A method of obtaining a solid component of catalyst for the (co) polymerization of ethylene, a solid component of catalyst for the (co) polymerization of ethylene, the catalyst for the (co)polymerization of ethylene and method for producing (co)polymers of ethylene


C08F4/652 -

 

(57) Abstract:

The inventive solid component of catalyst for the preparation of catalysts, which allow to obtain (co)polymers of ethylene ultra-high molecular weight, get in the form of particles having an average diameter of less than 10 μm, the reaction conducted in the presence of H2O, between: 1) a liquid obtained as a result of interaction: a) compounds of titanium, containing at least one link Ti-OR, where R is a C1-C20alkyl, C3-C20cycloalkyl or C6-C20aryl radical, with (b) a magnesium compound selected from: halides; compounds containing at least one group - or, - OCOR, associated with magnesium, where R is a C1-C20alkyl, C3-C20cycloalkyl or C6-C20aryl; ORGANOMETALLIC compounds; reaction products between the above-mentioned compounds and electrondonor compounds, and 2) a compound or composition capable of halogenate and may recover (a). 4 S. p. f-crystals, 4 PL.

The invention relates to the components of the catalysts in the form of very fine particles and to obtain from them the catalysts. These catalysts allow to obtain polymers and SOPs shall be in the compression processes of formation and in the production processes, typical polymers with very high molecular weight.

It is known (U.S. patent N 4296223) how to get solid component of catalyst for the reaction between these compounds in various combinations:

a) an alcoholate of titanium or halogenoalkanes titanium;

b/ magnesium halide, or an organic or ORGANOMETALLIC compound of magnesium, or the products of interaction with electrondonor connection;

c) the compound or composition capable of halogenate and possible, to restore the connection (a).

By activating the catalyst components connection alkylate formed catalysts active in the processes (co)polymerization of olefins and particularly ethylene.

Next, using the above catalyst components, you can get the homopolymers of ethylene with a narrow molecular weight distribution.

In the case of copolymers of ethylene with a-olefins, the components of the catalyst of the above-mentioned types lets get physical-mechanical properties, very high compared to the low content of co monomer (application of Europatent N 7647).

The above results can be attributed especially good rastreamento catalysts is stimulated their deposition from the liquid phase (either using simple reagents, when possible, either in solution), mixing them in a special way so as to obtain particles of the possible correct morphology and controlled distribution of particle sizes.

Catalysts based on components of the catalysts thus obtained, allow, thanks to a well-known phenomenon of morphological copies from the polymer to obtain a polymer in the form of particles with the correct and controlled morphology and high fluidity.

Thus, these polymers have good machinability during polymerization and a high degree of extraction of the reactors of the polymerization, they can be easily directed to apparatus for processing.

However, as mentioned (Europatent N 7647), while working on the above method of deposition from the liquid phase, cannot, as a rule, to obtain particles of the catalyst component with diameter less than 10 microns.

When used in the process of (co)polymerization of ethylene, these particles give polymers in the form of particles with a diameter much greater than 100 μm, from 100 to 500 μm, an average is usually from 200 to 400 microns.

It is also known that in the case of polymers of a-olefins, in particular ethylene, having a very high molecular weight (i.e., when akusherstvo consist in the use of very fine powders of polymers, having good fluidity and compressibility.

Actually, under the condition of high viscosity that these high molecular weight polymers remain in the molten state even at a high temperature, for the production of products not suitable standard methods of molding, which uses molten polymer.

The correct solution in this case will be the compression molding, which receive, at the expense of adhesion and compaction of powders of the polymer at high temperatures, the finished product, physico-mechanical properties which generally improves with increasing malabaristas source powders of the polymer, and these powder particles have the correct form and controlled size distribution. In order to obtain good workability and quality of the finished product, it is also desirable that the polymer particles were sufficiently porosity.

The finished products derived from polyethylene with high molecular weight, suitable in particular for use in a number of areas that require high physical-mechanical characteristics (for example, in the manufacture of the hinge parts or components of the prosthesis WM catalyst (application for EUROPATAT N 317200), containing a solid component obtained by the reaction between:

and/ reaction product of dihalogenide magnesium and tetrachlorogallate titanium;

b/ the reaction product of trihalogen aluminum and tetrachlorogallate silicon.

However, despite the fact that one of the purposes of the above-mentioned way is to obtain a polymer in the form of very fine particles specified in the examples, the average particle diameter does not fall below 195 ám.

Thus, it would be a great advantage if there were components of the catalysts of the above type in the form of very fine particles, with the correct morphology and controlled particle size distributions, which allows to obtain, at the expense of copying, powders of polymers with good form, density and fluidity, especially suitable for use in manufacturing processes sheets (compression forming) or rods (extrusion with a plunger).

This goal cannot be achieved sufficiently by using milling powders of the solid component of catalyst or polymer, as the grinding gives powders too different in size, irregular shape, and can not control the distribution of particle sizes. In addition tohosomnia morphological irregularities lead to poor fluidity of the powders of the polymer and generally a deterioration of the physico-chemical properties of the products, the resulting compression molding.

In order to satisfy the above requirements, a fine solid component of catalyst (co)polymerization of ethylene, containing products of the reaction between:

1) the liquid obtained by the interaction of:

a) compounds of titanium, containing at least one link Ti-OR, where R is a C1-C20alkyl, C3-C20cycloalkyl or C6-C20aryl;

b/ magnesium compounds selected from halide compounds containing at least one group or or OCOR associated with an atom of magnesium, where R is a C1-C20alkyl, cycloalkyl or aryl; ORGANOMETALLIC compounds; reaction products between the above-mentioned compounds and electron donor compounds;

2) compounds or Compositae able to substitute in the compound (a) at least one group OR a halogen atom, and it is possible to recover the titanium compound (a) before oxidation state lower than 4, and the specified component catalysts receive in the form of particles having an average diameter less than 10 microns, typically from 1 to 8 μm, preferably from 2 to 6 microns, including limit values, and it allows you to get when doing a standard test μm, preferably from 40 to 120 microns, including limit values.

Further, the polymer obtained by the above-mentioned standard test, preferably has a turnover of less than or equal to 40 seconds (measured to method ASTM 1895-69A).

Component of the catalyst according to this invention can be obtained by a special deposition method, which is described below, and which allows to obtain particles with high porosity.

The compound (a) preferably selected from galogenarenov titanium, where the halogen atoms are preferably chlorine or bromine. Examples of the titanium alcoholate or galogenarenov titanium are compounds of General formula:

(I) Ti(OR)nX4-n< / BR>
where R is C1-C20alkyl, C3-C20cycloalkyl or C6-C20aryl;

X is a halogen atom, preferably chlorine or bromine;

1 n 4.

Specific examples of compounds of formula (I) are:

Ti(OC2H5)4, Ti(OC4H9)4, Ti(OC8H17)4, Ti(OC6H5)4, Ti(OC6H11)4, Ti(OC4H9)3CI, Ti(OC4H9)3Br, Ti(OC2H5)2CI2, Ti(OC4H9)CI3, Ti(OC6H5))Cl3.

Compounds (a) can also be used in mixture with halides or organic compounds Z2or V. Specific examples of such compounds are:

VOCI3Vo(OC4H9)3V(OC2H5)3V(OC6H5)2CI, VCI4, Z2CI4, Z2(OC3H7)4,

Z2(OC6H13)2CI2, Z2(OC4H9)3Br.

Compounds (b) preferably selected from compounds of the General formula:

(II) XnMg(OR)2-n< / BR>
where X is a halogen atom, preferably chlorine, or a radical C1-C20alkyl, C3-C20cycloalkyl or C6-C20aryl;

R radical C1-C20alkyl, C3-C20cycloalkyl when C6-C20aryl or the radical COR', where R' - C1-C20alkyl, C3-C20cycloalkyl or C6-C20aryl;

n is a number from 0 to 2;

(III) RMgX,

where X is a halogen atom, preferably chlorine;

R radical C1-C20alkyl, C3-C20cycloalkyl or C6-C20aryl.

As mentioned earlier, can also be used as compounds (b) the reaction product or complex formation, Visayas) are:

MgCI2, MgBr2, Mg(OC2H5)CL, Mg(OC2H5)2, Mg(OC4H9)2, Mg(OC4H9)CI, C6H5Mg(OCH3), C8H17Mg(OC6H5), magnesium acetate, (C8H17)2)Mg, (C6H5)2Mg,

(C6H11)2Mg.

Specific examples of compounds of the formula (III) are:

CH3MgCI, C2H5MgBr, C2H5MgCI, C4H9MgBr, C4H9CIMg.

Examples of electron-donor compounds that can be used to obtain the compounds (b) are alcohols, ethers, carboxylic acids, esters, aldehydes, ketones, silanol, polysiloxanes and silanes.

Silanol preferably selected from compounds of the formula:

(IV) RnSi(OH)4-n< / BR>
where n is 1, 2 or 3;

R is hydrogen, or a radical C1-C20alkyl, or the radical C3-C20cycloalkyl, or the radical C6-C20aryl.

Polysiloxane preferably selected from compounds containing Monomeric link

< / BR>
where R may be the same or different from R' and R' is the radical C1-C20alkyl, C6-C20cycloalkyl or C6-C20aryl; R' water and C6-C20aryl.

Specific examples of electron-donor compounds are:

C2H5OH, C4H9OH, C6H5OH, (C6H5)3O, C8H17OH, (C4H9)2O, C4H8O,

CH3-O-CH2-CH2-CH2-OCH3CH3-O-CH2-C(i-C3H7)2-CH2-OCH3CH3COOH, CCI3COOH, C6H5COOC2H5CH3-C6H4-COOCH3C6H4(COOC4H9)2C6H5Si(OC2H5)3,

C6H5SICH3(OCH3)2, (CH3)2Si(OCH3)2, (CH3)2Si(OCH3)2, (C6H5)2Si(OH)2diphenylsiloxane.

Component (2) consists of one or more compounds with halogenation and possibly restoring action, in the above sense, with respect to the compound (a).

Preferably, component (2) has halogenation, and restoring action.

For use as component (2) are particularly suitable, individually or in mixtures with other compounds, such silicon compounds that contain galam).

Examples of such compounds are the following compounds of the formula: SiX4-nYnwhere X and Y are halogen atoms; n is a number from 0 to 3, such as SiCI4; chloralosane formula: SinOn-1CI2n+2where n is a number from 2 to 7, such as Si2OCI6; for example; halogenated polysilane formula: SinXn+2, where X is a halogen; n is a number from 2 to 6, such as Si4CI10; for example, halogenosilanes formula: SiH4-nXn, where X is a halogen; n is a number from 1 to 3, such as, for example, SiHCI3alkylhalogenide formula: RnSiHxXywhere R C1-C20aliphatic or aromatic radical; X is halogen; n is a number from 1 to 3; x is a number from 0 to 2; y is a number from 1 to 3, such as, for example,2H5SiCI3CH3SiCI2H and (CH3)3SiCI2; halogenated alkoxysilane formula: Si(OR)4-nXn, where X is a halogen; R is C1-C20alkyl or aryl radical; n is a number from 1 to 3, such as, for example, (OC2H5)CI3.

Examples of compounds having a reducing effect, which can be used in combination with a halogenation compound are compounds alkyl sodium, alkylate; alkylzinc and the corresponding aryl p is nominee link which corresponds to the following General formula:

< / BR>
where R is hydrogen, halogen, C1-C10aryl, alkoxyl, aryloxy or carboxyl;

n varies from 2 to 1000, preferably from 3 to 100.

If the halogen atoms are present in all the above-mentioned compounds, it is preferably CI or Br.

Examples of polyhydroxybenzenes are:

(CH3)3SiO[(CH3)HSiO]nSi(CH3)3; (CH3HSiO)4.

The hydrogen atoms in the above polyhydroxyalkane can be partially substituted by methyl groups.

As reductants can be used other compounds of silicon, such as silane of the formula SinH2n+2where a number greater than or equal to 1, preferably greater than or equal to 3, such as Si3H8; polysilane containing the group(SiH)xwhere x2; alkyl or arisian formula RxSiH4-xwhere R is alkyl or aryl, and x is a number from 1 to 3, such as a /C6H5/3SiH; alkoxy - or arelatively formula /RO/xSiH4-xwhere R C1-C20alkyl or C6-C20aryl, and x is a number from 1 to 3, such as, for example, /C2H5O/3SiH.

In addition, as examples of compounds which can be used as Ethan, already mentioned as examples of compounds (a); AICI3; AI(C2H5)CI2AI(C4H9)2CI, AI(i-C4H9)3CI3AI(C3H7)Br2; SnCI4C6H5CCI3C6H5COCI, CI3CCOCI, CI3CCOOC2H5, SOCI2.

Among the latter, only ORGANOMETALLIC aluminum compounds have a restorative effect.

A preferred example of component (2) is a combination SiCI4and polyhydroxyalkane.

As mentioned previously, the components of catalysts according to this invention receives a special way, which is an additional objective of the present invention and which includes:

the interaction of compounds (a) and (b), which gives the liquid reaction product (possible solution);

subsequent interaction with stirring, the thus obtained liquid product with the component (2); and in the process, water is added in an amount of not more than 0.5 mol per mol of compound of titanium, one or more of the above reagents, except for the connection (b), compounds (a) containing Halogens and halogenated compounds present in (2), or VI compounds, present in (2).

In many cases, the interaction of the compounds (a) with compound (b) leads to the formation of a liquid at the temperature and pressure of reaction product or at least product, soluble in aliphatic, cycloaliphatic, aromatic hydrocarbons, such as isobutane, pentane, hexane, cyclohexane and toluene.

In some cases, in order to obtain a soluble product, it may be beneficial or necessary to add the compound (b) to the compound (a) in the presence of excess electron-donor compounds belonging to one of the above types.

Even if the product of the interaction of compounds (a) and (b) is a liquid, it may be that it is better to dilute it with a hydrocarbon solvent described above.

The solvents may be present in the reaction mixture in varying amounts, preferably from 1:1 to 1:4 by volume relative to total (a) + (b).

The reaction product (a) + (b), it is possible in solution, as described above, is then introduced into contact, with stirring, with component (2).

It is preferable to add a component (2) to the reaction product (a) + (b) dropwise.

Compo is Yes component (2) includes more than one connection (one of halogenation and one regenerating), you can also hold separately the interaction of each of the above compounds with the reaction product (a) + (b).

The temperature at which carry out the reaction, is preferably from 0 to 250oC, more preferably from 20 to 200oC.

The process can be conducted at atmospheric or higher pressure.

The compound (a) and (b) is preferably introduced into the reaction in amounts providing Mr. atomic ratio Ti/Mg from 0.02 to 20, more preferably from 0.1 to 3, whereas the component (2) is preferably used in amounts that provide from 0.5 to 100, more preferably from 1 to 30 g-atoms of halogen in g-atom of titanium, and 0.1 to 100, more preferably from 0.5 to 20 grams-the equivalent of reducing agent on g-atom of titanium.

In accordance with the above-described method, water is added in a molar ratio, based on titanium, preferably from 0.1 to 0.5, more preferably from 0.1 to 0.3 including extreme values.

The method of adding water is not critical; usually it is added dropwise with stirring.

Acting in accordance with the above-described method, the get component of the catalyst in the form of spheroidal particles with controlled distributed is as a catalyst with the same size distribution, that the ratio ranges from 1 to 0.5.

In the above expression d, D10 and D50 are the values of the diameters, which are, respectively, 90, 10, and 50% of the particles.

In addition, depending on the used method of adding water, get a solid component of catalyst according to the invention with a relatively high porosity, typically above 0.8 cm3/g, preferably in the range from 1 to 3.5 cm3/g, more preferably from 1.2 to 3 cm3/g as measured by the method of absorption of mercury. Surface area typically ranges from 5 to 70 m2/,

Remember that when measuring porosity conventional methods of absorption of mercury, the obtained value includes the volume of voids between the particles.

You can calculate the actual porosity of the particles of the catalyst component by subtracting from the total porosity objerror having a diameter greater than the set value, which, depending on the specific of the analyzed particles is assumed to correspond to the voids between the particles.

Calculated true porosity components of catalysts according to this invention ranges preferably from 0.1 to 1.5 cm3/,

The same amendment should nosim correct values do not differ significantly from the values of total surface area, i.e., area, including the pores between the particles.

The above-mentioned interval from 5 to 70 m2/g can be attributed to the full surface area.

The above-mentioned porosity is another advantage in achieving the objectives of the invention, since it increases the yield of the polymerization catalyst and allows to obtain, at the expense of morphological copy of the polymer particles is also porous and therefore especially suitable for use in the processes of production sheets.

It was found that when water is added directly to the compound (b), surface area and porosity of the catalyst component is particularly low, while the average particle diameter is usually greater than 10 microns.

Therefore, the addition of water to the compound (b) is not an advantage.

Is not also the advantage of adding water to the compound (a), which contains halogen, and also to present in component (2) halogenated compound. It is preferable to add water to the compound (a) or the reaction product (a) + (b).

The components of the catalyst according to the invention, in combination with an organic compound of aluminum, preferably alkyl soedinenie-olefins.

Examples of alkyl aluminum compounds are Al(C2H5)3and Al(i-C4H9)3.

Organic compound of aluminum is usually used in quantities of from 0.1 to 1000 mol per mol of compound of titanium. Organic compound of aluminum can also be used together with an electron-donor compound, such as, for example, ether carboxylic acids.

As mentioned above, components of catalysts according to the invention allow, when conducted standard tests for the polymerization of ethylene (described in the examples), the polymer in the form of particles with an average diameter of less than 150 microns.

The distribution of particles and average particle diameter of the component of the catalyst determines through diffraction of the laser beam on the installation Malvern Instrument 2600.

The size distribution and average particle diameter of the polymer is determined by sieving, using sieves with smaller holes.

The average diameter is a diameter, which corresponds to 50 wt. particles.

Examples of polymers of ethylene of ultra-high molecular weight, which can be obtained by using the components of catalysts for izobreteny is as propylene, 1-butene, 1-hexene, 4-methyl-1-penten, 1-octene.

As mentioned earlier, these copolymers and polymers of ultra-high molecular weight are values characteristic viscosity [] tetraline at 135oC higher than or equal to 10 dl/g, preferably in the range from 10 to 25 dl/g.

Components of catalysts according to the invention is preferably used in the processes of the suspension polymerization.

As suspendida environment it is possible to use aliphatic, cycloaliphatic or aromatic hydrocarbon solvent, such as, for example, n-heptane, pentane, hexane or toluene.

Preferred operating conditions:

the pressure of ethylene and 5 to 20 ATM

temperature 50 85oC,

the duration of polymerization of 1 to 5 o'clock

The comonomers can also be added in liquid form. The process is carried out in the absence of molecular weight regulators or in the presence of their limited quantities, in particular, in the presence of hydrogen.

It is clear that if necessary, you can use two or more stages of polymerization with different, for example, temperature and hydrogen concentration, conditions.

Examples 1 and 2 and comparative examples 1 and 2

275 g of Ti(OCorelative to each other.

Then raised the temperature to 140oC and withstand the contents of the reactor with stirring for 5 hours This led to the formation of a liquid phase, which is then cooled to 90oC and diluted 530 cm3heptane.

After that, the content was cooled to 50oC and maintaining the liquid under stirring speed 800 rpm, introduced for 2 h 148 cm3polymethylhydrosiloxane brand BAYSILION MH 15, supplied by BAYER; then, for 1.5 h, added 152 cm3SiCI4.

Then the temperature was raised to 60oC for 30 min and kept content with stirring for 2 h

Thus obtained solid red color separated from the liquid phase, washed with hexane to remove from the filtrate chlorine ions, and then dried at 50oC in a furnace for 3 h in vacuum.

In example 1 to Ti(OC4H9)4added, before the introduction of MgCI22 cm3water.

In example 2, after dilution with heptane and to add BAYSILON introduced 2 cm3water.

In with the water.

In comparative example 2, the water is not used.

Characteristics of the thus obtained components of the catalysts are summarized in table. 1.

In particular, the porosity and surface area was calculated by introducing a known amount of a component of the catalyst in the dilatometer, filling the last mercury using mercury brand "Porosimeter 2000", supplied by the firm C. Erba Instruments for measurement.

To obtain the correct values of porosity and surface area, we subtract the contribution of pores with a diameter exceeding 0.1 μm for the components of the catalysts of examples 1 and 2, and greater than 0.2 and 0.5 μm, respectively, for the components of comparative examples 1 and 2.

Example 3. The standard test for the polymerization of ethylene

In a steel reactor with a capacity of 2.5 liters, equipped with a stirrer and a heating jacket, introduced in a light stream of nitrogen 950 cm3the 1.5 millimolar solution of AI(C2H5)3in hexane. Then introduced ethylene at a pressure of 6 bar, and 0.02 g component of the catalyst in suspension in 50 cm3the solution above AI(C2H5)3in hexane.

Polymerization was continued for 180 min at 60oC, and the pressure of ethylene was maintained at a level of 6 bar.

Note: when using the catalyst of example 1, in the standard test received 378 g of polyethylene with ultra-high molecular weight and with the characteristics listed in table. 2.

When testing the specified polyethylene impact strength Charpy, according to the following method, the obtained value 123,9 7 MJ/mm2.

Example 4. The process was carried out as in example 3, using 0,0154 g component of the catalyst of example 1 by conducting the polymerization in two successive stages.

In the first stage, the pressure of ethylene was maintained at a level of 6 bar and a temperature of 55oC for 120 minutes

In the second stage for 30 min maintained pressure of ethylene of 10 bar and a temperature of 75oC.

Received 379 g of polyethylene with ultra-high molecular weight. Characteristics of this polyethylene are given in table. 2.

Example 5. The process was carried out as in example 3, using 0,0157 g component of the catalyst of example 2 and conducting the polymerization in two successive stages.

In the first stage kept the pressure of ethylene of 6 bar and a temperature of 60oC for 90 minutes

In the second stage for 150 min rest molecular weight. Characteristics of this polyethylene are given in table. 2.

Comparative example 3. The process was performed as in example 4, using 0,0159 g component of the catalyst obtained in comparative example 2, and holding the first stage polymerization for 135 min, and the second 15 minutes

Received 398 g of polyethylene with a very high molecular weight. Characteristics of this polyethylene are given in table. 2 and 3.

Test compression molding

Using the polymers of examples 3, 4, 5 and comparative example 3, prepared sample plates approximately h mm, 12 mm thickness by compression molding under the following conditions:

temperature 216oC;

pressure 25 t 30; 14 t for 10 minutes

Then the plate was left to cool for 7 minutes at a pressure of 15 tons, after which they took from the form.

On the above plates, we have conducted measurements the results of which are presented in table. 4.

1. A method of obtaining a solid component of catalyst for the (co)polymerization of ethylene by the interaction of tetrabutyrate titanium to magnesium chloride, polymethylhydrosiloxane tetrachloride and silicon with an atomic ratio of titanium to magnesium is from 0, the 1 g and titanium, characterized in that the process is carried out in the presence of 0.1 to 0.5 mol.of water per 1 g of titanium introduced into tetrabutyl titanium before or after administration of magnesium chloride, followed by washing with hexane and consistent introduction of polymethylhydrosiloxane and silicon tetrachloride.

2. A solid component of catalyst for the (co)polymerization of ethylene, which is a product of the interaction of tetrabutyrate titanium to magnesium chloride, polymethylhydrosiloxane tetrachloride and silicon with an atomic ratio of titanium to magnesium from 0.1 to 1.0 1 to 3, halogen in the silicon tetrachloride titanium 1 1 30 1 and the content of 0,5 20,0 g-equivalent polymethylhydrosiloxane 1 Mr. and titanium, characterized in that it is obtained in the presence of 0.1 to 0.5 mol.of water per 1 g of titanium introduced into tetrabutyl titanium before and after administration of magnesium chloride, followed by washing with hexane and consistent introduction of polymethylhydrosiloxane and silicon tetrachloride, in the form of particles up to 10 microns.

3. The catalyst for the (co)polymerization of ethylene, comprising alyuminiiorganicheskikh compound and a solid component, wherein the solid component it contains a solid component of catalyst for the (co)polymerization of ethylene under item 2.

4. The way pvii catalyst, including alyuminiiorganicheskikh compound and a solid component, wherein as the catalyst use of catalyst for the (co)polymerization of ethylene under item 3.

 

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