DK151969B - Solid catalyst component for use in catalysts during polymerisation of alpha-alkenes - Google Patents

Description

DK 151969B

The invention relates to a solid catalyst component useful in a single catalyst for the polymerization of α-alkenes and of the kind set forth in the preamble of claim 1. The corresponding catalyst is useful for homo- and copolymerizing α-alkenes having at least three carbon atoms and for polymerizing these α-alkenes in admixture with ethylene.

Because the catalysts based on the solid catalyst component of the invention have high activity and stereospecificity in the polymerization of α-alkenes, they are particularly suitable for the preparation of crystalline polymers of the α-alkenes and of crystalline copolymers of α-alkenes with ethylene.

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2 |

It is an object of the invention to provide a solid catalyst component of the kind set forth in the preamble of claim 1, by means of which a catalyst suitable for the preparation of the specified crystalline polymers and copolymers can be prepared.

In particular, the invention relates to a catalyst component by which catalysts can be prepared capable of stereo-specific polymerization of propylene and mixtures thereof with ethylene, and to produce polypropylene with a high isotactic index and crystalline copolymers of propylene and ethylene. .

Examples of catalysts that exhibit high activity and stereo-specificity in the polymerization of α-alkenes and especially of propylene are described in English Patent No. 1,387,890 and in German Publication No. DOS 2,504,036.

The catalysts disclosed in English Patent No. 1,387,890 are generally prepared by reaction between an Al trialkyl compound, especially complexed with an electron donor compound, and the product resulting from comminution of an Mg dihalide in mixture with an electron donor compound and a halogenated Ti compound. The activity of these catalysts, expressed in g of polymer / g Ti, is sufficiently high when the reaction is carried out in liquid phase, in the absence of inert, as diluents serving hydrocarbons.

Conversely, it is reduced to unsatisfactory values as to the possibility of avoiding purification of the catalyst residue polymer when the polymerization is carried out in the presence of inert solvents serving as hydrocarbons.

Furthermore, the isotacticity index of the polymers obtained with these catalysts is significantly reduced when the polymerization is carried out in the presence of hydrogen as a modifier for the molecular weight of the polymer.

The catalysts of DOS 2,504,036 are prepared by reacting

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3 sets an Al-alkyl compound with the product obtained by reaction between a liquid Ti compound and a mixture prepared by fine grinding a mixture of an Mg dihalide with an organic ester and with an organic Si connection.

These catalysts exhibit a high stereospecificity when the polymerization is carried out in the absence of hydrogen; conversely, a very significant decrease occurs when hydrogen is used as a molecular weight modifier.

Attempting to improve the stereospecificity of the catalysts by adding an electro-donor compound to the Al-alkyl compound used as a co-catalyst results in an improvement of the polymer's isotactivity index, but the catalytic activity is significantly reduced.

Japanese Patent Application No. SH 049-25088 discloses polymerization catalysts obtained from an Al-alkyl compound (Al-trialkyl) and from a catalyst component prepared by grinding mixtures of MgCl with an organic ester and by subsequent reaction of the ground product with TiCl 2. The catalysts described in this patent application possess high activity and stereospecificity in the polymerization of propylene carried out in the absence of hydrogen as a molecular weight modifier. If the polymerization is carried out in the presence of hydrogen, the isotacticity index is greatly reduced.

It has now surprisingly been found that on the basis of the solid catalyst component of the invention it is possible to synthesize catalysts useful for polymerizing α-alkenes and mixtures thereof with ethylene, which are characterized by a high stereospecificity, even when the polymerization are carried out in the presence of hydrogen and are capable of providing high yields of polymer, even when the polymerization is carried out in the presence of an inert, hydrocarbon serving diluent.

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4

The solid catalyst component according to the invention, which is of the kind set forth in the preamble of claim 1, is characterized by that specified in the characterizing part.

i i

As mentioned above, the surface area of the catalyst component as such is 2 2 higher than 20 m / g, and preferably higher than 40 m / g.

The catalysts are preferably prepared by contacting the catalyst component of the invention with the product obtained by pretreating a) a metal organic Al compound which does not contain halogen atoms directly bonded to the Al atom, and b) an electron donor compound; in such an amount that 15 - 100% by weight of the compound a) is reacted with the electron donor compound, for a period which is generally shorter than 1 hour.

Catalysts with good operating properties can also be prepared by simultaneously mixing the components or by first contacting the catalyst component of the invention with component a) and then with component b) and vice versa. The amount of electron donor compound used as component b) is preferably such that the molar ratio of the electron donor groups of the electron donor compound reacted with the metal-organic Al compound to the total amount of the specified Al compound preferably between 0.2 and 0.4. This means that from 20 to 40% of the metal-organic Al compound is combined with the electron donor compound.

Any electron donor compound (or Lewis base) capable of providing complexes with the metal-organic Al compound used as component a) or to provide a substitution reaction with such compound (such as, for example, according to the following reaction scheme: in 2 AIR ^ + RNH ^ -> R2AI-N-AIR + 2RH, can be exchanged as component b).

R

Some examples of electron donor compounds useful as component b) are amines, ethers, ketones, nitriles, thioesters, aldehydes, alcoholates, amides and salts of organic acids and of metals belonging to groups I and IV of the periodic table. system.

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In the case of Al salts, they can be formed in situ by reaction between an organic acid and the metal-organic Al compound used as component a).

Suitable organic acids are the aromatic organic acids, e.g. benzoic acid and p-hydroxybenzoic acid.

Some examples of specific compounds are triethylamine, N, N'-dimethylpiperazine, diethyl ether, di-n-butyl ether, tetrahydrofuran, acetone, acetophenone, benzonitrile, tetramethylurea, nitrobenzene, Li-butylate, dimethylaminophenyl-lithium and Na-dimethylamide.

The most interesting results in terms of both activity and stereo-specificity of the catalysts have been obtained with the esters of the organic and inorganic oxygen-containing acids with ethers such as di-n-butyl ether. Particularly suitable esters are e.g. alkyl esters of aromatic acids such as benzoic acid, p-methoxy or ethoxy benzoic acid and p-toluyl acid such as e.g. ethyl benzoate, ethyl p-methoxybenzoate, methyl p-toluate, ethyl p-butoxybenzoate.

Further examples of useful esters are diethyl carbonate, triethylborate, ethyl pivalate, ethyl naphthoate, ethyl o-chlorobenzoate, ethyl acetate, dimethyl maleate, alkyl or aryl silicates and methyl methacrylate.

The metal inorganic Al compounds useful as component a) preferably consist of Al trialkyl such as e.g. Al-triethyl,

Al-tripropyl, Al-triisobutyl, Al (C1-6 -CH- (CH2) 2- ^ 3) 3> akch2-ch- (ch2) 3-ch3) 3 and ch3 C2H5 A-UC12H25 ^ 3 '

It is also possible to use metal-organic Al compounds containing two or more Al atoms bonded via O or N atoms.

They are usually prepared by reacting an Al trialkyl compound with water, ammonia or a primary amine according to known methods.

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6

Examples of such compounds are in (02 ^) ^ 1-0 ^ 1 (02 ^) 2 and (c2h5) 2-ai-n-ai- (c2h5) 2.

C6H5

The metal-organic Al compounds disclosed in English Patent No. 1,513,480 are further examples of useful compounds.

Other useful compounds are e.g. the hydrides of aluminum dialkyl, the alkoxides of aluminum dialkyl, such as: Α1 (02Η ^) 2 (002, ^), j Al (Ο ^ Η ^) 2 (OC ^H ses), and the sesquial coxides of Al ethoxy-aluminum-ethyl and sesquibutoxy-aluminum-butyl.

The electron donor compound present in combined form in the catalyst component of the invention may be the same compound as component b) or a deviating compound therefrom.

Also in this case, any electron donor compound capable of forming complexes with the Mg halides can be used to prepare the catalyst component of the invention.

Preferably esters, ethers and diamines are used. Examples of esters are those already listed as being useful as component b) of the catalyst.

A particularly effective diamine is N, N, N ', N'-tetramethylethylenediamine.

The solid catalyst component according to the invention preferably comprises, at least in the surface, reaction products of magausium halides selected from Mg dichloride and dibromide, and halogenated compounds of tetravalent Ti, especially TiCl4, TiBr4, Ti-halogen alcoholates , with an electron donor compound selected from organic esters, especially esters of the aromatic acids, such as e.g. benzoic acid. The nature and composition of this component is further defined by the following parameters.

The Mg / Ti ratio is between 3 and 40, preferably between 10 and 30; the halogen atom / Ti ratio is between 10 and 90, preferably between 20 and 80, and the ratio of moles of electron donor compound / Ti is greater than 0.2 and is in particular between 0.4 and 3, especially between

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7 1,2 and 3.

At least 80% by weight and preferably 90% of the Ti compounds found in the catalyst component of the invention are insoluble in boiling n-heptane, while more than 50% by weight, especially over 70% by weight of the Ti compounds which are insoluble in boiling heptane, are insoluble in Ti-tetrachloride at 80 ° C.

The surface area of the catalyst component of the invention as well as the area of the product insoluble in TiCl. at 80 ° C, semen 2 is usually greater than 100 m / g and is most preferably between 100 and 200 m / g.

The solid catalyst component of the invention, which is particularly well suited for the production of highly active catalysts which simultaneously have a high stereospecificity, is further characterized in that the most intense line present in the spectrum of the normal type Mg chloride and bromide , as defined in ASTM 3-0854 and 15-836 for chloride and bromide, respectively, exhibit a reduced relative intensity and appear asymmetrically flattened, thus forming a ring exhibiting an intense maximum offset with respect to the interplanar distance. c in the maximum intensity line, or the spectrum is characterized by the fact that the maximum intensity line no longer exists and that instead a ring has an intensity maximum offset with respect to the distance cJ of this line.

As for MgCl2, the ring intensity maximum lies between cl = 2.44 and 2.97 A.

In general, the composition of the solid catalyst component can be expressed as consisting of Mg chloride or dibromide for 70-80% by weight, whereby the difference up to 100 consists of the Ti compound and the electron donor compound.

However, the solid catalyst component of the invention, in addition to the compounds cited above, may also comprise inert solid solvents in amounts which can reach 80% and above relative to the weight of the solid catalyst component according to [DK 151969B | s! find introduction. Examples of such materials are: LiCl, CaCO3 and CaCl3 Na2SO4, Na2CO3, Na2O1, CaSO4, AlCl2, Β, Ο »» SiO2 09 TiO2 *

In particular, it has been observed that the surface area generally decreases if the solid catalyst component of the invention is produced in the presence of inert solid materials.

In particular, it has been observed that the resulting product has a surface area which is generally below 10-20 m / g when the solid catalyst component of the invention is homogeneously mixed with agglomerating materials, especially f₂O₂ and AlCl₂.

However, the properties of the catalyst resulting from the thus treated solid catalyst component of the invention are still acceptable in terms of polymer yield.

In the preparation of the solid catalyst component of the invention, it is possible to support the active ingredients of the solid catalyst component of the invention on inert carriers such as SiO₂ and Al₂O₂ with high porosity. In this case, the halogenated Ti and Mg compounds and the electron donor compound represent a reduced proportion to the total amount, enabling catalysts to be obtained in which the amount of undesirable materials such as halogens is minimal.

It should be remembered that the ratio of Mg / Ti in the solid catalyst component of the invention is generally higher than 1, but it is lower than 1 when TiO 2 and similar Ti compounds which do not react with the halogenated Mg compound are used as fillers. .

The solid catalyst component of the invention can be prepared in various ways.

A general method consists initially of a particular mixture or 1 carrier comprising an Mg halide and a complex between this Mg halide and an electron donor compound, wherein the ratio of Mg / mol electron donor compound is higher than 2 and preferably is

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9 between 2 and 15, and in treating this mixture or carrier with a liquid, tetravalent Ti compound under conditions such that a quantity of Ti compound is fixed to the carrier and then separating the solid reaction product from the liquid phase under such conditions that practically no Ti compounds, which are soluble in boiling n-heptane and extractable with Ti-tetrachloride at 80 ° C, remain on the product.

The particular feature of the carrier to be treated with the liquid Ti compound is that it provides a Rontgen beam spectrum in which the line of the maximum intensity present in the spectrum of the normal type Mg halide , exhibits a reduced relative intensity and exists asymmetrically flowing to form a ring in which the intensity maximum is offset relative to the maximum intensity line or where the maximum intensity line is not present in the spectrum and there is instead a ring with an intensity maximum offset from the distance jd of the maximum intensity line.

This carrier, i.e. the starting product for the preparation of the solid catalyst component of the invention can be obtained in various ways. A preferred way is to subject mixtures of an Mg halide, especially the dichloride and dibromide, to comminution with an electron donor compound, optionally working in the presence of a Ti compound and / or an inert co-carrier and / or materials which promote the comminution, such as silicon oils, until the rings indicated above, whose intensity maxima are offset relative to the maximum intensity line, occur in the X-ray spectrum of the comminuted product.

The finely divided product is then treated with a liquid, halogenated Ti compound, especially TiCl 3, at such a temperature (generally between room temperature and 200 ° C) and for such a time as to fix the appropriate amount of Ti compound.

The solid product from the reaction is then separated from it

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ίο in the liquid phase, e.g. by filtration, sedimentation, etc., under conditions of temperature and / or dilution with the liquid Ti compound, that in the solid product after extraction first with boiling n-heptane and then with TiCl there are any amounts of extractable Ti compound exceeding 20 and 50 weight percent, respectively.

Other methods of preparing a carrier suitable for preparing the solid catalyst component of the invention are those wherein in an inert solvent of a hydrocarbon an anhydrous Mg halide is reacted with an organic compound containing active hydrogen in the presence of an organic ester and then treating the reaction product with a metal-organic Al compound.

It is also possible to reverse the order of reactions, ie. treating the complex between the Mg halide and the active hydrogen-containing compound with the metal-organic compound and then reacting the resulting product with the organic ester.

These preparation methods are illustrated in English patent no.

1502886. .

The product thus obtained is washed with a solvent, inert hydrocarbon to remove any traces of free metal-organic compound, and then reacted with a liquid Ti compound, especially TiCl 2, at a temperature between 20 and 200 ° C. C and the solid reaction product is separated from the liquid phase under such filtration and sedimentation conditions that no Ti compounds extractable with boiling n-heptane and with Ti-tetrachloride remain on the solid component. 80 ° C.

in

Another method of preparing a carrier suitable for preparing the solid catalyst component of the invention is illustrated in English Patent No. 1,505,315. Also in this case, the carrier is reacted with a liquid Ti compound and

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The elution product is separated from the liquid phase under such conditions that no Ti compounds remain soluble in liquid heptane and in Ti tetrachloride at 80 ° C.

When using an Mg halide, according to the above preparation methods, this is preferably as anhydrous as possible (content of h 2 O lower than 1 wt Si), especially when the catalyst component is prepared by comminution.

However, it is possible that starting materials for the preparation of the solid catalyst component of the invention can be used a hydrated Mg halide, which generally contains between 0.1 and 6 moles of H moles of halide. In addition, it is possible to use oxygen-containing Mg compounds such as MgO, MgCOH) Mg (OH) Cl, Mg carbonate, Mg salts of organic acids, Mg silicate, Mg aluminates, Mg alcoholates and halogenated derivatives thereof. . Metal organic Mg compounds containing at least one Mg-C bond may also be used. Examples of such compounds are Grignard's reagents and the compounds MgF 2, wherein R is an alkyl, cycloalkyl or aryl radical containing up to 20 carbon atoms. In all these cases, the Mg compound is reacted with the Ti-tetrachloride in excess, preferably operating at the boiling point of the tetrachloride, and then separating the solid product hot, preferably at the boiling point of TiCl 2.

The resulting solid product is treated in suspension in an inert hydrocarbon with an organic ester, especially with an ester of an aromatic carboxylic acid in amounts equal to 1-20 moles per liter. gram atom Ti contained in the carrier, operating at temperatures ranging from room temperature to 200 ° C.

The solid product treated in this way is accurately separated from the unreacted ester and then reacted with a liquid halogenated Ti compound and separated from the liquid reaction phase under the conditions set forth above for the other preparations.

12

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In all of these preparation methods, it is essential that at least 80% by weight of the Ti compounds found in the solid catalyst component of the invention are insoluble in boiling n-heptane and that less than 50¾ of the Ti compounds which are insoluble in boiling heptane are extractable with Ti tetrachloride at 50 ° C. Indeed, the presence of soluble Ti compounds is detrimental to both the activity and the stereospecificity of the catalyst, especially when the polymerization is carried out in the presence of hydrogen.

The catalysts are preferably used in the polymerization of alpha alpha-olefins having at least three carbon atoms, and especially in the preparation of crystalline polymers and copolymers of propylene. They can also be used in the polymerization of ethylene, in which case component b) can be omitted. It has been found that it is possible that, as components of the catalysts having good properties, solid catalyst components of the invention can also be used, wherein the valence of tetravalent Ti is reduced to values below 4 by treatment with reducing agents before providing contact between the solid catalyst component of the invention and component a). Suitable reducing agents are metal inorganic Al compounds, metallic Al and hydrogen.

The polymerization is carried out according to conventional methods, operating in liquid phase, either in the presence or absence of a diluent serving hydrocarbon such as hexane, heptane and cyclohexane, or in the gas phase.

The polymerization temperature is generally between 0 and 150 ° C, preferably between 40 and 90 ° C. One works under atmospheric pressure or under a higher pressure.

When preparing crystalline copolymers of propylene, it is preferable to polymerize the propylene until an amount of homopolymer equal to 60 - 90¾ of the total mixture is obtained and this step is followed by one or more polymerization steps of mixtures of propylene and ethylene. or solely of ethylene, such that the content of the polymerized ethylene may be between

13 DK 15196 9 B

limbs 5 and 30? ό, calculated in relation to the weight of the final material. Mixtures of propylene and ethylene are also polymerized to obtain a copolymer containing no more than 3% by weight of ethylene.

The following examples are intended to illustrate the present invention.

EXAMPLES 1 - 11 and Comparative Examples 1-2 A. Formulation

Anhydrous MgCl 2 (containing less than 1 wt.% Water), ethyl benzoate (EB) and optionally a silicone were simultaneously milled in two vibration mills with a total volume of 1 and 6 liters and containing 3 and 18 kg stainless steel balls with 16 respectively. mm diameter.

The milling was carried out using a filling coefficient of 135 g / liter total volume (vacuum) at a temperature in the mill interior of approx. 40 ° C and with grinding times different from trial to trial, varying from 50 to 100 hours.

Supply to the mill of the products to be milled, subsequent milling and removal of the co-milled product from the mill took place in a nitrogen atmosphere.

In Example 10, the milling was carried out in a rotary mill having a capacity of 1 liter and containing 120 stainless steel balls with a diameter of 15.8 mm, keeping the rotary mill rotating at a speed of 50 rpm. per. minute.

The following Table 1 shows, for the various experiments, the data related to the type and quantity of the products to be ground, to the grinding conditions and to the properties of the products obtained.

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14 B. Treatment with TiCl 2

A portion (15 - 50 g) of the co-milled product was always transferred in a nitrogen atmosphere to a 500 cm 2 reactor where it was contacted with an excess of TiCl 2. The treatment with TiCl3 took place at temperatures between 80 and 135 ° C for a 2-hour period, during which excess TiCl3 and the products soluble therein were removed by filtration at the temperatures listed in Table 1. Then two or more washes of boiling hexane followed.

The resulting solid product was dried in a nitrogen atmosphere and a portion thereof was analyzed to determine the percent content of Ti and Cl.

The data relating to the operating conditions used in the various experiments during the treatment with TiCl 2, as well as the properties of the solid products thus obtained, are also given in Table 1.

The stereospecificity and activity of these solid products (catalyst components) was determined in experiments with the polymerization of propylene in a hydrocarbon solvent or in liquid monomer using aluminum trialkyls treated with electron-donor compounds as co-catalyst.

C. Polymerization in a solvent

One operated in a 2500 cm 2 autoclave, equipped with a stirrer and previously purified with nitrogen at 60 ° C. The polymerization was carried out at 60 ° C, under a propylene (C ^ -) pressure of 5, 8 or 9 eff.atm. (kept constant by the addition of propylene during the polymerization experiments) for a 4- or 5-hour period.

As hydrocarbon solvent, technically dearomatized in and anhydrated (1000 cm 2) n-heptane (nC 2+), hexane (Cg +) or heptane (Cy +) were used. Work was carried out in the presence of hydrogen as a molecular weight modifier.

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A1 (C 2 H 5): 5 (TEA) or (AKiC 2 H 2 molar ratio of Al-trialkyl to donor was between 2.74 and 3.14.

To the autoclave was added the solvent (870 cm 2), a portion of Al-alkyl and of donor previously mixed in 10 'to 130 cm 2 of the indicated solvent, in the order and in a propylene atmosphere, supported catalyst component in suspension in 80 cm 2 of solvent containing the remaining portion of Al-alkyl and donor. Hydrogen and propylene were then introduced into the autoclave until the polymerization pressure was reached and the temperature was raised to the required value.

At the end of the polymerization experiment, the solvent was removed by steam distillation and the resulting polymer was dried in a nitrogen atmosphere at 70 ° C.

D. Polymerization in Liquid Monomer

The 30-liter and 135-liter autoclaves were equipped with a stirrer at a temperature of 65 ° C with propylene at 26.3 eff. atmospheres for a 5-hour period in the presence of hydrogen (15 NI and 50 NI) as molecular weight modifier.

A1 (C2H5) ^ in an amount of 12.5 g (experiment in a 30 liter autoclave) and AldC ^ Hg) ^ in an amount of 36 g (experiment in a 135 liter autoclave), both treated with electron donor compounds such as p-Ethylanazate or ethyl p-toluate in molar ratios of 2.2 to 2.74 were used as aluminum trialkyls.

To the autoclave was added in the order indicated in a propylene atmosphere Al-alkyl in a 12 wt.% Heptane solution with liquid propylene and with the donor.

The autoclave was heated to polymerization temperature and the catalyst component and hydrogen were then introduced therein.

16 DK 151969 B.

At the end of the polymerization, the residual propylene was evaporated and the polymer was then dried in a nitrogen atmosphere at 70 ° C.

In both cases (polymerization in a solvent and in liquid monomer), the dry polymer was weighed to calculate the yield relative to the amount of Ti present in the catalyst. In addition, the polymer was extracted with boiling n-heptane to determine the percentage of polymer which is insoluble in boiling n-heptane.

Apparent density and logarithmic viscosity (in tetralin at 135 ° C) of the polymer thus obtained were also determined. The following Table 2 contains the data relating to the various polymerization experiments and the properties of the polymers thus obtained.

The solubility in boiling heptane of TiCl 2 in the products similar to oak. 1 to 5 and 7 to 11 were tested using 25 g of ground product and 2125 cm 2 of n-heptane and found to be less than 1.5 wt. Also the solubility ratios in TiCl. at 80

4 I

° C was within the scope of the main requirement. j j j i i i i i i i! 17

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Table 1 - Preparation of the Supported Catalyst Component

Examples The measure-

Formal_Heder_1_2_3

Vibration mill volume 1666

Volume of rotary mill 1

MgCl2 g 530 651.5 651.5 EB amount g 280 150.5 158.5

MgCl2 / EB molar ratio 3/1 6.5 / 1 6.5 / 1

Type and amount of silicone oil g

TiCl4 g B2 ° 3 g

Grinding time h 100 50 50

Properties of the ground product

X-ray spectrum (x) A A

Treatment with TiCl 2

TiCl4 g 375 375 375

Milled product g 25 25 25

Ground product from Comparative Example 1 g

Treatment temperature ° C 80 80 135

Filtration temperature ° C 80 80 135

Wash with boiling heptane (amount) g

Properties of the product treated with TiCl4

Elemental Analysis: Ten% by weight 1.30 1.60 1.80 basis

Cl, 63.15, 65.25, 68.60

Surface area m 2 / g 20D 150 190 (x) Spectrum A means a spectrum in which the maximum intensity line of magnesium chloride occurring at jd = 2.56 Å has reduced relative intensity and flattens out asymmetrically to form a ring whose intensity maximum is between 18

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d = 2.44 A and d = 2.97 A.

Spectrum B means a spectrum in which the previously stated maximum! paint intensity line is absent and there is instead-; then a ring with an intensity maximum offset from this line, and lying between d ^ = 2.44 A and d = 2.97 A.

(xx) PDSM 500, PDSM 100 and PDSM 50 are polydimethylsiloxanes having a viscosity of 500, 100 and 50 centistokes, respectively.

! ! ! i i! in

Table 1 - (continued) 19

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'Examples The measure- Sainmenlig-

Formalization_horses_4_5 ninqsx. .

Vibration mill volume 1 6 6 6

Volume of rotary mill 1

MgCl2 g 651.5 651.5 651.5 EB amount g 158.5 158.5 158.5

MgCl2 / EB molar ratio 6.5 / 1 6.5 / 1 6.5 / 1

Silicone oil type and amount of g 200

TiCl4 g b203 g

Heal time h 100 100 100

Properties of the ground product

X-ray spectrum (x) B B B

Treatment with TiCl 2

TiCl4 g 375 375

Milled product g 25 25

Ground product from Comparative Example 1 g

Treatment temperature ° C 80 130

Filtration temperature ° C 80 135

Washing with boiling heptane (amount) g

Properties of the product treated with TiCl 2

Elemental Analysis: Ten% on 1.95 2.15 5.1 weight basis

Cl "67.30 67.7 61.6

Surface area m ^ / g 176 185 3

Table 1 - (continued)

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20

Examples The measure- Comparable-

Formation_units_6 ninqsx. 2 7

Vibration mill volume 1 1

Volume of rotary mill 1

MgCl2 g 96.5 EB amount g 30.6

MgCl3 / EB molar ratio 5.1

Silicone oil type and amount of PDMS 500 13.5 (xx)

TiCl4 g B2 ° 3 g

Grinding time h 100

Properties of the finely divided product X-ray spectrum (x)

Treatment with TiCl 2

TiCl4 g 375 150

Ground product g · 18

Ground product from Comparative Example 1 g 25 25

Treatment temperature ° C 80 80

Filtration temperature ° C 80 80

Washing with boiling heptane (amount) g 800

Properties of the product treated with TiCl 2

Elemental Analysis: Ten% on 2.6 1.65 1.55 weight basis

Cl "63.05 58.4 61.75

Surface area m ^ / g! 50 4 125

Table 1 (continued) 21

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Examples The measure-

Formalinq_heder_8_9_10

Vibration mill volume 116

Volume of rotary mill 1 1

MgCl2 · g 96.5 651.5 20 EB amount g 30.6 157 6

MgCl2 / EB molar ratio 5/1 6.5 / 1 5.2 / 1

Silicone oil type and quantity of g (xx) PDFTS 100 / (xx) PDM!

Tici4 9 13'9 50/3 B2 ° 3 9

Grinding time h 100 100 100

Properties of the ground product X-ray spectrum (x)

Treatment with TiCl 2

TiCl4 g 375 375 150

Ground product g 25 25 28

Ground product from Comparative Example 1 g

Treatment temperature ° C 80 80 80

Filtration temperature ° C 8Q 80 80

Washing with boiling heptane (amount) g

Properties of the product treated with TiCl 2

Elemental Analysis: Ten% on 1, -65 2.00 1.1 wt basis

Cl - 62.05 62.55 66.1

Surface area m2 / g 172 160 150

Table 1 (continued) 22

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t The measure-

Formation_Example 11

Vibration mill volume 1 1

Volume of rotary mill 1

MgCl2 g 45 EB amount g 10.1

MgCl2 / EB Molar ratio 6.8 / 1

Silicone oil type and quantity g

TiCl4 g B203 g 54

Grinding time h

Properties of the ground product X-ray spectrum (x)

Treatment with TiCl 2

TiCl4 g 135

Ground product g 20

Ground product from Comparative Example 1 g.

Treatment temperature ° C 80

Filtration temperature ° C 80

Washing with boiling heptane (amount) g

Properties of the product treated with TiCl 2

Elemental Analysis: Ten? Ό by weight 1.4

Cl 3.1 3.1 2

Surface area m / g 80 23

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Table 2 - Results of the propylene polymerization

Reference Example in Table 1 Measurement Units_1_1_2_

Catalyst component Amount of catalyst component mg 80 450 70

Ten% by weight 1.30 1.60 basis

Cl, 63.15, 65.25

Polymerization Experiments

Autoclave capacity 1 2.5 30 2.5

Polymerization medium and ^ nCy + / 1000/23000 nC ^ + / 1000 volume cin C3 "effective pressure atm 5

Polymerization temperature ° C 60 65 60

Polymerization time h 4 54

Type of Al-alkyl TEA TEA TEA

Amount of Al-alkyl g 1.135 12.5 1.135

Type of donor PEA PEA PEA

Al-alkyl / donor molar ratio 3.14 2.75 3.14

Hydrogen Amount Ncm ^ 110 15000 110

Results of polymerization experiments

Yield gpoly- 113,500 274,000 103,000 mer / g Ti

Isotactic index% 94.0 94.5 93.5

Properties of Polymer The apparent density of polymer kg / l 0.47 0.45 0.44

Intrinsic viscosity of the polymeric dl / g 1.6 2.3 1.8

Table 2 (continued) 24

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Reference example in Table 1 Measurement Units_3_4_ 4

Catalyst component Amount of catalyst component mg 127 66 310

Ten% on a 1.80 1.95 weight basis

Cl, 68.0, 67.30

Polymerization Experiments

Autoclave capacity 1 2.5 2.5 2.5

Polymerization medium and volume of crn nCy + / 1000 nC ^ + / 1000 nC ^ / 23000 C3 'effective pressure atm 5 5 26.5

Polymerization temperature ° C 60 60 65

Polymerization time h 4 45

Type of Al-alkyl TEA TEA TEA

Amount of Al-alkyl g 1,135 1,135 12.5

Type of donor PEA PEA PEA

Al-alkyl / donor molar ratio 3.14. 3.14 2.75

Hydrogen Amount Ncm ^ 110 110 15,000

Results of polymerization experiments

Yield g / polymer / g Ti 107,000 155,000 324,000

Isotactic index% 91.5 93.0 93.5

Properties of the resulting polymer Apparent density of the polymer kg / l 0.48 0.48 0.50

Intrinsic viscosity of the polymer dl / g 2.0 1.8 2.1

Table 2 (continued)

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25

Reference Example in Table 1 Measurement Units_5_6_7_

Catalyst Component Amount of Catalyst Component mg 82 11 110

Ten% on 2.15 2.6 1.55 weight basis

Cl - 67.7

Polymerization Experiments

Autoclave capacity 1 2.5 2.5 2.5

Polymerization Medium and Volume Volume cm 5 nCy + / 1000 nC ^ / 1000 nC ^ / 1000 effective pressure atm 555

Polymerization temperature ° C 60 633 60

Polymerization time h 4 4 4

Type Al-alkyl TEA TEA TEA

Amount of Al-alkyl g 1,135 1,135 1,135

Type of donor PEA PEA PEA

Al-alkyl / donor molar ratio 3.14 3.14 3.14 3

Hydrogen Amount Easy 110 110 110

Results of polymerization experiments

Yield g of polymer / g Ti 174,000 164,000 123,000

Isotactic index% 90.5 91.5 94

Properties of the resulting polymer Apparent density of the polymer kg / l 0.43 0.48 0.49

Intrinsic viscosity of the polymeric dl / g 2.0 1.8

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Table 2 (continued) 26

Reference Example in Table 1 Measurement Units_8_9_10_

Catalyst component Amount of catalyst component mg 63 65 110

Ten% on a 1.65 2.00 1.1 weight basis

Cl - 62.05 65.00 66.1

polymerization

Autoclave capacity 1 2.5 2.5 2.5

Polymerization medium and volume crn C * / 1000 C * / 1000 C, * / 1000 6 6 7

Cj effective pressure atm 9 9 9

Polymerization temperature ° C 60 60 60

Polymerization time h 4 4 4

Type of Al-alkyl TIBAL TIBAL TEA

Amount of Al-alkyl g 1.97 1.97 1.135

Type of donor EPT EPT PEA

Al-alkyl / donor molar ratio 3.14 '3.14 3.14

Hydrogen amount Easy · 3 190 190 110

Results of polymerization experiments

Yield g of polymer / g Ti 333,000 344,000 141,000

Isotactic index% 92.0 92.5 92

Properties of the resulting polymer Apparent density of the polymer kg / l 0.50 0.43 0.48

Intrinsic viscosity of the polymeric dl / g 2.4 3.0 1.7

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Table 2 (continued) 27

Reference example in Table 1 The measure- Comparison- Comparison_11 ningsetcs. 1 sex. ri

Catalyst component Amount of catalyst component mg 100 105 105

Ten% on 1.3 5.7 1.65 weight basis

Cl - 3.1 61.0 58.4

polymerization

Autoclave capacity 1 2.5 2.5 2.5

Polymerization medium and ..

-volume cm Cg + / 100 C ^ + / 1000 C ^ + / 1000

Cj effective pressure atm 989

Polymerization temperature ° C 60 60 60

Polymerization time h 4 5 4

Type of Al-alkyl TIBA TEA TIBA

Amount of Al-alkyl g 1.97 1.00 1.135

Type of donor ΕΡΤ PEA EPT

Al-alkyl / donor molar ratio 3.14 2.9 3.14

Hydrogen Amount Ncm ^ 190 170 190

Results of polymerization experiments

Yield g / polymer / g Ti 290,000 70,000 89,500

Isotactic index% 90 90.5 88.5

Properties of the resulting polymer Apparent density of the polymeric kg / l 0.4 0.43 0.28

Intrinsic viscosity of the polymeric dl / g 1.9

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EXAMPLE 12

Anhydrous MgCl 2 (containing less than 1 wt% t 2 O) was simultaneously ground with the electron donor compounds listed in Table 3, under the conditions set forth in Example 4. The milled product was treated with TiCl3 under the conditions of Example 4. The reaction product thus obtained exhibited the Cl and Ti contents indicated in Table 3.

The above catalyst components were used in polymerization experiments under the conditions set forth in Example 8, with the only difference that the effective C₂ pressure was 5.4 atm. The data relating to the yield of polymer and isotactivity index are given in Table 3.

TABLE 3

Electron Donor EPT PEA MB MMA NBE

Ten% by weight asis 1.3 1.75 1.8 2.0 2.1

Cl% by weight 59.8 60.9 61 62 63.9

Yield (g polymer / g Ti) 250,000 183,000 170,000 167,000 185,000 Isotactivity Index 92 93 94 94.5 92 EPT = ethyl p-toluate PEA = p-ethylanate MB = methyl benzoate MMA = methyl methacrylate NBE = di- (n-butyl) ether EXAMPLE 13 500 ml of kerosene was introduced into a container equipped with a stirrer.

Propylene was introduced at a rate of 30 liters per liter. hour for 1 hour to expel air and moisture.

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2.5 mmol of Al triethyl and 0.884 mmol of the electron donor compound listed in Table 4 were introduced at room temperature. After 5 minutes, a catalyst component prepared according to Example 7 was introduced only with the exception of using a silicone oil having a viscosity of 20 centistokes at 20 ° C. The molar ratio Al / Ti in the catalyst was 25.

The mixture was heated to 60 ° C. The propylene was polymerized for 1 hour under atmospheric pressure and introduced at such a rate that the pressure was kept constant during polymerization. The propylene was then replaced with nitrogen and the reaction mixture was cooled to room temperature. The solid product was filtered off, washed twice with methanol and then dried at 70 ° C. The soluble polymer was recovered by evaporation of the kerosene layer in the filtrate. The data relating to the yield and the total isotactic index of the polymer are given in Table 4.

TABLE 4

Electron donor BA_POBA AAC BAA NBE

Yield (g polymer / g Ti) 47,900 43,140 40,430 41,900 31,500

Isotactivity Index 7c, flQ o on x g q? in (relative to the total) 75'6 89'2 80'3 73'9 92> 1 BA = benzoic acid POBA = p-oxy-benzoic acid AAC = alpha-aminoacetic acid BAA = benzoic acid amide NBE = di- (n-butyl) EXAMPLE 14 10 g of a catalyst component prepared according to Example 13 and containing 2.1 wt% Ti were suspended in 150 ml of kerosene. Diethyl aluminum chloride (2.2 mmol) diluted with kerosene was added at room temperature, then 2.2 mmol of ethyl benzoate was added and the mixture was stirred for 1 hour. The solid product was filtered, washed with hexane and dried in vacuo.

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Into a 2 L capacity autoclave containing 750 ml of n-hexane and 3.75 mmol of A1 (C 2 H / 1 Ti.

The polymerization experiment was carried out for 4 hours at 60 ° C under a pressure of 8 atm propylene. and in the presence of 400 N liters of hydrogen.

After removal of the dry matter by filtration and drying, 225.9 g of powder was obtained, the index of isotacticity being 94.2.

5.9 g of polymer which is soluble in n-hexane were recovered from the filtrate.

EXAMPLE 15 10 g of MgCl 2 containing less than 1 wt% water suspended in kerosene (100 ml) was treated with 18.4 ml of ethyl alcohol at 20 ° C. The complex of MgCl 2 with ethanol was reacted with 2.5 ml of 2,6-dimethylphenol at 20 ° C for 1 hour, 11.7 ml of ethyl benzoate at 80 ° C for 1 hour and 22.9 ml of AKC at 20 ° C for 2 hours, in the order given above.

The solid product was separated by filtration, washed with n-hexane and dried in vacuo. 10 g of the product was treated with 100 ml of TiCl 2 at 100 ° C for 2 hours. The excess TiCl4 was separated by filtration. The solid product was repeatedly washed with n-hexane and then dried in vacuo.

Elemental analysis of the product gave the following results:

Ti = 3.60% by weight

Cl = 58.0% by weight.

31 mg of the solid product was used in a polymerization experiment under the conditions set forth in Example 14. After removing the op- 31

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The solvent by filtration and drying afforded 130 g of polymer. The isotactic index of this polymer was 95.4. The hexane-soluble polymer recovered from the filtrate was 30 g.

EXAMPLE 16

Catalyst preparation 1 kg of anhydrous MgCl3, 0.23 liters of ethyl benzoate and 0.15 liters of PDMS 50 (PDMS means polydimethylsiloxane having a viscosity of 50 centi-stoke) was introduced into a 100 liter vibration mill (containing 350 kg stainless steel balls, each having a diameter of 15 mm) in which the components were brought into common contact for 120 hours at 70 ° C.

Of the thus copolymerized product, 500 g in 5 liters of TiCl 3 was suspended and the resulting suspension was allowed to react for 2 hours at 80 ° C. After completion of the reaction, the resulting system was filtered at the same temperature to recover the solid thereof, and then washed thoroughly with hexane until the presence of free TiCl 2 was no longer detectable.

The resulting solid component contained 2.0, 23.0 and 64.0 wt% Ti, Mg and Cl respectively, calculated as atoms, and 10.5 wt Si 2 ethyl benzoate, and exhibited a specific surface area of 200 m g. polymerization

An equipment comprising four reactors arranged in series was used, namely reactors A, B, D and E (each having an affective volume of 190, 120, 140 and 200 liters, respectively) and a drum of " flash type C (with an effective volume of 30 liters) mounted between reactors B and D.

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To the reactor A was added 0.75 mmol Ti per ml. as a hexane slurry of the solid catalyst component prepared as described above and a hexane solution of triethyl Al and ethyl p-toluate (EPT) in amounts such that the molar ratios Al / Ti and Al / EPT will be 50 and 2.75 respectively, at the same time supplying the total amount of hexane at a rate of 21 liters per liter. hour.

In addition, 7 Nm 2 per reactor was added to the reactor. per hour of propylene and 13 NI per hour. hour of hydrogen while maintaining the manometer pressure in the reactor at 7 kg / cm and the polymerization temperature of 60 ° C.

As a result, in the reactor A PP (PP means polypropylene) with an isotacticity index and an MI (MI means melt index) of 92.83! and 0.36 at a rate of 240,000 g PP / g Ti.

The polymeric slurry withdrawn from reactor A was then passed to reactor B, to which, again per 4.5 mmol of triethyl-Al and 5 NI of hexane were added hourly. The polymerization was then carried out in the reactor B under a pressure of 3.0 kg / cm and 60 ° C as the polymerization temperature.

PP with an isotactic index of 92.2% and MI of 0.32 were prepared in reactors A and B collectively at a rate of 290,000 g PP / g Ti.

The polymer slurry carried out from reactor B was then fed to the "flash" type C drum, where no unreacted monomer propylene was removed, and then to reactor D, to which was added 1,000 Nl / h of ethylene and 80 Nl / h hydrogen, together with nitrogen gas, to maintain the reactor pressure at a value of 2.5 kg / cm 2

The composition of the gas held in reactor D was: hydrogen 7.3%, nitrogen 45.5%, ethylene 25.8%, propylene 0.9% and hexane 20.4%.

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As a result of the polymerization in the reactor D at 60 ° C as the polymerization temperature, a polymer having a value of MI of 0.29 and a loose density of 0.350 at a rate of MI of 0.29 and a loose density of 0.350 at a rate of 27,000 g polymer / g Ti.

The polymeric slurry taken from reactor.mD was then fed to reactor E to which ethylene was supplied at a rate of 1,700 Nl / hr, hydrogen at a rate of 70 Nl / hr, triethyl-Al with a rate of 4.5 mmol / hour and additional hexane at a rate of 10 liters / hour.

The polymerization was carried out under the polymerization pressure of 2.0 kg / cm G and the polymerization temperature of 60 ° C, while the composition of the gas present in the reactor E was: hydrogen 38.2%, nitrogen 3.4%, ethylene 35, 6%, propylene 0.1% and hexane 22.6%.

As a result of the polymerization in the reactor E, a polymer having a value of MI of 0.24 and a loose density of 0.350 g / cm 3 was prepared at a rate of 24,000 g polymer / g Ti. The polymer thus prepared contained 17.6 parts by weight of ethylenic polymer per liter. 100 parts by weight of PP.

Claims (3)

A solid catalyst component useful in a catalyst for the polymerization of α-alkenes, comprising at least on the surface the reaction product between a magnesium halide, a tetravalent titanium compound and an electron donor compound, whereby the electron-donor / Ti molar ratio the product is higher than 0.2, whereby the ratio of halogen atoms / Ti is higher than 4, characterized in that at least 80% by weight of the compounds of tetravalent titanium contained therein are insoluble in boiling n-heptane that at least 50% by weight - n of the Ti compounds which are insoluble in n-heptane are also insoluble in TiCl 2 at 80 ° C and that the surface area of the product is insoluble in TiCl. at 80 ° C, and the surface area of the catalyst component as such is greater than 20 m / g, preferably greater than 40 m / g. Solid catalyst component according to claim 1, characterized in that the X-ray spectrum thereof exhibits a ring whose maximum intensity is offset relative to the distance c1 of the maximum intensity line present in the X-ray spectrum of the Mg dihalides. Solid catalyst component according to claim 1 or 2, characterized in that the magnesium halide is obtained by reaction between a titanium tetrahalide and an oxygen-containing magnesium compound.