Precatalysts for the production of polymers of ethylene, method of its production and use

 

(57) Abstract:

The invention relates to precatalytic component of the catalytic composition of the Ziegler-Natta, suitable for the production of polymers of ethylene. Precatalysts includes inorganic carrier, chlorine compounds, magnesium and titanium on the specified media. The balance of activity of AV procatalyse under given conditions of polymerization is determined by the expression AB>3,2, where

< / BR>
A - polymerizing activity in CT PE/g cat.h; MFR2- speed melt flow g/min under a load of 2.16 kg according to ISO 1133), the absence of a Superscript (') means the polymerization with a low rate of flow of the melt, the presence of a Superscript (') means the polymerization with a high rate of flow of the melt. These compounds improve the efficiency polymersomes catalyst, the duration of its use and other properties of the catalytic mixture and primarily the properties of the polymer obtained by using the mixture of catalysts. 3 S. and 36 C.p. f-crystals, 2 tab., 1 Il.

The invention relates to precatalytic component of the catalytic composition of the Ziegler - Natta, suitable for the production of polymers of ethylene. The composition includes a mixture consisting retina relates also to the method of its production and use.

Ethylene, alone or together with other olefinic unsaturated monomers may be polymerized in the presence of a composite catalyst having two components: a transition metal compound 4 - 6th group of the Periodic system of elements (Hubbard,IUPAC 1970), which is often referred to as proletarization, and the connection metal 1 to 3 groups of the Periodic system of elements, the so-called socialization. The catalyst of the Ziegler-Natta was further improved by premises pronatalistic on a more or less inert carrier particles and by introducing at the stage of its preparation of various additives, among which the compounds of donor electrons. These compounds improve the efficiency polymersomes catalyst, the duration of its use and other properties of the catalytic mixture, and primarily the properties of the polymer obtained by using the mixture of catalysts.

In the formation of ethylene and other polymers are not identical in molecular weight molecules, and their mixture with narrow or wide distribution of molecular weights. Can be dened in a number average molecular weight in the polymer mixture for a description of the most common molecular weights by determining the maximum of p is the weight in the polymerization reaction, you can add the connection, call agent chain transfer. To obtain polymeric products with different molecular weights in a polymerization reaction, you need to enter different amounts of the agent controlling the molecular weight. The most common and preferred agent of chain transfer is hydrogen, because of a growing chain does not remain foreign atoms or groups, which could interfere with the polymerization process, or to impart desirable properties of the polymer product.

Ease of modification of the molecular weight of the obtained polymer, depending on the amount of hydrogen, or the so-called change of the hydrogen sensitivity is strongly dependent on the composition of the catalyst. The problem usually is that in the production of polyethylene polymerization activity of some catalysts for obtaining polymers with high molecular weight is higher, usually many times, and even ten times higher than for obtaining polymers with a low molecular weight.

This lack of balance catalytic activity is a common disadvantage of all known catalysts. The imbalance manifests itself when, when using the known catalysts, there is a sharp drop in productivity is to consider melt), the conditions of polymerization, giving polymers with a low molecular weight (high fluidity of the melt). Even if this kind of commercial catalyst has a quite good performance in the case of a polymer with a value of melt flow MFR = 1 (1 MFR, determined according to ISO 1133), during the transition to polymer with a MFR of 500 only 10% of the performance of the catalyst. Thus, it is desirable to obtain a catalytic system having a high activity, regardless of the molar mass of the resulting polymer.

According to the invention proposes a new precatalysts, which can be obtained with equal and high activity ethylene homopolymers or copolymers with low or high molecular weight. Regardless introduced into the polymerization reactor hydrogen, can be achieved in the balance of activity in both cases when using procatalyse under item 1 of the claims.

The unique properties of the catalyst according to the invention, include a good balance of activity in a very wide range of values of partial pressure of hydrogen used in the polymerization to regulate the molar mass. Thus, it is possible to carry out the universi high performance. This balance HONEY/activity makes the catalyst universal fit for most types of polyethylene resins in all polymerization processes using heterogeneous catalytic system.

The invention solves the problem at the same time to get the maximum catalytic activity and its independence from the pressure of the polymerization of hydrogen, i.e., the flow rate of the polymer melt by choosing an appropriate balance of activities. The balance of the activities of AB can be defined as a

< / BR>
what gives

< / BR>
where

A - polymerizing activity in units of kg PE /g catalizadores,

MFR2- speed melt flow g/min under a load of 2.16 kg according to the standard ISO 1133,

without Superscript (') - low MFR2,

with the upper index (') - high MFR2.

According to the invention, the problem is solved by the condition

AB 3,2.

Thus, it is preferable to select the value of the balance of activities of conditions

AB5.

According to another variant of the invention precatalysts includes inorganic carrier coated with a chlorine compounds, magnesium, titanium. It is prepared in processee formula

(RnMeCl3-n)m(1)

where R is an alkyl radical with C1- C20, Me is a metal from III (13) group of the Periodic system of elements, n = 1 or 2, m = 1 or 2

this forms a first reaction product;

b) a first reaction product interacts with the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium, with the formation of the second reaction product,

C) a second reaction product interacts with the connection of titanium containing chlorine, with the General formula

ClxTi(ORIV)4-x(2)

where

RIV- hydrocarbonyl radical with C2-C20< / BR>
and x = 3 or 4, with the formation of the specified pronatalistic.

Described in this patent, the catalyst includes, therefore, alkylmethacrylamide, which is the internal soluble gloriouse agent, which also acts as acetalization soluble compound or mixture of compounds of magnesium (hereinafter referred to as the magnesium complex) with a sufficiently low viscosity and a compound of titanium containing chlorine. Under the solubility soluble compounds referring to their solubility in nonpolar hydrocarbon solvents. The components of the catalyst p is monentary catalyst, having sufficiently low viscosity that can be achieved with good structure of the catalyst and then the polymer.

The material of the carrier should have an appropriate particle size, the greater the porosity and large specific surface area. A good result is achieved if the material of the carrier has a specific surface area of 100 to 500 m2/g media and pore volume of 1 to 3 ml/g of carrier. The material of the carrier should also be pre-treated, for example the silane treated or alkilani aluminum, etc., Suitable oxides of some metals, but the preferred oxides of silicon, aluminum, titanium, chromium or zirconium, or mixtures thereof. Most preferred is silicon dioxide or silica.

Prior to impregnation of the other catalyst components, it is desirable to dry the media. Good results are obtained if the media is subjected to heat treatment at a temperature of from 100oC to 900oWith sufficient time, the number of surface hydroxyl groups, in the case of silica decreases to below 2 mmol/g SiO2. Internal socialization and gloriouse agent must be a connection metal containing chlorine, and to be soluble in nonpolar Aglaia (1):

(RnMeCl3-n)m(1)

where R is an alkyl radical C1-C20. Me is a metal from group III (13) of the Periodic system of elements, preferably aluminum, n=1 or 2, and m=1 or 2. The alkyl radical R may be linear, branched, or cyclic, or a mixture of them preferred C2-C20alkyl. Can also be used in combination with different gloriously agents. Good results are obtained when using alkylhalogenide, preferably lower alkylaminocarbonyl, the most preferred ethylaminoethanol.

Magnesium complex used in this catalytic synthesis must be completely soluble in non-polar hydrocarbon solvent. Magnesium complex compound, mixture) must have a General composition formula

Mga(OR')bRcXd(3)

where X is halogen, preferably chlorine, R' is a hydrocarbon radical, preferably a hydrocarbon radical with C2-C20that may or may not contain heteroelement, R" is a hydrocarbon radical with C2-C20and where a > 1, b > 0, C > 0, a = 1/2(b+c+d), d 0 and the molar ratio C/b < 1, preferably from 0.05 to 0.1.

Other preferred and>/BR>Mg(OR"')p(R)2-p(4)

Mg(OCOR"')p(R)2-p(5)

Mg(O-CH2-O-R"')p(R)2-p(6)

In (4), (5) and (6) R' and R" may be different or identical hydrocarbon radicals. Preferably, a linear or branched aliphatic or aromatic radicals, and the most preferred R' is an alkyl radical, p is in the range 1 <p< 2, and most preferably 1,2 < p < 2,0. OCO - carboxyl group of the carboxylic acid. Significantly for the composition to p was less than 2.

Connection (3) - (6) in the following text referred to as magnesium complexes. It is necessary that all the compounds (3) - (6) there were a small number alkilinity radicals. One way to obtain these magnesium complexes is in the processing of soluble alkaline alcohol. In order to have a good balance of the effect of hydrogen and a polymerization activity, the ratio of feed MgR2/ROH must be greater than 1:2 and less than 1: 1, preferably between 1:1.75 and 1:1,99, and most preferably between 1: 1,80 1: 1,98. This attitude should not be created immediately when preparing a magnesium complex, but can be created and later, after the pulse is required ratio MgR2/ROH. The relationship between feed rate and composition of the complex can be obtained from the stoichiometry of the following equations

MgR"2+pR"'OH - - - > Mg(OR"')pR2-p+pR"H

where p is the number of moles R"'OH one mol MgR"2.

As the magnesium complex is the preferred reaction product of di-C2-C20- alkylamine (preferably dibutylamine, butylamine or butylaniline) and alcohol. As the magnesium complex is the preferred reaction product diallylamine and alcohol with a branched chain, more preferred 2 - alkylalcohol, most preferred 2 - ethylhexanol or 2 - propylpentyl.

The titanium compound may be chlorinated alcoholate, i.e., TiCl3Or, or only chloride-containing compound, such as TiCl4. The overall composition of this compound is as follows:

ClxTi(OR(IV))4-x(2)

The complex (2) RIV- C2-C20a hydrocarbon radical and x = 3 or 4, preferably 4. Connection Ti must be completely soluble in non-polar hydrocarbon at the temperature. If you use pure TiCl4there is no need to add a hydrocarbon , since this reagent is a liquid which Yale media as the first chemical in the synthesis of the catalyst. Preferably, the molar ratio between alkylmethacrylamide and surface hydroxyl inorganic oxide was greater than 1, preferably between 1 and 1.5. Uniform deposition is achieved in the case when the viscosity of the agent or its solution below 10 mPas at the temperature. In order to achieve such a low viscosity reactant alkylmethacrylamide may be diluted non-polar hydrocarbon. However, the best deposition is achieved in the case when the total amount of solution deposited alkylmethacrylamide does not exceed the pore volume of the carrier, or if the excess solvent is a hydrocarbon is removed by evaporation after deposition of alkylmethacrylamide. A good option is the use of 5 - 25% of the hydrocarbon solution of ethylaminoethanol. The precipitation agent can be conducted in a wide range of temperatures, preferably between 0oC and 110oC. Time and technique of introducing chemicals must be adjusted to ensure uniform distribution of the chemical in the material medium.

Good deposition of a solution of magnesium complex is achieved, if the amount of the magnesium complex is approximately two times the pore volume of material media. This avodarto. The ratio between magnesium and chlorine in the reagent alkylmethacrylamide should be from 1:1.0 to 1:2,5. A good result is obtained if the ratio is from 1:1.5 to 1:2,0.

During the precipitation of the magnesium complex on material media, it should have a viscosity of less than 10 mPas at the temperature. The viscosity of a solution of magnesium complex can be adjusted, for example, by selecting the radical R' in formulas (3) to (6), by selecting the concentration of the hydrocarbon solution, by selecting the ratio between alkylamines and alcoholate, or using any substance that reduces the viscosity.

The connection of titanium can be introduced into the material of the carrier with the preliminary heating of the catalyst to remove volatile hydrocarbons with or without him. TiCl4or a similar compound of titanium is introduced into the reaction mixture in a molar ratio of Ti/Mg, greater than 0.1 and less than 1, preferably 1: 5 to 1:1,43. A good result is achieved when the molar ratio of Ti/Mg is in the range of 0.2 to 0.7. Components are given the opportunity to interact with a sufficient amount of time at the desired temperature. The remaining hydrocarbon may optionally be removed using is not the way.

If you are using the media, it is first dried, as already mentioned. Then the carrier is treated with alkylmethacrylamide (1), preferably by ethylaminoethanol (AADH) which is fixed on the surface of the carrier particles due to the interaction with the surface hydroxyl groups. Thus is formed particle of the medium in which the so-called internal socialization with gloriouse the ability to chemically associated with the formation of-O-Al-X2groups. Between the particles are to some extent free alkylaminocarbonyl.

Then on the particles of the medium are deposited atoms Mg. The most common method consists in the precipitation of the magnesium particles from its solution. The most readily available compounds of Mg, such as halides of Mg, in particular MgCl2soluble only in polar solvents, but insoluble in non-polar liquid hydrocarbon. For the preparation of the magnesium alcoholate may be used, for example, lower aliphatic alcohols, such as methanol or ethanol. The resulting alcoholate Mg is not fully mixed with the hydrocarbon solvent, and this mixture is divided into layers. The alcoholate Mg, directly deposited on the carrier, e.g. the, -ethylhexanol or 2-propylpentanoic has a steric hindrance of the molecules near the Mg-O links in the Mg-alcoholate and coordinated difficult, but because it forms insoluble compounds. Formed solution of the alcoholate Mg, which is completely miscible with liquid hydrocarbons. It is this sort of a hydrocarbon solution should be used for impregnation of the carrier particles, so that the Mg atoms were located possibly more evenly on the carrier particles and can penetrate most inside the particles during the evaporation of the hydrocarbon.

The alcoholate Mg, thus, is prepared from a branched aliphatic monosperma and diallylamine. This alcohol has a large hydrocarbon moiety which hinders its tight coordination. In dialkylamino alkyl radical contains from 2 to 10 carbon atoms and may be linear or branched. Suitable dibutylamine (DBM), butylethylmagnesium (BEM), butylaniline (BOMAG) and other prepared When the alcoholate Mg, solution monosperma and dialkylamino has a very high viscosity near the stoichiometric equivalent point, so this reaction is difficult. The viscosity of the solution can be reduced by adding tetraalkoxysilane Mg, which contains a small amount dealkylase (from 1 to 20 mol%, preferably about 10 mol%), group-O-Al-X2on the surface of the particles of the medium are transformed into the group-O-Al-(OR)R and on the surface of particles deposited monomolecules MgX2. Those and other groups formed in the reaction between compounds of Mg and internal socialization. The alkyl radicals R, associated with the Al atoms that appear in the surface groups of dialkyl magnesium, which are very easily react with the internal socialization.

Finally, to obtain the active pronatalistic media, processed as described above, titanotheres a halide of tetravalent Ti, preferably TiCl4. In titansilver precatalysts a small number of CNS and alkyl groups in the groups with Al-related media, turns into a halide group and a small amount of TiCl4restored to the trivalent form.

Examples.

Below are non-limiting examples illustrate the invention and comparison with known methods. First described how to prepare the complex compounds of Mg, then described the synthesis of pronatalistic from this complex and other reagents, is proletarization.

Preparation of complex 1.

9,5 ml of toluene (0,089 mol) and 68,6 ml (to 0.060 mol) of 20% BOMAG - AND were added in a separating flask. 16,65 ml (0,1065 mol) 2 - ethyl - 1 - hexanol slowly added to the reactor. The temperature was maintained below 40oC. the Molar ratio between BOMAG - a and 2 - ethyl - 1 - hexanol was 1:1,775.

Preparation of complex 2.

6 kg of toluene (65,12 mol) and 27.8 kg (33,21 mol) 19,9% BOMAG - AND were added in the multipurpose reactor. The reactor was cooled to 0oC. 7,89 kg (60,45 mmol/g Si) of 2 - ethyl - 1 - hexanol was introduced into the reactor with the speed (flow) 10 - 30 g/min. and the Temperature was maintained below 20oC. the Molar ratio between BOMAG - a and 2 - ethyl - 1 - hexanol was 1:1,8. 25,6 kg of this complex was transferred to a container and aliquot part was used for preparation of the catalyst in example 1.

Preparation of complex 3.

By remaining in the multipurpose reactor complex in example 2 preparation of the complex was still added 0,887 kg (6,795 mol) 2 - ethyl - 1 - hexanol. Finally, it was added 0,34 kg (1 mmol) of tetraisopalmitate. The molar ratio between BOMAG - a and 2 - ethyl - 1 - hexanol was 1:2,03. The molar ratio of Mg:Ti was 30:1.

Cooking comp - and 2 - ethyl - hexanol was 1:2,19.

Preparation of complex 5.

87 kg of toluene was introduced into the reactor. Then the reactor was added to 45.5 kg 20,3% BOMAG - AND in heptane. 161 kg 99.8% of 2 - ethyl - 1 - hexanol was introduced into the reactor with the speed (flow) 24 - 40 kg/h Molar ratio between BOMAG - a and 2 - ethyl - 1 - hexanol was 1:1,83.

Cooking pronatalistic.

Example 2.

54,9 ml (2 mmol/g Si) EACH slowly added to 30 g of oxide silica (Crosfield ES70X activated at 600oC) at 25oC. the Mixture was stirred for 2.0 hours at 20oC. was Added 81,0 g (2 mmol Mg/g Si) of the complex prepared according to the method of preparation of complex 2, and was stirred for 3.5 h at 20 - 45oC. the Catalyst was dried at 45 - 75oC for two hours. The catalyst was cooled down to 46oC, and 3.33 ml (1 mmol/g Si) TiCl4dissolved in 10 ml of toluene, were added to the previous reaction product. The catalyst was stirred overnight at 45oC. the Catalyst was dried at 45 - 70oC for 2.5 hours the composition of the dried catalyst was as follows: 2.6% of Ti, 3,05% Mg, And 14.3%, Cl and 2.4% Al. The results of polymerization are shown in table 1.

Example 3.

275 g of silica (Grace 955 is a, was introduced into the reactor at ambient temperature for 1 h the Temperature was increased to 35oC. the Treated silica was stirred for 1H. The treated silica was dried at 50oC for 8.5 h 655 kg of the complex (2 mmol Mg/g Si), prepared according to the method of preparation of complex 5, entered during the 23oC for 10 min 86 kg of pentane was introduced into the reactor at the 22oC for 10 min, the Suspension was stirred for 8 h at 50oC. Finally, 52 kg TiCl4were introduced for 0.5 h at 45oC. the Suspension was stirred at 40oC for 5 hours, the Catalyst was dried in a stream of nitrogen. The dry catalyst was as follows: 2.4% of Ti, and 2.3% Mg, 14,1% Cl and 2.9% Al. The results of polymerization are shown in table 1.

Example 1.

54,9 ml (2 mmol/g Si) of 20% EACH slowly added to 30 g of silica (Crosfield BS70X activated at 600oC) at 25oC. the Mixture was stirred for 2.5 h at 20oC. Was added 72,1 g (2 mmol Mg/g Si) of the complex prepared according to the method of preparation of complex 1, and the mixture was stirred for 3.5 h at 20 - 45oC. the Catalyst was dried at 45 - 75oC for two hours. The catalyst was cooled to 46oC and added to 3.33 ml (1 mmol/g Si) TiCl4, rastvoreno is UP>C for 2.5 hours, the catalyst Composition was: a 3.2% Ti, 2.4% of Mg, 16.4% Of Cl and 2.8% Al. The results of polymerization are shown in table 1.

Example 4.

54,9 ml (2 mmol/g Si) of 20% EACH slowly added to 30 g of silica (ES70X activated at 600oC) at 25oC. the Mixture was stirred for 2 h at 20oC. Added to 76.6 g (2 mmol/g Si) of the complex prepared according to the method of preparation of complex 3, the mixture was stirred for 3 h at 20 - 45oC. the Catalyst was dried at 45 - 70oC for two hours. The catalyst was cooled to 46oC and added to 3.33 ml (1 mmol/g Si) TiCl4diluted in 10 ml of toluene. The catalyst was stirred overnight at 45oC. the Catalyst was dried at 45 - 70oC for 2,0 including the Composition of the catalyst was: 2.8% of Ti, 2.0% of Mg, 14.6% Of Cl and 2.5% Al. The results of polymerization are shown in table. 1.

Example 5.

54,9 ml (2 mmol/ g Si) of 20% EACH slowly added at 25oC to 30 g of silica (Crosfield ES70X activated at 600oC). The mixture was stirred for 2.0 h at 20oC. Added to 76.7 g (2 mmol Mg/g Si) of the complex prepared according to the method of preparation of complex 4, and the mixture was stirred for 3 h at 20 - 45oC. the Catalyst was dried at 45 - 70oC for the ml toluene. The catalyst was stirred overnight at 45oC. the Catalyst was dried at 45 - 70oC for 2,9 including the Composition of the catalyst: 3.0% of Ti, 2.1% of Mg, 14.4% Of Cl and 2.7% Al. The results of polymerization are shown in table 1.

The polymerization.

Ethylene was polymerizable in suspension with the formation of products with different average molecular weights or viscosities of the melt as follows.

1.8 liters of purified n-pentane was injected 3-liter reactor. The mixture was heated to a temperature of 90oC. Meanwhile, 500 ml vessel filled with hydrogen under pressure up to 500 kPa during polymerization in low-speed melt flow (LMFR), and up to 1750 kPa during polymerization under conditions of high flow velocity of the melt (HMFR). When the temperature reached 90oC, the pressure in the reactor was about 420 kPa. Then the reactor was introduced precatalysts and socialization triethylaluminium (tea). Then the reactor was passed a stream of ethylene through a balloon containing hydrogen. The total pressure was increased to 1440 kPa; it was maintained at this level by continuously introducing ethylene. The polymerization was continued for one hour. The molar ratio Al/Ti was equal to 15.

The results of polymerization presents the ü is given as a function of the average molecular weight, expressed as a rate of flow of the melt (determined according to ISO 1133).

Precatalysts BC-200 compared with the known catalysts NC-20 (FI 916192), FI 886056, FI 906281 + FI 895526, commercial catalyst and a catalyst for U.S. patent N US 4354009.

1.8 l of purified isobutane were introduced into the reactor with a volume of 3 L. the Contents were heated to 95oC. Simultaneously vessel with a capacity of 500 ml was filled with hydrogen to the pressure to 6.2 bar, if the polymerization was carried out at low speed melt flow (LMFR), and to 18.7 bar, if the polymerization was carried out at a high speed of flow of the melt. When the temperature reached 95oC, the reactor was introduced this precatalysts and triethylaluminium (tea). Then the reactor was introduced through the above ethylene capacity with hydrogen, and the total pressure was raised to 28.5 bar and kept constant by introduction of ethylene, the Molar ratio Al/Ti was equal to 30. The results are presented in table 2 and in the drawing. Index AB catalyst BC - 200 according to the invention was clearly higher than the index of the known catalysts.

1. Precatalysts for the production of polymers of ethylene, comprising an inorganic carrier, chlorine compounds, magnesium and titanium on the specified nostaligia fact, the balance of activity of AV procatalyse under given conditions of polymerization is determined by the expression AB>3,2, where

< / BR>
And - polymerization activity in cgpa/gcat.h;

MFR2- speed melt flow g/min under a load of 2.16 kg according to the standard AND FROM 1133 ISO 1133),

the absence of a Superscript 'denotes the polymerization with a low rate of flow of the melt, the presence of a Superscript' denotes the polymerization with a high rate of flow of the melt.

2. Procatalyse under item 1, characterized in that the balance of activity AB>5.

3. Procatalyse under item 1 or 2, characterized in that the above specified conditions of polymerization of the following: 1.8 l of purified n-pentane are introduced into a 3 l reactor and heated to a temperature of 90oC. in a Separate 500 ml capacity filled with hydrogen to a pressure of 500 kPa, when the polymerization is carried out at a low flow velocity of the melt, and up to 1750 kPa, when the polymerization is carried out under conditions of high flow velocity of the melt. When the temperature in the reactor reaches 90oC, the pressure is approximately 420 kPa. Then the reactor enter precatalysts and triethylaluminium socialization in a molar ratio of AL:Ti equal to 15:1. Stemmeries constant by feeding ethylene. Polymerization is continued for 1 h, after which the ethylene polymer is extracted and determined the yield of polyethylene, the value of MFR2and on the basis of output and the quantity of used pronatalistic evaluated its activity.

4. Precatalysts for the production of ethylene polymers, including inorganic carrier, chlorine compounds, magnesium and titanium on the specified carrier, characterized in that it is obtained by the method comprising the following operations: a) inorganic carrier interacts with alkylmethacrylamide with the General formula

(RnMCl3-n)m, (1)

where R is an alkyl radical with C1-C10;

IU is a metal from group III(13) of the Periodic system of elements;

n=1 or 2

m=1 or 2;

this forms a first reaction product, b) the first reaction product interacts with the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium, forming a second reaction product; (C) a second reaction product interacts with the compound of titanium, which contains chlorine, with the General formula

ClxTi(ORIV)4-x, (2)

where RIV- hydrocarbonyl radical C2-C20;

x=3 or 4,

at the same time the mixture, containing hydrocarbon, Hydrocarbonated and magnesium, on the specified operation (b) has the following formula or composition

Mgand(OR1)bR"withXd,

where R'- hydrocarbonyl radical C2-C20containing or not containing heteroelement;

R"- hydrocarbonyl radical C2-C20;

X is halogen, preferably chlorine;

A1; b>0; c>0; d0; a=1/2 (b+c+d), c/b<1.

7. Procatalyse under item 5 or 6, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), have the following formula or composition:

Mg(OR"')p(R")2-R, (4)

Mg(OCOR"')p(R")2-R, (5)

Mg(O-CH2-OR"')p(R")2-R, (6)

where R"'- hydrocarbonyl radical C2-C20preferably a linear or branched aliphatic or aromatic radical C2-C20;

R"- the specified C2-C20is an alkyl radical;

1<p<2, preferably of 1.78<p<1,99, most preferably 1,80<p<1,98.2-C20preferably the aliphatic radical is C4-C20branched in 2-position with respect to oxygen, most preferably 2-lower alkyl radical-C3-C19-alkyl, such as 2-ethylhexyl or 2-propylpentyl.

9. Precatalysts according to any one of paragraphs.4-8, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), are the product of interaction diallylamine and alcohol.

10. Precatalysts according to any one of paragraphs.4-9, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b) are a product of the interaction of di-C2-C10-alkylamine, preferably dibutylamine, butylamine or butylaniline, and alcohol.

11. Precatalysts according to any one of paragraphs.4-10, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), are the product of interaction between dialkylamines and branched alcohol, preferably 2-alkylamino, most preferably 2-ethylhexanol or 2-propylpentanoate.

12. Precatalysts according to any one of paragraphs.4-11, otlichuy), are the product of interaction between dialkylamines and alcohol, while dialkylamino and alcohol interact in a molar ratio of 1:1,78 - 1:1,99, preferably 1:1,80 - 1:1,98.

13. Precatalysts according to any one of paragraphs.4-12, characterized in that the compound or the mixture of the specified operation (b) containing hydrocarbon, Hydrocarbonated and magnesium interact with the first reaction product, so that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium are in a carbonate solution, preferably a hydrocarbon solution whose viscosity is less than 10 mPas.

14. Precatalysts according to any one of paragraphs.4-13, characterized in that it is manufactured according to the method, the specified operation (s) which the inorganic carrier is an inorganic oxide, preferably silicon dioxide (silica), which has a surface hydroxyl group.

15. Procatalyse under item 14, wherein the inorganic carrier is inorganic carrier, preferably silica, which part of the surface hydroxyl groups removed, mainly silica, containing not more than 2 mmol of surface hydroxyl groups per gram of silica.

17. Precatalysts according to any one of paragraphs.4-16, characterized in that it is manufactured according to the method, an operation (a) inorganic carrier interacts with alkylmethacrylamide, which is alkylamidoamines, preferably lower alkylamidoamines, most preferably by ethylaminoethanol.

18. Precatalysts according to any one of paragraphs.4-17, characterized in that it is manufactured according to the method, an operation (a) inorganic carrier interacts with alkylmethacrylamide so that alkylmethacrylamide is in the form of 5-25% of the hydrocarbon solution whose viscosity is preferably less than 10 mPas.

19. Precatalysts according to any one of paragraphs.4-18, characterized in that the number of compounds or mixtures containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b) and alkylmercury on the specified operation (s) such that the ratio of atoms of magnesium and chlorine in alkylmethacrylamide is 1:1.0 to 1:2.5 and preferably 1:1.5 to 1:2,0.

20. Precatalysts on lubaid titanium.

21. Precatalysts according to any one of paragraphs.4-20, characterized in that the ratio between the compound of titanium on the specified operation (s) and the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b) is such that the ratio of titanium atoms, magnesium Ti:Mg is 0.1 to 1.0, preferably 0,1 - 0,7.

22. The method of manufacturing pronatalistic for the production of polymers of ethylene, with the specified precatalysts contains inorganic carrier, chlorine compounds, magnesium and titanium on the specified carrier, characterized in that it comprises the following operations: a) the interaction of inorganic media alkylmethacrylamide General formula

(RnMCl3-n)m, (1)

where R is an alkyl radical C1-C20;

IU is a metal from group III(13) of the Periodic system of elements;

n=1 or 2 and m=1 or 2

this forms a first reaction product, b) the interaction of the first reaction product with a compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium, forming a second reaction product; (C) the interaction of the second reaction product with a compound of titanium, which contains chlorine and has a General formula

ClxT this produces the specified precatalysts.

23. The method according to p. 22, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), have the following formula or composition

Mgand(OR SIG')bR"withXd, (3)

where R'- hydrocarbonyl radical C2-C20containing or not containing heteroelement;

R"- hydrocarbonyl radical with C2-C20;

X is halogen, preferably chlorine;

A1 b>0, c>0, d0, a=1/2 (b+C+d), c/b<1.

25. The method according to p. 23 or 24, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), have one of the following formulas or compounds:

Mg(OR"')p(R")2-R, (4)

Mg(OCOR"')p(R")2-R, (5)

Mg(O-CH2-OR"')p(R")2-p, (6)

where R"'- hydrocarbonyl radical C2-C20preferably a linear or branched aliphatic or aromatic radical;

R"- the specified alkyl radical C2-C20,

1<p is m, the radicals R'and R"presents branched aliphatic radical C2-C20preferably aliphatic radical C4-C20that is branched in the 2-position relative to oxygen, the preferred radical is 2-lower alkyl-C3-C19- alkyl, such as 2-ethylhexyl or 2-propylpentyl.

27. The method according to any of paragraphs.22-26, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b) are the product of interaction between dialkylamines and alcohol.

28. The method according to p. 27, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), are the product of the interaction of di-C2-C10-alkylamine, preferably dibutylamine, butylamine or butylaniline, with alcohol.

29. The method according to p. 27 or 28, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), are the product of interaction between dialkylamines and branched alcohol, preferably 2-alkylamino, most preferably 2-ethylhexanol or 2-propylpentyl rbil, Hydrocarbonated and magnesium on the specified operation (b), are the product of interaction between dialkylamines and alcohol, and dialkylamino and alcohol interact in a molar ratio of 1: 1,78-1:1,99, preferably 1:1,80-1:1,98.

31. The method according to any of paragraphs.22-30, characterized in that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium interact with the first reaction product so that the compound or mixture containing hydrocarbon, Hydrocarbonated and magnesium in the solution, hydrocarbon, preferably in a hydrocarbon solution whose viscosity is lower than 10 mPas.

32. The method according to any of paragraphs.23-31, wherein the inorganic carrier in the specified operation (a) is an inorganic oxide having surface hydroxyl, preferably silica (silicon dioxide).

33. The method according to p. 32, wherein as the inorganic carrier is preferably used silica, a portion of the surface hydroxyl groups of which is removed, preferably silica, containing not more than 2.0 mol of surface hydroxyl groups per gram of silica.

34. The method according to p. 32 or 33, characterized in that on this Opera is tallarida so, that the molar ratio of alkylmethacrylamide and surface hydroxyl inorganic oxide is at least 1, preferably 1-1,5.

35. The method according to any of paragraphs.22-34, characterized in that the specified operation (a) inorganic carrier interacts with alkylmethacrylamide, which take alkylhalogenide, preferably lower alkylhalogenide, most preferably ethylaluminum.

36. The method according to any of paragraphs.22-35, characterized in that the specified operation (a) inorganic carrier interacts with alkylmethacrylamide, with alkylmercury take the form of 5-25% solution in hydrocarbon whose viscosity is preferably less than 10 mPas.

37. The method according to any of paragraphs.22-36, characterized in that the number of compounds or mixtures containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), and alkylmethacrylamide on the specified operation (a) is such that the atomic ratio between magnesium and chlorine in alkylmethacrylamide is 1:1-1:a 2.5, preferably 1:1.5 to 1:2,0.

38. The method according to any of paragraphs.22-37, characterized in that compounds of titanium on the specified operation (s) take the titanium tetrachloride.

39. The method according to any who) and the compound or mixture, containing hydrocarbon, Hydrocarbonated and magnesium on the specified operation (b), is such that the atomic ratio between titanium and magnesium is 0.1<Ti:Mg<1, preferably of 0.1 to 0.7.

 

Same patents:

The invention relates to a ball of solid catalytic components for the polymerization of olefins containing compound of titanium deposited on a magnesium halide containing more than one relationship Ti-halogen and, optionally, containing groups other than halogen, in the amount of less than 0.5 mol per 1 mol Ti

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The invention relates to a spherical solid components of catalysts for the polymerization of olefins, comprising deposited on dihalogenide magnesium in an activated form of a compound of titanium, containing at least one link with a titanium halide and one OR group with the specified group OR is linked to an atom of titanium in such quantities that the molar ratio OR/Ti is greater than or equal to 0.5

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