KR800001213B1 - Components of catalysts for polymerizing alpha-olefins - Google Patents

Abstract

Mg halide-contg. particles with diam. 1-100m, surface area > 90m2/g and porosity<0.3cm3/g are treated with a compd. esp. TiCl4 to prep. polymn. catalyst[XnXg(OR)2-n; n ; O<=n<=2, R; C1-20 alkyl, aryl, cycloalkyl group, X;halogen atom or OR group forα-olefins. The catalysts have high activity and stereospecificity and give α-polyolefins with controlled particle size and good powder flow properties.

Description

Catalyst Component for Polymerization of Alpha-Olefins

The present invention relates to catalyst components useful for the polymerization of olefins CH ₂ = CHR, wherein R is hydrogen or alkyl of 1 to 6 carbon atoms.

More specifically, the present invention relates to a small amount of alpha-olefin CH ₂ = CHR, wherein R is hydrogen or alkyl of 1 to 6 carbon atoms, such as propylene, butene-1, 4-methyl-pentene-1 and mixtures thereof. A catalyst component suitable for stereospecific polymerization with ethylene.

Many polymerization catalysts are known which exhibit high activity and stereospecificity in the stereoregular polymerization of alpha-olefins. Essential components for the preparation of these catalysts are alkyl Al compounds which form complexes with electron donating compounds and halogenated Ti compounds which are supported on electron halide compounds, preferably Mg, on a halogenated salt. Some examples of these catalysts have been described in British Patent 1,387,890.

However, such known high-stereospecific and highly active catalysts make it impossible to obtain free-flowing particulate polymers of controlled morphology, in particular narrow particle size distribution. In general, the polymers produced by such catalyst means exhibit rather broad particle size distribution curves and are not free flowing.

Most particles have a particle size of 1,000 to 100 microns. However, there are also significant fractions of more than 1,000 microns and less than 100 microns.

It is most preferred to use high activity and high stereospecific catalysts which result in polymers in the form of free flowing particles with a narrow particle size distribution.

US 3,954,414 describes a polymerization catalyst useful for obtaining polymers in the form of elliptical particles with controlled particle size distribution. However, the activity and stereospecificity of these catalysts are not high enough.

Accordingly, an object of the present invention is to provide a high activity, high stereospecific catalyst useful for preparing an olefin polymer in a particle form having a controlled particle size distribution.

These and other objects are achieved by the catalyst component and catalyst of the present invention. The catalyst component which achieves the objective of this invention is a Ti compound of the following general formula whose average particle diameter is 1-100 micrometers, surface area is 100m <_2> / g or more, especially 200m <_2> / g-700m <_2> / g and porosity is less than 0.25cc / g. It is prepared by reacting with a carrier of elliptical particles consisting of Mg compounds or mixtures thereof.

XnMG (OR) _2-n

Where

0 ≦ n ≦ 2,

R is an alkyl, aryl, cycloalkyl group having 1 to 6 carbon atoms,

X is a halogen atom or an OR 'group wherein R' is also the same as or different from R as an alkyl, aryl or cycloalkyl group having 1 to 20 carbon atoms.

Among the catalyst components of the present invention, those suitable for stereospecifically polymerizing alpha-olefins,

a) Ti compound

b) the carrier described above, and

c) prepared by reaction with the Ti compound and an electron donating compound (or Lewis salt) capable of forming an additional compound.

Particularly suitable for the stereospecific polymerization of alpha-olefins, the present catalyst component is

a) a Ti compound selected from halogens and compounds containing at least one Ti halogen bond, in particular a tetravalent Ti halogen bond,

b) a carrier having a surface area of 200 to 700 m ² / g, a porosity of 0.1 to 0.2 cc / g, a particle size of 5 to 25 microns, in particular 8 to 20 microns, composed of a compound of the general formula:

XnMg (OR) _2-n

Where

O≤n≤2, in particular 0≤n≤1,

X is a halogen atom selected from Cl and Br,

R is an alkyl, cycloalkyl and aryl group having 1 to 12 carbon atoms.

c) reaction products between the electron donating compounds selected from esters of organic and inorganic oxygenated acids, in particular esters of aromatic acids.

Particularly suitable halogenated Ti compounds for preparing the present catalyst component are Ti tetrahalides, in particular TiCl ₄ . However, halogen-alcoholates and halogen-phenolates such as Ti (OnC ₄ H ₉ ) ₂ Cl ₂ , TiOC ₂ H ₅ Cl ₃ , Ti (OC ₆ H ₅ ) ₂ Cl ₂ may also be suitably used. Examples of non-halogenated Ti compounds are tetraalcoholates such as Ti (OnC ₄ H ₉ ) ₄ . Non-halogenated Ti compounds are generally used for the preparation of ethylene polymerization catalysts.

Compounds of the general formula XnMg (OR) _2-n containing one or more Mg-OR bonds are represented by magnesium as alcohol salts and monohalogen alcoholates. Examples of these compounds include Mg (OC ₂ H ₅ ) ₂ , Mg (OiC ₄ H ₅ ) ₂ , Mg (OC ₆ H ₅ ) ₂ , Mg (OC ₆ H ₄ CH ₃ ) ₂ , Mg (OC ₆ H ₄ C ₂ H ₅ ) ₂ , Mg (OCH ₃ ) (OCH ₂ C ₆ , H ₅ ), C ₂ H ₅ OMgCl, C ₄ H ₉ OMgCl, CH ₃ C ₆ H ₅ O-MgCl, (CH ₃ ) ₂ C ₆ H ₃ OMgCl.

Mg alcoholic acid salts can also be used in the form of complexes with alcoholic acid salts of other metals such as alcoholic salts of Al, B, Zn, and Zr.

As the carrier, in addition to the above-mentioned Mg compound, an organic solid co-carrier or in particular, a group III and IV metal compound of the periodic table, such as SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , ZrO ₂ , TiO ₂ , or Periodic Table I Group 2 and Group II metal compounds such as NaCO ₃ , NaCl, Na ₂ SO ₄ , MgO, MgCO ₃ , Mg (OH) Cl, CaCl ₂ , are inorganic inert solid carriers which are inert to Mg compounds.

When n is 2 in the compound XnMg (OR) _2-n , Mg can be represented by a halide, in particular MgCl ₃ .

In addition to the surface area and porosity characteristics described above, the carrier is generally characterized by an ultrasonic vibration resistance of at least 3 Watt h / 1, in particular at least 30, that is, 30 to 70 Watt h / 1.

See US Pat. No. 3,953,414 for the definition of ultrasonic vibration resistance and its measurement.

Electron-donating compounds c) suitable for the above-mentioned purposes are selected not only from esters of oxygenated acids, but also from P compounds such as ketones, aldehydes, ethers, amides and phosphines and phosphoramides. Preferred compounds are alkyl esters of aromatic acids. Representative examples of these esters are alkyl benzoates, alkyl toluene salts and alkylanistic acid salts. Esters can also be used in the form of addition salts of Mg halides with different Lewis acid halides. Halides of Al and Sn, in particular AlCl _3, are Lewis acid halides.

Aromatic esters can be prepared by the exchange reaction between the OR group of the carrier containing the compound of the compound XnMg (OR) _2-n in which n is not more than 2, in particular n = 1, and the halogen atom of the halide of the aromatic acid. For this purpose, for example, benzoyl chloride can be used.

From the viewpoint of improving the stereospecificity of the catalyst, it is preferable to use an aromatic ester mixed with a small amount of phenol, especially ortho-substituted phenol. It is preferable to react the electron donating compound c) with the carrier before the reaction with the Ti compound. However, it is possible to react both the compound and the carrier with the electron donating compound at the same time. It is also possible to react the Ti compound with the carrier and then treat the solid reaction product with the electron donating compound. The Ti compound may be reacted in the form of an addition compound with the electron donating compound.

The reaction between a), b) and c) described above is such that the amount of the electron donating compound present in bound form in the solid product separated in the reaction mixture is not more than 1 mole per gram atom of Mg, in particular 0.1 per gram atom of Mg It advances on conditions which become an amount of 0.3 mol.

The molar ratio between the electron donating compound and the Ti compound is 0.2 to 2, preferably 0.5 to 1.5.

In order to increase the catalytic activity and stereospecificity, it is important that less than 50% by weight of the tetravalent Ti compound contained in the catalyst component can be extracted with TiCl ₄ at 80 ° C. The extractable Ti compound should be less than 20% by weight.

The reaction between the compound containing the Mg-OR bond of the carrier and the halogenated Ti compound produces a Mg dihalide in which the Ti compound is chemically immobilized. This reaction proceeds under conditions where such conversion is as complete as possible.

The reaction between a carrier, a halogenated Ti compound such as TiCl ₄ and an electron donor compound c) yields a halide of Mg composed of an electron donating compound and a Ti compound chemically immobilized on an Mg halide.

The fact that the Ti compound and the electron donor compound are chemically bonded to Mg on the halide can be proved by various methods, including infrared extraction and Raman analysis, which are solvent extraction methods.

In another aspect of the present invention, it was found that the product between the Ti compound and the carrier did not change the form of the carrier and the surface area of 90 to 700 m ² / g regardless of the presence or absence of the electron donating compound.

The porosity is somewhat high, in the range of 0.2 to 0.3 cc / g.

Similarly, in another aspect of the present invention, a carrier containing at least one Mg compound having an Mg-OR bond prior to reaction with a Ti compound may be substituted with a halogenating agent capable of replacing the OR group of the carrier with a halogen atom. When reacting, a product having the form and properties of the raw material carrier can be obtained. Examples of such halogenating agents are halogenated Si compounds such as SiCl ₄ , benzoyl chloride, AlCl ₃ , Al-alkylmonohalides or Al-alkyldihalides, BCl ₃ , PCl ₃ .

In particular, Mg dichloride is formed when both the halogenating agent and the carrier contain chlorine atoms. The halogenating agent is used in an amount such that the molar ratio between the OR group of the compound XnMg (OR) _2-n and the halogen atom of the halogenating agent is usually 1 or less.

An example of a reaction for forming Mg dihalide that retains morphological properties, including surface area and porosity of the raw material carrier, is the reaction of ClMgOC ₂ H ₅ with SiCl ₄ , AlCl ₃ and similar halogenating agents.

As described below, compounds of n <2 in XnMg (OR) _2-n , in particular n = 1, are compounds of XnMg (OR) _2-n in the presence of a halogenating agent, i.e., a substance capable of causing Mg-halogen bonds. By causing a production reaction, it can be decomposed into Mg dihalide.

In both cases of the final catalyst component (after the reaction with the Ti compound) and of the product obtained by treatment with a halogenating agent, the particle size distribution is within a narrow range. Generally at least 80% of the particles have a particle size of 5 to 25 microns, in particular 8 to 20 microns.

If the halogenating agent is a hydrogen halide, such as anhydrous gaseous HCl, the resulting product is an adduct between alcohols or phenols produced during the reaction of Mg dihalide. In the case of components suitable for the preparation of stereospecific polymerization catalysts of alpha-olefins, these adducts are compounds which can be removed by reacting alcohols or phenols in the adducts prior to reaction with the halogenated Ti compounds, such as Al-trialkyl, SCl ₄ , AlCl ₃ can be treated with benzoyl chloride.

However, it is also possible to react the adduct directly with the Ti compound, preferably in the presence of an electron donor free of active hydrogen, or to extract the residual electron donor immobilized on the catalyst component after extraction with TiCl ₄ at 80 ° C. for 2 hours. If the amount is from 0.5 to 3 moles per gram atom of Ti, the electron donor is introduced in the form of a bond with the adduct itself. Moreover, it is important that the catalyst component contain less than 50%, preferably less than 20%, Ti compounds which can be extracted with TiCl ₄ at 80 ° C.

Pretreatment of the carrier with hydrogen halide can yield a catalyst component, which, in addition to the morphological properties of the raw material carrier, contains a high content of Ti compounds that cannot be extracted with TiCl ₄ at 80 ° C.

This is beneficial because it lowers the halogen / Ti ratio of the catalyst and subsequently produces a polymer with a low halogen content, and the catalytic activity is likewise.

Prior to the reaction with the halogenating agent, the carrier can be treated with the electron donor c), and the electron donor can also be present during the halogenation reaction and can also be reacted at the end of the reaction.

The preparation of adducts based on X _n MG (OR) _2-n is carried out by various known methods, preferably by reacting anhydrous halides or mixtures thereof with alcohols, or by the production of phenol having already produced X _n MG (OR ) By the method of reacting with _2-n , wherein O ≦ _n ≦ 2, X and R are as described above.

This reaction is usually carried out in a suspension in an inert hydrocarbon medium (hexane, heptane, etc.) at a temperature ranging from room temperature or below to boiling point in the hydrocarbon solvent. The reaction with anhydrous hydrogen halide is preferably carried out at a temperature below room temperature, such as 0 ° C.

Anhydrous hydrogen halide is preferably used for 1 mole with respect to each OR group of compound X _n Mg (OR) _2-n .

The reaction of Ti compounds with adducts of Mg dihalides and alcohols or phenols can take place in the presence of electron donors, or the compounds can be reacted with the adducts or introduced into the adducts during their formation or Or, before conversion to an adduct, can be reacted with an X _n Mg (OR) _2-n compound. The amount of electron donor present in bound form in the adduct is generally from 0.05 to 1 mole relative to 1 mole of alcohol or phenol in the adduct.

The reaction of the Ti compound with the carrier or its adduct with alcohol or phenol occurs by suspending the carrier in a liquid reaction medium, which consists of a solution of the compound dissolved in a liquid Ti compound or an inert hydrocarbon rare solvent.

This reaction is preferably carried out using a liquid Ti compound as the reaction medium. Temperatures generally range from room temperature to 150 ° C. In the case of TiCl ₄ , it can be operated at its boiling point or below, for example at a temperature of 80 to 120 ° C. Generally, it is good to operate at the temperature of 110-135 degreeC.

The solid reaction product is separated from the liquid medium or excess of the Ti compound at a temperature at which the undesired Ti compound extractable with TiCl ₄ at 80 ° C. remains dissolved in the liquid reaction matrix and is removed with it.

When TiCl ₄ is used as the reaction medium, the separation of the solid powder is usually carried out at a temperature of 80 ° C or higher. However, low temperature operation is also possible if the amount of TiCl ₄ used is sufficient to dissolve unnecessary Ti compounds. It is also convenient to repeat the treatment once or several times with TiCl ₄ .

The reaction between the electron donor c) and the carrier (in this case compound c) reacts with the carrier prior to the reaction with the Ti compound) usually suspends the carrier in a hydrocarbon solution containing the electron donor and room temperature to 100 ° C, preferably 40 to It advances by making it react at the temperature of 80 degreeC.

The solid reaction product separated in the liquid phase is first washed with a hydrocarbon rare solvent and then reacted with the Ti compound.

The reaction between the carrier and the halogenating agent also proceeds by suspending the carrier in a liquid medium consisting of the halogenating agent or a solution thereof and reacting at a temperature of usually room temperature to 150 ° C.

The solid product is separated from the reaction mixture, washed and reacted with the electron donor and / or Ti compound.

As mentioned above, the electron donor may be added during the halogenation reaction.

The preparation of compounds with n <2 in compounds X _n Mg (OR) _2-n , in fact is consistent with the preparation of carriers, _{where 0} ≦ _n ≦ ₂ and R is 1 carbon atom in the compound of the general formula X _n MgR _2-n . Carried out by an exchange reaction with orthosilicate esters of Mg metal organic compounds having from 20 to 20 alkyl, aryl or cycloalkyl groups and X is alkyl, aryl or cycloalkyl having from 1 to 20 carbon atoms, identically or differently from halogen or R Can be.

The organometallic compound X _n MgR _2-n may be formed or formed in a generator state by reaction of an Mg metal with an organic halide RX (where X is halogen and R is the same as described above).

At least one of the R groups of the organometallic compound X _n MgR _2-n is transferred to the orthosilicate ester and at least one of the OR groups of the ester is bonded to the magnesium atom in the exchange reaction step.

Similar results to those obtained with orthosilicic acid occur with esters of other oxygenated inorganic acids, including, for example, alkyl borate, alkyl carbonate and alkyl phosphate.

The preferred method is to react Mg metal, organic halide and orthosilicate ester in only one step.

In compound RX, a compound wherein X is halogen, preferably Cl or Br, and R is an alkyl, alkenyl, allyl or cycloalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, is used as the organic halide do.

These compounds include, for example, chlorides and bromide of methyl, ethyl, n-butyl, n-amyl, n-octyl, t-butyl, isobutyl and cyclohexyl, 0-chlorotoluene, 2-chloroethylbenzene, vinyl chloride, chloride There is benzyl.

General formula of the silicic acid ester is as follows.

X _m Si (OR) _4-m

Wherein R is as defined for RX compounds, X is a halogen or an alkyl aryl or cycloalkyl group having 1 to 20 carbon atoms, and m is a number from 0 to 3.

Preferred Si compounds include aryl silicate Si (OC ₂ H ₅ ) ₄ . Examples of other Si compounds include Si (OCH ₃ ) ₄ , CHSi (0CH ₃ ), (CH ₃ ) ₂ , Si (OnC ₄ H ₃ ) ₄ , Si (OC ₆ H ₅ ) ₄ .

The Si compound is usually used in an amount equal to, or more than 1, preferably 3: 1 to 5: 1 of the ratio of the gram atoms of the OR group and the Mg. It is preferable to use 1-2 mol of organic halides per gram atom of Mg.

The operating temperature is 50 to 250 ° C, preferably 60 to 100 ° C. The order of addition of the reagents is not limited, but it is preferable to add magnesium and organic halides to the liquid or solution Si compound.

The preferred reaction medium is the Si compound itself or a mixture with an organic halide thereof, and the reaction can also proceed in the presence of an inert rare solvent such as, for example, a fatty, cycloaliphatic or aromatic hydrocarbon (hexane, hetane, benzene, toluene, etc.). have.

Inorganic halides such as oxo, alkyloxides or CaCl ₂ , CuCl, AgCl and MnCl can be used as reaction aids. Magnesium is used in the form of powder or slices.

According to another preparation, the Si compound may be reacted with a Grignard reagent of the general formula RMgX or MgR ₂ , wherein R is an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms. Examples of Grignard reagents include CiMg-nC ₄ H ₉ , ClMg-iC ₄ H ₉ , ClMgC ₅ H ₁₁ , C ₆ H ₅ MgCl, C ₆ H ₅ CH ₂ MgCl, CH ₂ = CHMgCl.

Grignard reagent and compound MgR ₂ are prepared by known methods. It is possible to use Grignard reagents prepared with nonpolar solvents such as ethers or hydrocarbons. For example, you may use Grignard reagents prepared from hydrocarbon / ether mixtures such as toluene / n-butylether mixtures.

The reaction conditions between the silicic acid ester and the Mg metal organic compound are the same as those in the one-step reaction between Mg, RX and the organosilicate.

Examples of known preparation methods which can be used to prepare the components according to the invention as producing the compound XMgOR, wherein X is halogen, are described in US Pat. Nos. 2,380,057, 2,442,053 and 591,440.

As mentioned above, the one-step reaction between Mg, RX and silicate and the reaction between silicate and compound X _n MgR _2-n can all proceed in the presence of a halogenating agent. In this case, the final product of the reaction must consist essentially of Mg dihalide in the form of spherical particles exhibiting the morphological, area and pore properties described above.

When hydrogen halide is used as the halogenating agent, the final reaction product is an adduct between the Mg dihalide and the alcohol produced during the reaction.

The catalyst component of the present invention forms a catalyst which is particularly effective for the polymerization of olefins by reaction with organometallic compounds of metals belonging to Groups II and III of the Periodic Table. The polymer obtained therefrom is a non-flowable particulate with a flow index of less than 25 seconds, in particular 12 to 20 seconds (index determined according to the method of ASTM 1895-69 / A).

In particular, when the main catalyst component contains an electron donor, and particularly an Al organometallic compound complexed with a charge donor is used as a promoter, it is suitable for alpha-olefin polymerization showing high activity and high stereospecificity. It is possible to prepare a catalyst which can obtain a polymer such as polypropylene in a nonflowable form with a narrow particle size distribution.

Suitable electron donors for forming complexes with organometallic compounds belong to the same class as the electron donor c) already described.

The amount of the electron donor is preferably such that at least 10%, particularly 20 to 80%, of the Al organic metal compound forms a complex. It is preferable to use alkyl esters of aromatic acids, such as esters of benzoic acid or toluic acid.

Al-trialkyls such as Al-triethyl, Al-triisobutyl and the like are preferably used as the Al compound. Further examples of useful Al-alkyl compounds include those described in British Patent No. 1,387,890. Al-trialkyl can also be used as a mixture with Al-dialkyl.

The ratio of Al / Ti in the catalyst suitable for the stereospecific polymerization of the alpha-olefin is usually 10 to 1000. A ratio of less than 10 is used when no electron donor is used at all or when 20 mol% or less with respect to the Al-alkyl compound.

Polymerization conditions of the alpha-olefins using the catalyst according to the invention are conditions known in the art.

The polymerization can be carried out in the liquid or gas phase in the presence or absence of acyclic hydrocarbon solvent (hexane, heptane and the like).

The temperature is 40 to 150 ° C, in particular 50 to 90 ° C.

In particular propylene or mixtures with minor amounts of ethylene are polymerized with the stereospecific catalyst of the invention.

The polymer obtained using the catalyst of the present invention is characterized by high flow index (typically 12 to 20 seconds) and narrow particle size distribution. Flow index is measured by the method of ASTM 1895-69A. Generally, at least 50% of the particles have a particle size of 100 to 500 microns. The proportion of particles having an average particle size of 50 µm or less and 100 µm or more is negligible.

The present invention will be described in detail by way of examples. However, this does not limit the present invention.

Example 1

a) preparation of catalyst components

12.2 g of 30-50 mesh flaky Mg metals were washed with 250 ml of n-hexane in a 1000 ml flask at 60 DEG C for 1 hour and then dried in a dry nitrogen stream. Subsequently, the suspension was kept at 65 DEG C, 104.5 g of tetraethyl orthosilicate was added, 0.2 ml of a solution of 2 g of maize in 10 ml of methyl oxide was prepared as a preparation, and a solution of 50.9 g of n-BuCl in 100 ml of n-hexane was added for 45 minutes. Added dropwise. The exotherm due to this reaction was removed to maintain the temperature at 70 ° C. It was then operated at 70 ° C. for 6 hours. Each time, 200 ml of n-hexane was used for decantation for 6 hours, followed by n-hexane washing at 50 ° C. The resulting solid product was vacuum dried at 50 ° C. to obtain 60 g of a solid product. His analysis is as follows (% by weight).

Ng = 18.65%, Cl = 27.05%

The surface area (measured by the method by BET-SORPTOMATIC 1860 Apparatus-C.ERBA) was 550 m ² / g and porosity 0.156 ml / g.

13.1 g of the dried product thereof was suspended in a solution containing 4.67 g (33.3 mmol) of benzoyl chloride in 200 ml of anhydrous n-hexane, and reacted at 60 ° C for 2 hours. The solid obtained by filtration at room temperature was washed twice with 200 ml of n-hexane each time.

The resulting solid was treated with TiCl ₄ , 110 ml at 120 ° C. for 2 hours. The solid which TiCl ₄ was then filtered at 120 ° C. was washed with n-hexane at 65 ° C. until no chlorine ions were detected.

Analytical Value: Ti = 1.85%, Mg = 20.7%, Cl = 70%.

b) polymerization of propylene

Al- butyl flow (Al-i-Bu ₃ 54.4 mol% and Al-n-Bu ₃ 45.5 mol%) n- heptane (anhydrous) 5.05 mmol of mixture of 80ml of p- toluic acid methyl 1.69 mmol (254mg) at room temperature and The reaction was carried out for 5 minutes at. Diluted with 50 ml of anhydrous n-hexane and contacting the catalyst component prepared by the method described above with an amount equivalent to 79 mg (equivalent to 1.43 mg of Ti) for 5 minutes. The suspension is charged into a dedicated 2.5 liter stainless steel autoclave containing 870 ml of n-hexane saturated with propylene at 40 ° C., equipped with a screw magnetic stirrer and thermocouple in a nitrogen stream, followed by the remaining Al—. 50 ml of butyl and methyl p-toluate solutions were charged in a propylene flow.

After the autoclave was sealed, 300 Ncc of hydrogen was introduced to bring the temperature to 60 DEG C, and propylene was introduced until the voltage reached 9 atm. The monomer was continuously supplied during the polymerization reaction to keep the pressure constant.

After 4 hours, the polymerization was stopped by rapid cooling and degassing the polymerization slurry. The polymer was separated by deodorizing the solvent with steam and dried in a hot nitrogen stream at 70 ° C.

Thus, 427 g of flake dry polymer was obtained. The yield was 292,000 polypropylene / g.Ti and the boiling n-heptane extraction residue was 90 weight.

The properties of the obtained polypropylene were as follows.

The apparent density of the polymer was 0.485 kg / 1 (DIN 53194) and the flow index was 16 seconds (ASTM 1895-69 / A).

Example 2

a) preparation of catalyst components

13.1 g of the product obtained by reacting Mg, Si (OEt) ₄ and n-BuCl with each other according to the method a) of Example 1 was suspended in a solution containing 3 g of ethyl benzoate in 200 ml of anhydrous n-hexane, followed by 2 hours at 60 ° C. Reacted. It operated according to the method a) of Example 1.

The dried product obtained by treatment with TiCl ₄ twice was analyzed and the following results were obtained.

Ti = 2%, Mg = 18.65%, Cl = 62.40%

Surface area = 345 m ² / g, porosity = 0.291 ml / g.

b) Polymerization of propylene in n-hexane solvents.

71 mg of the catalyst component (1.42 mg Ti) prepared in Method a) of this Example was introduced and operated according to Method b) of Example 1. At the end of the polymerization 493 g of flaky dry polymer were obtained, yielding 347,000 g polypropylene / g. Ti and boiling n-heptane residues were 91% by weight. The polymer had the following properties.

The apparent density was 0.505 kg / 1 and the flow index was 15 seconds.

Example 3

a) preparation of catalyst components

A solution of 224 g (2.42 mol) of n-BuCl and 459 g of Si (OEt) ₄ diluted in 53.5 g (2.2 gran atoms) of Mg metal and 400 ml of hexane was used. Unlike the method of Example 1 a), a solution containing n-BuCl and Si (OEt) ₄ was added to the preactivated magnesium at 70 ° C. for 45 minutes in the presence of agate crystals. The temperature of 70 degreeC was hold | maintained for 6 hours. After washing with hexane at 50 ° C and vacuum drying at 50 ° C, 264 g of a solid product having the following composition was obtained.

Mg = 16.7%, Cl = 33.9%, Si = 0.55.

The surface area was 450 m ² / g and the porosity was 0.157 ml / g.

12.35 g of its dried product was reacted with 4.67 g (33.3 mmol) of benzoyl chloride and 200 ml of TiCl ₄ at 130 ° C. for 2 hours.

It was similarly treated with TiCl ₄ after heat filtration. Heat filtration again and wash with hot hexane until no chlorine ions were detected in the filtrate. The product was dried at 40 ° C., and the result of analyzing the dried product was as follows.

Ti = 1.4%, Ng = 20.65%, Cl = 70.65%.

The surface area was 385 m ² / g and the porosity was 0.280 ml / g.

b) polymerization of propylene.

78 mg of the catalyst component prepared according to the polymerization conditions described in Example 1 b) was used. 360 g of flaky polymer having a boiling heptane extraction residue of 89.5% by weight was obtained. Yield was 330,000 g polypropylene g.Ti. The properties of this polymer are as follows.

The apparent density was 0.50 // 1 and the flow index was 18 seconds.

Example 4

a) preparation of the catalyst component.

12.2 g (0.5 gram atom) of metal was heated to 130 ° C. with 104.5 g (0.5 mol) of tetraethyl orthosilicate as cocatalyst and 150 mg of CuCl. To this was added 0.2 ml of a solution of 2 g of oxo in 10 ml of CH3I, and 84.5 g (0.75 mol) of chlorobenzene was added dropwise within 2 hours. In this way, the internal temperature was raised to 160 ° C. It was made to react at 160 degreeC temperature for 5 hours at the end of this operation. The product was washed three times with 300 ml of toluene each time at 50 ° C. followed by four times with 200 ml of hexane each time. The solid separated in this way was vacuum-dried at 50 degreeC, and 50.7g of dry products were obtained. Its composition was as follows.

11.1 g of the solid dried product was reacted with 4.67 g (33.3 mmol) of benzoyl chloride and 110 ml of TiCl ₄ at 130 ° C. for 2 hours.

This was filtered hot and washed with hexane at 65 ° C. until no chloride ions were detected in the filtrate. The composition of the vacuum product dried at 40 ℃ was as follows.

Ti = 1.25%, Mg = 18.8%, Cl = 62.9%, Si = 0.22%

Surface area 94 m ² / g, porosity 0.24 ml / g.

b) polymerization of propylene.

Propylene was polymerized under the same conditions as those of Example 1 b) using the dried product 70 prepared as described in Example a). 217 g of flaky polymer were obtained, the yield of which was 248.000 g polypropylene / g. Ti and boiling heptane extraction residue was 90% by weight.

The properties of this polymer were as follows.

Intrinsic viscosity: 1.7 dl / g. Melt Index: 9.3g / 10min

Example 5

a) preparation of catalyst components

42.2 g (0.45 mol) of n-BuCl and 52 g of si (OEt) ₄ diluted in 100 ml of toluene were added to 10.95 g (0.45 gram atom) of Mg metal at 45C for 60 minutes. This was made to react at 60 degreeC for 6 hours. Washed with cold hexane. The residual solid product was dried in vacuo at 50 ° C. to obtain 49.4 g of a solid dried product of the following composition.

Mg = 18.2%, Cl = 31.2%, si = 0.42%.

12.35 g of this solid product were reacted with sicl ₄ , 169.8 g (1 mol) and 3 g (20 mmol) ethyl benzoate at 60 ° C. for 24 hours. Sicl ₄ was removed by filtration at 60 ° C. and washed successively with hexane at 65 ° C., and then the solid residue product was washed twice with 200 ml of Ticl ₄ each time for 1 hour at 130 ° C. and no chlorine ion was detected in the filtrate. Wash further at 65 ° C. until no.

The composition components of the dried product were as follows.

Ti = 1.05%, Cl = 66.75%, Mg = 20.3%, si = 0.21%.

Surface area = 302 m ² / g. Porosity = 0.27 ml / g.

b) polymerization of propylene

The same polymerization conditions as described in Example 1 b) were used, and 66 mg of the solid product prepared in Example 5 a) was used. 220 g of irregular and nonuniform thin sheet polymer was obtained. The yield was 318,000 g polypropylene / g.Ti and the boiling heptane extraction residue was 87% by weight.

This polymer has the following composition.

Apparent Density: 0.4kg / 1. Melt Index: 5.2g / 10min

Intrinsic Viscosity: 1.7dl / g

Example 6

a) preparation of catalyst components

32.5 g of the product (MgcloEt thin) prepared according to Example 3 a) were suspended in 200 ml of anhydrous hexane, the temperature was brought to 0 ° C., and then gaseous HCl was injected in an amount of 14.1 N1 for 2 hours. After the HCl feed was stopped, the suspension was kept at 60 ° C. for 1 hour. Hexanes were washed until no chlorine ions were detected at room temperature. The solid product was vacuum dried (residual pressure 20mmHg) at 30 degreeC, and 34.8g of dried products were obtained. His analysis is as follows.

Mg = 15.65% Cl = 50.55%, Si = 0.07%.

14.2 g of the solid product thus obtained were reacted with sicl ₄ , 340 g (2 mol) and 3 g (20 mmol) ethyl benzoate at 60 ° C. for 24 hours. Sicl ₄ was filtered off at 25 ° C., and the residue was washed repeatedly with cold hexane successively, then suspended in 200 ml of TiCl ₄ and reacted at 120 ° C. for 3 hours to perform a similar treatment after hot filtration.

After repeated washing with cold hexane until no chloride ion was detected, the solid product was washed and dried at 40 ° C. The analyzed value of the dried product was as follows.

Ti = 2.25%, Cl = 66.45%, Mg = 16.35%.

Surface area = 410 m ² / g, porosity = .185 ml / g.

b) polymerization of propylene

412 g of a thin polymer was obtained by operating in accordance with Example 1 b) using 60 mg of a catalyst component (Ti 1.35 mg) prepared by the above-described method. The yield corresponds to 305,000 polypropylene / g.Ti and the boiling heptane extraction residue was 89% by weight.

The properties of this polymer were as follows.

Example 7

a) preparation of catalyst components

32.5 g of the product (MgclOEt thin plate) prepared according to the method of Example 4 a) were suspended in a solution containing 11.52 g (0.25 mol) of anhydrous ethyl alcohol in 150 ml of hexane, and the suspension was heated at 0 ° C for 1 hour. The solid product was washed with cold hexane and then vacuum dried under partial pressure of 20 mmHg to give 45.6 g of dried product. His analysis was as follows.

Mg = 11%, Cl = 37.65%, Si = 0.1%.

20.3 g of the solid product thus obtained was reacted with 340 g (2 mol) of sicl ₃ and 3 g (20 mmol) of ethyl benzoate at 60 ° C for 24 hours. Sicl ₄ was then filtered off at 60 ° C. and the residual solid product was repeatedly washed with hexane at 60 ° C., suspended in 200 ml of Ticl ₄ and reacted for 2 hours. After hot filtration a similar treatment was carried out and washed at 65 ° C. After vacuum drying at 40 ° C., the analytical value of the dried product was as follows.

Ti = 2.15%, ci = 63.4%, Mg = 18.05%, si = 0.23%.

b) polymerization of propylene.

58 mg of the catalyst component prepared in Example 1 a) was polymerized under the same polymerization conditions as in Example 1 b). 400 g of thin polymer was obtained. The yield thereof corresponds to 320,000 g polypropylene / g.Ti and the boiling heptane extraction residue was 89.5% by weight.

The properties of this polymer were as follows.

Intrinsic viscosity: 2.1dl / g Melt index: 2.2g / 10min

Example 8

a) preparation of the catalyst component.

65.3 g of the product (MgCLOE _t sheet) prepared as described in Example 3 a) were suspended in 400 ml of hexane to bring the temperature to 0 ° C., and gaseous HCl was then introduced at a rate of 14.1 N1 / hour for 4 hours. The HCl feed was stopped and then the suspension was heated at 60 ° C. for 1 hour. After washing with hexane and drying at room temperature, 70.6 g of a solid dried product was obtained according to the method of Example 6 a). His analysis was as follows.

Mg = 15.85%, Cl = 48.5%.

15.4 g of the product thus treated was reacted with sicl ₄ , 340 g (2 mol) and 4.05 g (27 mmol) of benzoic acid at 25 ° C. for 2 hours, and then the mixture was heated at 60 ° C. for 18 hours. After this treatment, the mixture was filtered at 50 ° C and washed repeatedly with heptane at 50 ° C. The residual solid was dried, suspended in TiCl ₄ and reacted at 130 ° C. for 2 hours. After hot filtration, the TiCl ₄ treatment was repeated. After repeated washing and drying several times with heptane at 80 ℃, drying and the like was analyzed.

Ti = 1.65%, Cl = 66.15%, Mg = 19.80%, si = 0.19%.

Surface area = 288 m ² / g, porosity = 0.27 ml / g.

b) polymerization of propylene

The polymerization was carried out under the same conditions as in Example 1 b) using 64 mg of the catalyst component prepared in a) above. 296 g of thin polymer was obtained. This yield corresponds to 280,000 g polypropylene // g.Ti and the boiling heptane extraction residue was 87% by weight.

The properties of the polymer were as follows.

Intrinsic viscosity: 2.1dl / g Melt index: 2.5g / 10min

a) preparation of catalyst components

A solution obtained by dissolving 12.2 g of pre-activated Mg metal as described in Example 1 a) and 10 g of si (OEt) and 2 g of oxo in 10 ml of CH ₃ I was mixed at a temperature of 60 ° C., in which 100 ml of hexane was added. To this solution was added dropwise a solution of 51 g of n-BuCl, and at the same time gaseous HCl was introduced at 70 ° C. at a rate of 11.2 N1 / hour. At this time, n-BuCl-hexane solution is added dropwise over 1 hour and hydrochloric acid is introduced over a total of 6 hours. The introduction of HCl was stopped, diluted with 100 ml of hexane, and the suspension was stirred again at 70 ° C. for 1 hour, finally washed with hexane at 50 ° C. and dried to recover 76.3 g of dried product. The analysis was as follows.

Mg = 14.5%, Cl = 40.85%, si = 0.16%.

16.8 g of the solid product thus obtained was reacted with a mixture of 340 g (2 mol) of siCl ₄ and 3 g (20 mmol) of ethyl benzoate at 60 ° C. for 24 hours. The solid residue obtained by filtration at 55 ° C. was repeatedly washed with hexane at room temperature, and then reacted with 110 ml of TiCl ₄ at 118 ° C. for 2 hours. The mixture was filtered hot and introduced with fresh TiCl ₄ and reacted at 130 ° C. for 2 hours. This was filtered hot and washed repeatedly with hexane and dried to obtain a solid residue. The analysis was as follows.

Ti = 2.2%, Cl = 55.1%, Mg = 22%, Si = 0.21%.

b) polymerization of propylene

The polymerization was carried out under the same conditions as in Example 1 b) using 65 mg of the catalyst component prepared in a). As a result, 287 g of a polymer having 87% by weight of boiling heptane extraction residue was obtained. It was 201,000g polypropylene / g.Ti, and its characteristics were 1.4dl / g intrinsic viscosity and 11.6g / 10min of melt index.

Example 10

a) preparation of catalyst components

Example 1 a), 13.1 g of the product was prepared and suspended in a solution in which 3 g (20 mmol) of ethyl benzoate and 1.22 g (10 mmol) of 2,6-dimethylphenol were dissolved in 200 ml of anhydrous hexane, and the suspension was subjected to 60 ° C. The temperature was raised to and maintained at this temperature for 2 hours. The solid was separated at room temperature and washed twice with 200 ml of hexane each time.

The results were analyzed by treating the solid product with TiCl ₄ under the same conditions as described in Example 1 a) and then repeatedly washing with hexane at 65 ° C. and then drying under vacuum.

Ti = 2.5%, Cl = 63.25%, Mg = 20%, si = 0.21%.

b) polymerization of propylene

The polymerization was carried out under the same conditions as in Example 1 b) using 61 g of the catalyst component (Ti 1.525 mg) prepared in a). After completion of the polymerization, 456 g of dry polymer was obtained in the form of flakes, which amounted to 299,000 g polypropylene / g.Ti, and the boiling heptane extraction residue amounted to 91.5% by weight. The characteristic of the obtained polymer was as follows.

The temperature rises sharply to 70 ° C. (30 atmospheres), which was maintained for 3 hours and then the polymerization was stopped. 5 kg of dry polymer was obtained in pieces by pouring the polymerization slurry into water and removing unconverted monomer by flashing. The yield of this weight was 286,000 g polypropylene / gTi, the boiling heptane extraction residue was 93.5 wt%, and the polymer properties were as follows.

Intrinsic viscosity: 1.3dl / g Melt index: 18.7g / 10min

The elemental content of the catalyst residue analysis in the polymer was as follows.

Ti = 3.5ppm, Mg = 26ppm, Cl = 105ppm.

c) polymerization in liquid propylene.

In a 150 L autoclave capable of temperature control with water and steam, 36 g of Al-butyl mixture according to Example 1 b) was distilled off with 55.5 ml of hexane and introduced in a feed stream of 15 kg of liquid propylene in the absence of air and then stirred. Under dissolving 10.9 g of methyl paratoluate in 52 ml of hexane, the mixture was introduced again with 25 kg of liquid propylene (conducting content of propylene 40 kg). The temperature was raised to 60 ° C. for 20 minutes, and the catalyst component 0.7 (Ti 17.5 mg) prepared in a) was suspended in 200 ml of hexane and introduced under a hydrogen gas introduction pressure of 100 Nl at the same temperature.

Example 11

a) Preparation of the catalyst component is the same as described in Example 2 a).

b) 14.3 mg of the catalyst component prepared in Example 2 a) was suspended in a solution containing 2 g of Al-tri-isobutyl in 1000 ml of hexane, followed by weak ethyl flow with 2.5 l of the same substance as in Example 1 b). Introduced to the declave. The temperature rose sharply to 85 ° C, while hydrogen gas was introduced at a partial pressure of 7.4 atm and ethylene at a maximum of 6.6 atm.

The polymerization was carried out while introducing ethylene at 85 占 폚 for 4 hours under a voltage of 15 atm. At the end, 214 g of flaky dry polymer was obtained, which yielded 748,000 g of polyethylene / gTi, having an E degree of 7.8 g / 10 minutes and an N degree of 81.6.

Example 12

a) 14.2 g of the prepared solid product (composition Mg 15.65%, Cl 50.55%, Si 0.07%) were reacted with ethyl benzoate 3 in 60 cc of n-octane for 2 hours according to Example 6 a).

This suspension was added to 200 ml of TiCl ₄ , reacted at 120 ° C. for 2 hours, then filtered and then treated similarly to the above, followed by repeated washing with heptane at 80 ° C. so that no chlorine ions appeared, and then a portion of the solid product was suspended in heptane. The residue was dried at 40 ° C. under vacuum.

The result of analyzing the solid product thus obtained was as follows.

Ti = 2.2%, Cl = 60.8%, Si = 0.13%.

The surface area was 410 m ² / g, and the porosity was 0.190 ml / g.

b) polymerization of propylene

The polymerization was carried out in the same manner as in Example 1 b) except that 0.6 ml of the suspension containing the catalyst component prepared in accordance with a) and 0.6 ml of Ti was used.

In this way, 430 g of a polymer was obtained, which corresponds to a yield of 250,00 g · Ti. It was 91.5 weight% of the residue after boiling n-hexane extraction.

a) preparation of catalyst components

It carried out similarly to Example 12 except having made 2.8 g of benzoyl chloride react at 60 degreeC for 1 hour.

The dried product obtained after the reaction with TiCl ₄ was analyzed to obtain the following results.

Ti = 2.05%, Cl = 62.2%, Si = 0.04%, Ethyl Benzoate = 10%

b) polymerization of propylene

In the same manner as in Example 12 b), 473 g of a polymer was obtained, which yielded 222,220 g of polymer / g · Ti and the residue after boiling n-heptane extraction was 93% by weight.

Example 14

a) 32.5 g of the compound ClMgOet prepared according to Example 3 a) was reacted with HCl under the same conditions as in Example 6 a) except that 3 g of ethyl benzoate was carried out in the presence of 3 g of ethyl benzoate. The analysis results of the product thus obtained were as follows.

Mg = 14.02, Cl = 38.98%, ethyl benzoate = 17%

This product was reacted with TiCl ₄ under the same conditions as in Example 12 except that the reaction temperature was 110 ° C. The analysis results of the obtained dry product were as follows.

Ti = 2.65, Cl = 59.8, Si = 0.1%, ethyl benzoate = 9%

b) polymerization of propylene

The polymerization was carried out under the same conditions as in Example 12 b) to obtain 321 g of a polymer, which was equivalent to 222.100 g · polymer / g · Ti.

Example 15

a) preparation of catalyst components

Solid product prepared according to Example 9 a), i.e. 16.8 g of product containing Mg 14.5%, Cl 40.83%, Si 0.16%, was reacted with 3 g of ethyl benzoate in n-octane at 60 ° C for 1 hour. This suspension was added to 200 ml of TiCl ₄ , reacted at 120 ° C. for 2 hours, followed by filtration, and then subjected to a similar treatment as described above. After repeated washings at 80 ° C. with heptane, a portion of the product was suspended in heptane, while the remainder of the product was dried at 40 ° C. under vacuum.

The analysis results of the thus obtained dry product were as follows.

Ti = 2.2%, Cl = 55.1%, Si = 0.2%, ethyl benzoate = 8%

b) polymerization of propylene

This test was carried out under the same conditions as in Example 12) b). This gave 287 g of polymer, which amounted to 201,000 g of polymer / g · Ti.

Example 16

a) preparation of catalyst components

37.7 g of the product (containing 11% Mg, 37.65% Cl, and 0.1% Si) prepared according to Example 7 a) were reacted with 3 g of ethyl benzoate at 60 ° C. in 60 cc of n-octane for 1 hour. The result of the analysis of the dried product obtained by reacting the suspension with TiCl ₄ under the same conditions as in Example 12 was as follows.

Ti = 1.8%, Cl = 68.9%

b) polymerization of propylene

This test was carried out under the same conditions as in Example 12 b). This resulted in 350 g of polymer, which yielded 296,000 polymer / g Ti. Moreover, the residue after boiling n-heptane extraction was 91.5 weight%.

Claims (1)

In order to obtain α-olefin polymers of free flowing particles having a narrow particle size distribution, organometallic aluminum compounds (tri lower alkyl aluminum) (A), tetravalent Ti compounds (titanium tetrachloride) (B) and aliphatic esters of benzoic acid, aromatics In carrying out the polymerization in the presence of a catalyst component composed of an electron donor selected from an ester or an alicyclic ester, magnesium formed from a compound or a mixture of compounds in which both the tetravalent Ti compound and the electron donor are represented by the following general formula Chemically bound to a carrier consisting of a halide; Component (B) is a spherical particle having an average diameter of 1 to 100 µ, a surface area of about 90 m ² / g or more and a porosity of 0.3 cm ³ / g or less, and tetravalent Ti having a tetravalent titanium compound content extractable by TiCl ₄ at 80 ° C. 50% by weight or less of the compound, preferably 20% by weight or less, in the presence or absence of a solvent, characterized by the general formula CH ₂ = CHR (where R has a hydrogen atom or 1 to 6 carbon atoms) The catalyst component for superposition | polymerization of (alpha) -olefins represented by the alkyl group. XnXg (OR) _2-n wherein n is ₀ ≦ _n ≦ ₂ , R is an alkyl, aryl, cycloalkyl group having 1 to 20 carbon atoms, and X is a halogen atom or an OR ′ group (where R ′ Is an alkyl, aryl or cycloalkyl group having the same or different from R as 1 to 20 carbon atoms.