to 4 mmol dialkylamide. The resulting carrier contains 0.1 to 4, preferably 0.5 to 2.5 mmol of magnesium in the town of media. After receiving medium can be washed with a liquid hydrocarbon.

The method includes contacting the media with monochlorobenzene connection. This connection can be represented by a secondary or preferably tertiary alkylphenolate containing 3 to 19, preferably 3 to 13, carbon atoms and corresponding to the following General formula: R6R7R8CCl, in which R6and R7represent identical or different alkyl radicals containing 1 to 6, for example 1 to 4 atoms ug is the first radical, containing 1 to 6, for example of 1 to 4 carbon atoms, equal or different from R6and R7such as methyl, ethyl or n-propyl. Recommended secondary propylchloride, secondary butyl chloride, but especially tert.-the butyl chloride.

Monochlorobenzene connection can also be represented by a secondary or preferably tertiary cycloalkylation General formula

< / BR>
in which

R8represents a hydrogen atom or preferably an alkyl radical containing 1 to 6, for example of 1 to 4 carbon atoms, such as methyl or ethyl, n = 4 to 8, for example 5 to 8, especially 5. An example of such a connection can be cyclohexylurea or 1-methyl-1-chlorocyclohexane.

Monochlorobenzene connection can also be represented by a compound containing at least one aryl radical, of General formula

R9R10R11CCl

in which

R9represents an aryl radical containing 6 to 16, for example 6 to 10 carbon atoms, R10and R11represent identical or different radicals selected from hydrogen, alkyl radicals containing 1 to 6, for example of 1 to 4 carbon atoms, such as methyl, ethyl or n-propyl and aryl radicals containing 6 to 16, for example 6 - 10 ATR11usually are such aromatic hydrocarbon groups as phenyl, tolyl or naphthyl. Preferred benzylchloride and 1-phenyl-1-chlorate.

Stage contacting of granular media monochlorobenzene connection is usually carried out in most cases, after the stage of contacting media dialkylamines using, for example, methods ER-AND 453088. Usually g of granular media using 0.2 - 10 mmol monochloroacetic connection.

The method also includes the stage of contacting the carrier with the compound of tetravalent titanium. It is desirable to use a compound of titanium, soluble in the liquid hydrocarbon medium in which carry out the preparation of the catalyst. In particular, it is recommended that the compound of tetravalent titanium General formula

Ti(OR)nX4-n,

in which

R represents an alkyl radical containing 1 to 6, for example 2 to 4 carbon atoms, for example methyl, ethyl, propyl, isopropyl or butyl, X represents a chlorine atom or bromine, n is an integer or fractional number from O to 4, e.g. 0 - 3. Preferably, the application of titanium tetrachloride and dialogeditunchanged. However, if the catalyst is to apply for s is s titanium, for example, the compound of the above formula in which n is greater than 0.5. Recommended per mole of magnesium in the media to apply a 0.05 to 1 mol of titanium.

According to the present invention may hold the contacting of granular media with at least one electron-donor compound, preferably not containing hydrogen rolling. Examples of electron-donor compound can be a simple ester. The ether may be aliphatic ether, such as propyl ether or butyl ether, cyclic ether, such as tetrahydrofuran or dioxane, polyester, preferably the fluids, such as simple dimethyl ether of ethylene glycol or 2,2-dimethoxypropane. Electron-donating compound may also be complex aliphatic ether, such as ethyl acetate, aromatic ether complex, such as ethylbenzoic, aromatic polyester, such as dibutyl phthalate, tertiary amine, such as triethylamine, amidon, such as dimethylformamide, a silane, such as tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane or dichlorodioxane, silazanes, such as hexamethyldisilazane, orthoevra, such as triethylorthoformate. But usually, as stated above, as the electron is>Contacting the media with electron-donating compound are more preferable for the carrier, already processed monochlorobenzene connection, and, in addition, preferably before contacting the carrier with a compound of titanium. The contacting may be, for example, carried out using 0.01 to 2, preferably 0.05 to 1 mol of electron-donor compound per mole of magnesium in granular media. The contacting is usually carried out with stirring in a liquid hydrocarbon, such as n-hexane or n-heptane or a mixture thereof. This stage can be carried out in the temperature range 0 - 120oC, preferably 20 - 100oC. Contacting can last from 10 minutes to 10 hours To carry out this stage you can add electron-donating compound to a stirred suspension of granular media. The time necessary for this is 1 to 5 hours, preferably from 15 minutes to 2 hours May also stirring suspension of granular media in a liquid hydrocarbon containing electron-donating compound. Electron-donating compound may be used in pure form or in the form of a solution in a liquid hydrocarbon. In addition, the electron-donating compound to be used is the first carrier may be washed one or more times with a liquid hydrocarbon.

The method may also include one or more steps of contacting granular media ORGANOMETALLIC compound in addition to dialkylamide, which can be used for reconnection titanium. Reconnection titanium may be partial. ORGANOMETALLIC compound is typically a metal connection II or group III of the Periodic system of elements. For example, you can use alumoorganic, magyarkanizsa or tsinkorganicheskih connection. It is recommended to use triethylaluminium, triisobutylaluminum, tri-n - hexylamine or tri-n-octylamine. When using trimethylaluminum or dimethylammoniumchloride activity of the catalyst is significantly increased.

Stage contacting media ORGANOMETALLIC compound preferably carried out before contacting the carrier with a compound of titanium. This stage can also be successfully carried out after contacting media monochlorobenzene connection. Stage can be carried out in a liquid hydrocarbon, such as n-heptane, using 0.1 to 5 mol of ORGANOMETALLIC compound per mole of magnesium in the media. Usually per mole of magnesium in the medium p is such amount that the molar ratio between the ORGANOMETALLIC compound and the electron-donating compound is 1 to 5, preferably about 2. The contacting is usually carried out at a temperature of 20 - 120oC, preferably at 20 to 100oC for from 10 minutes to 10 o'clock the Received media may be washed one or more times with a liquid hydrocarbon.

After contacting the compounds with electron-donating compound and ORGANOMETALLIC compound obtained catalyst allows to obtain a polymer with improved morphology. Thus, the polymer may have a bulk density of 0.42 - 0.50 g/cm3.

According to the method according to the invention the carrier or the catalyst may be dried, for example, at 20 to 200oC, preferably at 50 to 150oC. the drying Operation can be carried out by passing a stream of dry nitrogen through mixed media or the final catalyst. The media is recommended to dry after contact with the electron-donating compound. It can also be dried after contact with the ORGANOMETALLIC compound.

The catalyst of the invention usually contain 0.1 to 1 mmol of titanium per gram of granular media. Titan may have a valence of minimalizatsii olefins, having, for example, 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, 4 - methyl-1-penten. The catalyst is well suited for polymers or copolymers of ethylene, preferably having a density of 0,880 - 0,970, and more preferably linear low density polyethylene with a relative density 0,910 - 0,930. The catalyst may be used in the form of a prepolymer containing, for example, 1 to 200 g, preferably 10 to 100 g of polymer per mmol of titanium.

(Co)polymers can be obtained in suspension in a liquid hydrocarbon, but preferably in the gas phase in the reactor with a fluidized bed and/or mixed layer. The catalyst is usually used in the presence of socializaton, which may be represented by ORGANOMETALLIC compound of a metal I-III group of the Periodic table. Usually as socializaton used trimethylaluminum or triethylaluminum.

Due to the good activity of the catalyst obtained (co)polymers have a low titanium content, in particular, less than 10 parts per million of titanium. (Co)polymers may have a melt index, determined at 190oC and a load of 2.16 kg (M12,16), from 0.01 to 200 g for 10 minutes (Co)polymers are characterized by a relatively narrow race-co monomer, such as linear low density polyethylene, as a rule, homogeneous, i.e. the distribution of the co monomer in the polymer statistiche.

Particles of different polymer morphology. The particles preferably have a spherical or spheroidal in shape with an average mass diameter of 300 to 1200 μm. Because of good morphology of the particles have the form of a powder with high bulk density, for example, in the range from 0.37 to 0.50 g/cm3. Usually, this powder has a low dust content.

The method of determining the mass-average diameter (Dm) and srednecenovogo diameter (Dn) of the particles

According to the invention the mass-average diameter (Dm) and srednetsenovoj diameter (Dn) of the particles of the medium is determined by the method specified in the application for the European patent 336545.

Determination of the distribution of molecular weight

The distribution of molecular weight (co)polymer calculated on the basis of the relationship srednevekovoi molecular weight (MW) to srednekamennogo molecular mass (PM) (co)polymer according to the curve of molecular weight, built using gel permeation chromatography on a Waters chromatograph 150 C (R) (high temperature chromatograph for gel permeation chromatography) under the following slave is the atur three columns Shodex (R) AT 80M/S 150oC,

the concentration of the sample with 0.1 wt.%,

injected volume: 500 ál,

detection with a Refractometer built into the chromatograph, with calibration on high density polyethylene sold by BP Chemicals S. N. C. under the firm name of Rigidex 6070 EA (R) and having a MW = 65000, MV/PM = 4, M12,16 = 6, as well as high-density polyethylene having MW = 210000 and MV/PM = 17,5.

Example 1. Obtaining a catalyst (D)

As the granular media used powder of silicon dioxide "SG332" (R) GRACE company (Germany) with a specific surface area (BET) 325 m2/g and pore volume of 1.84 ml/g, the Powder consists of particles with an average particle diameter by weight of 77 μm. The powder is dried for 5 h at 500oC. the Following operations are performed in an inert atmosphere.

In a reactor made of stainless steel of 1 l, equipped with a device for mixing, rotating at a speed of 250 rpm, load 800 ml of n-hexane, 60 g of dried silica and 23oC slowly over hours add 180 mmol hexamethyldisilazane (HMDS). The resulting mixture is stirred for 1 h at 23oC. the resulting solid product (A) three times washed with 600 ml of n-hexane at 23oC.

Then for 30 min at 23oC slowly every product (B) three of the 23oC washed with 600 ml of n-hexane, and after such a washing product contains 1.5 mmol of magnesium per gram of silica.

The reactor containing the solid product (B) in suspension in 600 ml of n-hexane, and then heated to 50oC. In a reactor under stirring for one hour add 180 mmol of tert.-the butyl chloride. At the end of this period the mixture is stirred for 1 h at 50oC, then cooled to room temperature (23oC). The obtained solid product (C) at the 23oC three times washed with 600 ml of n-hexane. After such washing, the product contains (per gram of silica) 1.5 mmol of magnesium, 3 mmol of chlorine and has no reducing ability with respect to titanium tetrachloride.

Then the reactor is heated to 50oC and for 30 min added 15 mmol of titanium tetrachloride. The resulting mixture was stirred for 1 h at 50oC, then cooled to room temperature (23oC). The obtained solid product (D) contains (per gram of silica) 1.5 mmol of magnesium, 4.5 mmol of chlorine and 0.54 mmol of titanium in the tetravalent state.

Example 2. Polymerization of ethylene in the reactor with mechanical mixed layer

In the reactor of stainless steel 2.6 l sozdat 350 rpm In the reactor load method for loading dry powder 200 g of completely anhydrous polyethylene powder obtained in the preceding reaction, and then 10 mmol of triethylaluminum and 1 g of catalyst (D). The reactor is heated to 80oC, then deliver hydrogen to a total pressure of 0.25 MPa and then introducing ethylene, until the pressure becomes equal to 0.75 MPa. The flow of ethylene continue with maintaining the total pressure of 0.75 MPa. After 2 h 30 min from the reactor extract 600 g of polyethylene with M12,16 3,93 g/10 min and a molecular weight distribution of 4.2.

Example 3. Obtaining a catalyst (H)

As the granular media used powder of silicon dioxide "SG332" (R) GRACE company (Germany) with a specific surface area (BET) 325 m2/g and pore volume of 1.84 ml/g, the Powder consists of particles with an average particle diameter by weight of 77 μm. Subsequent operations are performed in an inert atmosphere of nitrogen.

In the reactor of 1 l stainless steel, provided with a device for stirring speed 350 rpm, load 600 ml of n - hexane, 60 g of dried silica and slowly when 23oC for 30 min add 90 mmol dibutylamine. The resulting solid product (E) contains 1.5 mmol of magnesium per gram of duwamish stirred for 1 h at 23oC. the result is a solid product (F).

Then the reactor containing the solid product (F) in suspension in 600 ml of n-hexane heated to 50oC. In the reactor slowly over 30 min with stirring load 90 mmol of tert.-the butyl chloride. At the end of this period the mixture is stirred for 1 h at 50oC and then cooled to room temperature 23oC. the resulting solid product (G) contains (per gram of silica) of 1.4 mmol of magnesium and 1.4 mmol of chlorine.

Then the reactor is heated to 50oC and it slowly over hours to make 30 mmol of titanium tetrachloride. The resulting mixture was stirred for 1 h at 50oC and then cooled to room temperature (23oC). The obtained solid product (H) contains (per gram of silica) of 1.3 mmol of magnesium, 2.4 mmol of chlorine and 0.55 mmol of titanium.

Example 4. Polymerization of ethylene in the reactor with mechanical mixed layer

The method exactly reproduces the polymerization method of example 2 except that instead of 1 g of the catalyst (D) is administered 1 g of the catalyst (H). After polymerization for 2 h 28 min received 600 g of polyethylene with M12 16 4,37 g/10 min and a molecular weight distribution 4,1.

Example 5. The floor is RA 3.

The reactor containing the solid product (E) in suspension in 600 ml of n-hexane heated to 50oC. In a reactor under stirring slowly for one hour load 180 mmol of tert.-the butyl chloride. At the end of this period the mixture is stirred for 1 h at 50oC, then cooled to room temperature (23o). The obtained solid product (I) contains (per gram of silica) of 1.4 mmol of magnesium, 2.8 mmol of chlorine and has no reducing ability with respect to titanium tetrachloride.

Then slowly for 25 min at 23oC add 72 mmol hexamethyldisilazane (HMDS). The resulting mixture is stirred for 1 h at 23oC. the resulting solid product (J) at the 23oC three times washed with 600 ml of n-hexane. The product contains (per gram of silica) of 1.4 mmol of magnesium and 2.6 mmol of chlorine.

Then the reactor is heated to 50oC and it slowly over hours to make 30 mmol of titanium tetrachloride. The resulting mixture was stirred for 1 h at 50oC and then cooled to room temperature (23oC). The obtained solid product (K) contains (per gram of silica) of 1.3 mmol of magnesium, 2.9 mmol of chlorine and of 0.53 mmol tetravalent titanium.

Example 7. Obtaining a catalyst (L)

The technique mimics the procedure of example 5 to obtain a solid product (I). Then the reactor is heated to 50oC and it slowly over hours added 30 mmol of titanium tetrachloride. The resulting mixture was stirred for 1 h at 50oC, then cooled to room temperature (23oC). Then added to the mixture 72 mmol GMDS. The obtained solid product (L) contains (per gram of silica) 1.5 mmol of magnesium, 3.1 mmol of chlorine and 0.52 mmol tetravalent titanium.

Example 8. Polymerization of ethylene in the reactor with mechanical mixed layer

The method exactly reproduces the polymerization method of example 2 except that instead of 1 g of the catalyst (D) using 1 g of the catalyst (L). After polymerization for 2 h 33 min received 600 g of polyethylene with M12 16 of 4.54 g/10 min and a molecular weight distribution of 4.2.

Example 9 (comparative). Obtaining a catalyst (O)

As the granular media used in the/year The powder consists of particles with srednevekovym diameter of 77 mm. The powder is dried for 5 h at 500oC. the Following operations are performed in an inert atmosphere of nitrogen. In the reactor of 1 l stainless steel, equipped with a stirrer speed of 250 rpm, load 600 ml of n-hexane, 60 g of dry silica and within one hour at 23oC add 190 mmol dibutylamine. The resulting solid product (M) at the 23oC three times washed with 600 ml of n-hexane, and after such a washing product contains 1.7 mmol of magnesium per gram of silica.

The reactor containing the solid product (M) in suspension in 600 ml of n-hexane heated to 50oC. In the reactor slowly over 1 hour with stirring 204 mmol of tert.-the butyl chloride. At the end of this period the mixture is stirred for one hour at 50oC, then cooled to room temperature (23oC). The obtained solid product (N) at the 23oC three times washed with 600 ml of n-hexane. After such a washing product contains (per gram of silica) 1.7 mmol magnesium, 2.7 mmol of chlorine and has no reducing ability with respect to titanium tetrachloride.

Then the reactor is heated to 50oC and it slowly in mee then cooled to room temperature. The obtained solid product (O) at the 23oC three times washed with 600 ml of n-hexane. After such washing, the product contains (per gram of silica) 1.7 mmol magnesium, 4.8 mmol of chlorine and 0.54 mmol titanium only in the tetravalent state.

Example 10 (comparative). Polymerization of ethylene in the reactor with mechanical mixed layer

The method exactly reproduces the polymerization method of example 2 except that instead of 1 g of the catalyst (D) using 1 g of the catalyst (O). After 3 h 20 min get 600 g of polyethylene having M12,16 2.75 g/10 min and a molecular weight distribution 5.

Example 11. a) Obtaining catalyst

The experience carried out in a reactor with a fluidized bed, which is a vertical cylinder with a height of 75 cm and 5 cm in diameter, located under the boot of the camera. The reactor is equipped with a plate for the fluidization of porous material located in the lower part of the cylinder. In addition, the reactor is equipped with a heater, the current due to electrical resistance, and supply system pseudoviruses gas.

In the reactor, which has a temperature of 60oC and served pseudoviruses gas consisting of nitrogen content of vapors of silicon, sold under the brand name "ES 70 (R) firm Joseph Crosfild afnd Sons (UK). The mass-average diameter of spheroid particles of 45 μm. The particles are dried 8 hours at 900oC. the Following operations are performed in nitrogen atmosphere.

At the 23oC in the reactor stainless steel 1 l load 600 ml of n-hexane, 60 g of pre-dried spherical silica and 48 mmol GMDS. A reactor equipped with a stirrer rotating at 250 revolutions per minute. The resulting mixture was stirred for 4 h at 80oC. the resulting solid product (A) washed three times with 50oC n-hexane (600 ml).

Then, into the reactor containing the solid product (A) in suspension in 600 ml of n-hexane at 50oC for 30 min add 48 mmol dibutylamine. The resulting mixture was heated 1 h at 50oC. the resulting solid product (B) contains 0.8 mmol of magnesium per gram of silica. The reactor containing the solid product (B) in suspension in 600 ml of n-hexane heated to 50oC and under stirring for 30 min into it enter 96 mmol of tert. -butyl chloride. At the end of this period the mixture is stirred for 1 h at 50oC. the resulting solid product (C) three 50oC promol chlorine and has no basic functional groups with healing activity in relation to compounds of tetravalent titanium. Then the reactor is heated to 50oC during 15 min to a suspension of the solid product (C) in 600 ml of n-hexane added to 4.8 mmol of triethylorthoformate. After the addition the mixture is stirred for 30 min at 50oC. In a preheated 50oC reactor for 30 min add 19.2 mmol of trimethylaluminum. The resulting mixture was stirred for 30 min at 50oC. In a preheated 50oC reactor for 30 min add 9.6 mmol of diisopropylethylamine. The resulting mixture was heated 1 h at 50oC and then cooled to a temperature of about 20oC. the resulting solid catalyst contains (per gram of silica) 0.8 mmol of magnesium, 1.6 mmol of chlorine and 0.16 mmol of titanium.

(b) Copolymerization of ethylene in suspension

In the reactor 2.6 l stainless steel, equipped with a stirrer speed of 700 rpm, in which a nitrogen pressure of 0.1 MPa, load 1 l of absolutely anhydrous n-hexane and then 6 mmol of trimethylaluminum, the above-described catalyst in an amount corresponding to 0.1 mmol of titanium, and 80 ml of 4-methyl-1-pentene. The reactor is heated to 80oC and it serves hydrogen until the total pressure reaches of 0.16 MPa, and then served ethylene until the total pressure reaches 0.4 MPa. Ethylene and serves dimera, characterized by

melt index (M12,16) 0,86 g/10 min;

parameter yield n - 1,49, calculated according to the formula n = log(M121,6/M12,16)/log(21,6/2,16), where M,6 - the melt index of the polymer, determined at 190oC under a load of 21.6 kg;

relative density 0,933;

the weight content of 4-methyl-1-pentene 4,7%;

the distribution of molecular weight of 3.9.

Example 12. a) Obtaining catalyst

Powder microspheroidal particles of silicon dioxide sold by Joseph Crosfield and Sons (UK) under the trade designation "ES 70", is subjected to heat treatment for 12 h at 870oC in the reactor with a fluidized bed through which is passed a current of dry nitrogen. After heat treatment, the obtained dried powder of silicon dioxide is cooled to a temperature of about 20oC and kept in a nitrogen atmosphere.

In reactor 240 l stainless steel, equipped with a stirrer rotating at a speed of 166 rpm, load at an ambient temperature of 20 kg pre-dried silica and n-hexane in an amount necessary to obtain 110 litres of suspension, and then at a temperature of 50oC add 16 mmol GMDS. The resulting suspension in the Rami n-hexane.

At the 50oC for 2 h in the reactor lead 30 mol dibutylamine. The resulting suspension is stirred for 1 h at 50oC. In slurries containing solid product (E) magnesium content of 1.5 mmol per gram of silica.

The reactor containing the solid product (E) in the form of a suspension in n-hexane heated to 50oC for 2 h in the reactor is injected 60 mol of tert.-the butyl chloride. At the end of this period the resulting suspension is stirred for 1 h at 50oC. In slurries containing solid product (F), which is at the 50oC three times washed with 130 l of n-hexane.

Then heated to 50oC reactor quickly insert 6 mol triethylorthoformate. The resulting suspension is stirred for 1 h at 50oC.

Then the reactor at 50oC serves 12 mol of trimethylaluminum. The resulting suspension is stirred for 2 h at 80oC. the Reactor is cooled to 50oC and for 1 h enter 3 mol of Tetra-n-butoxide titanium and 3 mol of titanium tetrachloride. The resulting suspension is stirred for 2 h at 50oC, and then cooled to a temperature of about 20oC. Suspension contains the catalyst, which at 20oC five times washed with 130 l of n-hexane. The resulting catalyst contains (per gram dioxide BAP is e periodic operation of fluidized bed

The experience of conducting breakcore fluidized bed with a diameter of 15 cm, equipped with a compressor for recycling pseudoviruses gas. To create the initial fluidized bed in the reactor load 1000 g obtained in the preceding reaction of the polymer powder with a relative density 0,916, M12,16 1.63 g/10 min and a bulk weight of 0.39 g/cm3. Then the reactor was rinsed 3 hours at 95oC dry nitrogen. After that, the reactor is filled with a mixture of ethylene, 1-butene and hydrogen. The partial pressure of the components in the mixture following MPa.

Ethylene - 0,54

Hydrogen - 0,15

1-butene - 0,21

The speed of fluidization gas mixture support 25 cm/s, and the temperature pseudoviruses gas support at 80oC.

Then injected into the reactor 35 mmol of trimethylaluminum and previously the catalyst in an amount corresponding 0.33 mmol of titanium. Feed to the reactor of ethylene in it keep a constant pressure. At the end of the copolymerization reactor is cooled, Tegaserod and finally rinsed with nitrogen. The obtained powder of the copolymer is characterized by:

relative density - 0,919;

M12,16 to 1 g/10 minutes;

bulk weight - 0,41 g/cm3.

Example 13. a) Obtaining prepolymer

oC and then into the reactor at a constant flow rate of 15 kg/h for 5 h 20 min serves ethylene. By the end of the reaction terpolymerization obtained a suspension of the prepolymer is cooled to 60oC. Received 80 kg of the prepolymer with excellent yield in the dry state, srednevekovym a particle diameter of 90 μm and a bulk weight of 0.45 g/ml

b) Polymerization of ethylene and 1-hexene in the gas phase

In a reactor with a fluidized bed with a diameter of 45 cm load 100 kg of absolutely anhydrous polyethylene in the form load of the powder obtained in the preceding reaction. Loading is carried out in nitrogen atmosphere. After that, the reactor serves with the rising speed of 44 cm/s heated to 80oC gas mixture comprising hydrogen, ethylene, 1-hexene and nitrogen. The partial pressure of the components in this mixture the following, IPA:

Hydrogen - 0,07

Ethylene - 0,325

1-HEXEN - 0,058

Nitrogen - 0,85

bulk weight of 0.4 g/cm,

M12,16 - 0,9 g/10 min,

parameter yield n - 1,5,

relative density - 0,918,

srednevekovym diameter of 600 μm,

the content of fine particles with a diameter of less than 125 μm -0,4% by weight,

titanium content is 9 parts per million,

the distribution of molecular weight is 3.9.

1. The method of producing catalyst type catalyst of the Ziegler-Natta containing granular refractory oxide carrier and includes the use stage of processing dialkylamines or under certain conditions dialkylamines mixed with trialkylaluminium, the stage of processing monochlorobenzene compound and compound of tetravalent titanium, characterized in that the process includes the additional step of processing organosilicon compound.

2. The method according to p. 1, characterized in that the processing stage granular media organosilicon compound is the first stage of preparation of the catalyst, and the processing stage by dialkylamines or under certain conditions dialkylamines mixed with trialkylaluminium second stud the technical connection dialkylamines or under certain conditions dialkylamines mixed with triethylaluminium, monochlorobenzene compound and compound of tetravalent titanium carried out consistently.

4. The method according to p. 1, characterized in that as the organosilicon use compounds selected from the group including diethoxydimethylsilane, methyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane or hexamethyldisilazane.

5. The method according to PP.1 and 2, characterized in that it further includes a step of processing the electron-donating compound.

6. The method according to p. 5, characterized in that as electrondonor connection using a connection selected from the group comprising tetrahydrofuran, dimethylformamide, triethylorthoformate or tetraethoxysilane.

7. The method according to PP.1 - 6, characterized in that it additionally includes the stage of processing alyuminiiorganicheskikh connection.

8. The method according to p. 7, characterized in that as alyuminiiorganicheskikh connection using trimethylaluminum or dimethylammoniumchloride.

9. Catalyst type catalyst of the Ziegler-Natta obtained by the method according to PP.1 - 8.

 

Same patents:

The invention relates to a titanium containing catalyst component for the polymerization of ethylene, which in large polymerization activity can be obtained a polymer of ethylene with a narrow size distribution of particles, the catalyst for polymerization of ethylene comprising this titanium containing component and the polymerization of ethylene using a specified catalyst for polymerization of ethylene

The invention relates to the field of technology of macromolecular compounds, namely a process for the production of stereoregular Polivanov under the influence of the catalytic systems of the Ziegler-Natta

The invention relates to Socialisticheskaya composition used for the polymerization of alpha-olefins by catalytic system comprising the above composition and method for the polymerization of alpha-olefins, in particular, to method stereospetsifichno propylene polymerization conducted in the presence of catalytic systems

The invention relates to a solid catalyst type Ziegler-Natta suitable for polymerization or copolymerization of olefins, and to a method for producing this catalyst

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The invention relates to a new class of electron-donating organic silicon compounds for use as electron donor in the deposited catalytic systems of the Ziegler-Natta, especially for such catalytic systems, which have as a carrier of activated anhydrous magnesium chloride, for the polymerization of alpha-olefins

FIELD: polymerization catalysts.

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

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

3 cl, 1 tbl, 13 ex

FIELD: polymerization catalysts.

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

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

3 cl, 1 tbl, 4 ex

Catalyst and method // 2316396

FIELD: organic synthesis and catalysts.

SUBSTANCE: invention relates to esterification method utilizing organotitanium or organozirconium catalyst and provides catalytic composition useful in preparation of esters, including polyesters, which contains (i) product of reaction between metal M alcoholate or condensed alcoholate selected from titanium, zirconium, and hafnium alcoholates, (ii) alcohols containing at least two hydroxy groups, (iii) 2-hydroxycarboxylic acid, and (iv) base, wherein molar ratio of base to hydroxycarboxylic acid is within the range between 0.01:1 and 0.79:1. Esterification reaction in presence of above catalyst is also described.

EFFECT: avoided yellowness in final product, raised temperature for the beginning of crystallization and crystallization temperature of polyester.

14 cl, 4 tbl, 20 ex

FIELD: medicine.

SUBSTANCE: there is described catalyst component for ethylene polymerisation, containing reaction product of magnesium complex at least one titanium compound, at least one alcoholic compound, at least one silicon compound and optionally organoaluminium compound, wherein magnesium complex represents a product of magnesium halogenide in a solvent system containing organic epoxide and organophosphorous compound; alcoholic compound represents linear or branched alkyl or cycloalkyl alcohol containing 1 to 10 carbon atoms, or aryl or aralkyl alcohol having 6 to 20 carbon atoms, and alcoholic compound is optionally substituted with one or more halogen atoms; titanium compound has general formula Ti(OR)aXb wherein R means C1-C14 aliphatic or aromatic hydrocarbyl, X is halogen, and means 0, 1 or 2, b is an integer 1 to 4, and a+b=3 or 4; silicon compound is organic silicon compound of general formula R1xR2ySi(OR3)z wherein R1 and R2 independently represent hydrocarbyl or halogen atom, R3 means hydrocarbyl, 0 ≤ x ≤ 2, 0 ≤ y ≤ 2, 0 ≤ z ≤ 4 and x+y+z=4; organoaluminium compound has general formula AlR4nX13-n wherein R4 means hydrogen or hydrocarbyl containing 1 to 20 carbon atoms, X1 is halogen atom and n has a value satisfying the inequality 1 <n≤3. There is also described method for making the catalyst component for ethylene polymerisation therewith including the stages as follows: (1) magnesium halogenide dissolution in the solvent system containing organic epoxide and organic organophosphorous compound. The solvent system optionally, however preferentially in addition contains an inert thinner to form a homogeneous solution; (2) addition of alcoholic compounds prior to, after or during formation of homogeneous solution containing magnesium halogenide; (3) contacting the solution received at the stage (2) with titanium compound, with silicon compound added prior to, after or during contacting process to form a mixture; (4) slow heating of the mixture to temperature 60°C to 110°C and holding at this temperature for some time with a solid substance gradually deposited in heating; and (5) recovery of the solid substance formed at the stage (4) to produce the catalyst component, where: alcoholic compound represents linear or branched alkyl or cycloalkyl alcohol with 1 to 10 carbon atoms, or aryl or agalkyl alcohol with 6-20 carbon atoms, with alcoholic compound being optionally substituted with halogen atom (atoms); titanium compound has general formula Ti(OR)aXb wherein R represents C1-C14aliphatic or aromatic hydrocarbyl, X means halogen atom, and is equal to 0, 1 or 2, b represents an integer 1 to 4, and a+b=3 or 4; and silicon compound represents organic silicon compound of general formula R1XR2ySi(OR3)z wherein R1 and R2 independently represent hydrocarbyl or halogen atom, R3 means hydrocarbyl, 0 ≤ x ≤ 2, 0 ≤ y ≤ 2, 0 ≤ z ≤ 4, and x+y+z=4. There is also described a catalyst for ethylene polymerisation which contains a reaction product of: (1) the catalyst component described above; and (2) organoaluminium cocatalyst of formula AlR5nX23-n wherein R5 represents hydrogen or hydrocarbyl, with 1 to 20 carbon atoms, X stands for halogen atom, and n corresponds to the inequality 1<n≤3. There is also described method of ethylene polymerisation including the stages as follows: (i) contacting of ethylene and optionally comonomer (comonomers) with the catalyst described above in polymerisation environment to make polymer; and (ii) recovery of polymer prepared at the stage (i).

EFFECT: catalysts are characterised with high catalytic activity and narrow polymer particle size distribution, and especially applicable for the method of suspension ethylene polymerisation.

21 cl,4 tbl, 30 ex, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of producing organic carbonates and carbamates. Described is an alcoholysis method, involving: feeding reactants and a trace amount of a soluble organometallic compound, which is soluble in the reactants, into a reactor containing a solid alcoholysis catalyst, wherein the trace amount ranges from about 1 ppm to about 3000 ppm with respect to total mass of the added reactants; where the soluble organometallic compound and the solid alcoholysis catalyst each independently contains a Group II to Group VI element. Described is a method of producing dialkylcarbonates, involving: feeding an alcohol and an alcoholysis reactant, containing at least one compound from urea, organic carbamate and cyclic carbonate, in the presence of the catalyst system described above. Described is a method of producing diarylcarbonate, involving: feeding an aromatic hydroxy compound and dialkylcarbonate in the presence of the catalyst system described above. Described is a method of producing alkylarylcarbonate, involving: feeding an aromatic hydroxy compound and dialkylcarbonate in the presence of the catalyst system described above. Described is a method of producing biodiesel, involving: feeding an alcohol and glycerine in the presence of the catalyst system described above The methods described above involve reaction of a spent solid alcoholysis catalyst, involving: removal of polymer materials deposited on the catalyst; and redeposition of catalytically active metals on the solid catalyst.

EFFECT: longer duration of the cycle of the alcoholysis method.

36 cl, 7 tbl, 18 dwg, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing bicyclo[4,2,1]nona-2,4-dienes of general formula where R=H, -(CH2)6-; R1=Me, Bu, Hex, Ph, Bn, -(CH2)6-, -(CH2)5-, CH2TMS, R2=H, -(CH2)5-, Ph, CH2TMS via catalytic reaction of 1,2-dienes with 1,3,5-cycloheptatriene (CHT). The catalyst system used is Ti(acac)2Cl2-Et2AlCl, the 1,2-diene used is a compound of general formula (where R, R1, R2 are described above), the reaction is carried out with molar ratio 1,2-diene:CHT:Ti(acac)2Cl2:Et2AlCl=(10-14):10:(0.1-0.3):4 in an ampoule at 20-80°C, in benzene for 6-48 hours.

EFFECT: invention reduces power consumption and enables to use a more stable catalyst.

17 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method for combined production of pentacyclo[7.5.0.02.8.05.14.07.11]tetradeca-3,12-diene of formula

and pentacyclo[8.4.0.03.7.04.14.06.11]tetradeca-8,12-diene of formula

The method includes homogenisation of 1,3,5-cycloheptatriene (CHT) in the presence of a Ti-containing catalyst system, and is characterised by that the catalyst used is Ti(acac)2Cl2-Et2AlCl, the reaction is carried out with molar ratio CHT:Ti(acac)2Cl2:Et2AlCl=10:(0.1-0.3):4, in an argon atmosphere, at 5-80°C, in benzene for 6-72 hours.

EFFECT: method enables to use a more stable catalyst and reduces power consumption.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 2-endo-ethyl-5-exo-ethylpentacyclo[8.4.0.03.7.04.14.06.11]tetradeca-8,12-diene of formula (1) The method is characterised by that homogenisation of 7-ethyl-1,3,5-cycloheptatriene (C9H12) is carried out in the presence of a catalyst system TiX2Cl2-Et2AlCl (X=Cl, acac, i-PrO), with molar ratio C9H12:TiX2Cl2:Et2AlCl = 10:(0.1-0.3):4, in an argo atmosphere at 20-100°C in benzene for 8-48 hours.

EFFECT: method enables to separately obtain the desired compound.

9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates a catalyst component for ethylene polymerisation, a method of producing said component, a catalyst and a polymerisation method. The catalyst component includes a reaction product of (1) a magnesium complex, which is a magnesium halide solution in a solvent system; (2) at least one titanium compound of formula Ti(OR)aXb, where R, X, a, b are given in the claim, and (3) at least one organosilicon compound of formula (I), where the values of radicals are given in the claim. The solvent system is a system comprising at least one organic epoxy compound, at least one organoboron compound, at least one alcohol and optionally at least one inert diluent, or a system which includes at least one organic epoxy compound, at least one organophosphorus compound, at least one alcohol and optionally at least one inert diluent.

EFFECT: catalyst component obtained using said method provides excellent efficiency, including high catalytic activity, good hydrogen sensitivity, narrow particle size distribution of the polymer product, low content of the fine (dust-like) fraction and high bulk weight of the polymer product; a compound of formula (I):

.

13 cl, 2 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to catalytic material, having catalytic activity in chemical reactions. Material contains a hybrid compound consisting of metal oxides and polyvinyl alcohol or derivatives thereof. Metal oxides include at least one substance selected from compounds of silicic acid, compounds of tungsten acid and compounds of zirconium acid, metal catalyst particle is embedded in hybrid compound. Hybrid compound comprises polymer additives, which have a link -CH2-CH2-O- and have a branched structure and/or contains polymer additives, which have a link -Si(CH3)2-O- with carboxyl groups, added to part of silicon atoms. Also disclosed are methods of producing catalytic material.

EFFECT: invention enables to obtain materials with high catalytic activity, which can be used in catalytic processes in combination with different types of solvents.

4 cl, 8 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalyst for olefin polymerisation, in particular, to catalyst which contains compounds of silicon ethers with novel structure, as well as to application of claimed catalyst in olefin polymerisation, and in particular, in propylene polymerisation. Described is catalyst for olefin polymerisation, containing reaction product, consisting of the following components: (A) hard titanium-containing catalytic component including magnesium, titanium and halogen as obligatory components; (B) catalytic component containing organic aluminium compound; (C) catalytic component containing compound of silicon ether, where said compound of silicon ether is represented by general formula: , groups R1-R12 and A are determined in description of claimed invention. Also described is application of catalyst for polymerisation of olefins with formula CH2=CHR, in which group R represents hydrogen or C1-C6 alkyl or aryl, or for copolymerisation of said olefins with α-olefin co-monomer which contains from 2 to 20 carbon atoms. Also described is method of olefin polymerisation including bringing into contact olefin with formula CH2=CHR, in which R is hydrogen or C1-C6 alkyl or aryl. Also described is method of propylene polymerisation, including bringing into contact propylene.

EFFECT: application of catalyst, containing described above product, for olefin polymerisation.

9 cl, 26 ex

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