AU708459B2 - Catalyst systems of the Ziegler-Natta type - Google Patents
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- AU708459B2 AU708459B2 AU61958/96A AU6195896A AU708459B2 AU 708459 B2 AU708459 B2 AU 708459B2 AU 61958/96 A AU61958/96 A AU 61958/96A AU 6195896 A AU6195896 A AU 6195896A AU 708459 B2 AU708459 B2 AU 708459B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Description
BASF Aktiengesellschaft O.Z. 0050/46076 Catalyst systems of the Ziegler-Natta type The present invention relates to catalyst systems of the ziegler-Natta type comprising as active constituents a) a titanium-containing solid component comprising a compound of titanium, a compound of magnesium, a halogen, silica gel as support and a carboxylic ester as electron donor compound, and also, as cocatalyst, b) an aluminum compound and c) if desired, a further electron donor compound, wherein the silica gel used has a mean particle diameter of from 5 to 200 pm, a mean particle diameter of the primary particles of from 1 to 10 pm and voids or channels having a mean diameter of from 1 to 10 pm whose macroscopic proportion by volume in the total particle is in the range from 5 to In addition, the invention provides a process for producing such Ziegler-Natta catalyst systems, a process for preparing polymers of propylene using these catalyst systems, the polymers obtainable in this way and also films, fibers and moldings comprising these polymers.
30 Catalyst systems of the Ziegler-Natta type are known, inter alia, from EP-B 014523, EP-A 023425, EP-A 045975 and EP-A 195497. These systems are used, in particular, for the polymerization of
C
2 -Co 1 -alk-l-enes and comprise, inter alia, compounds of polyvalent titanium, aluminum halides and/or aluminum alkyls, and 35 also electron donor compounds, particularly silicon compounds, ethers, carboxylic esters, ketones and lactones which are used, on the one hand, in connection with the titanium component and, on the other hand, as cocatalyst.
The Ziegler-Natta catalysts are usually produced in two steps.
The titanium-containing solid component is produced first and subsequently reacted with the cocatalyst. The polymerization is subsequently carried out using the catalysts thus obtained.
Furthermore, US-A 48 57 613 and US-A 52 88 824 describe catalyst systems of the Ziegler-Natta type which comprise a titanium-containing solid component and aluminum compound plus I I i I *BASF Aktiengesellschaft 0.Z. 0050/46076 2 organic silane compounds as external electron donor compounds.
The catalyst systems obtained in this way have, inter alia, a good productivity and give polymers of propylene having a high stereospecificity, ie. a high isotacticity, a low chlorine content and a good morphology, viz. a low proportion of fines.
If films are produced from polymers obtained by means of the catalyst systems described in US-A 48 57 613 and US-A 52 88 824, the increased occurrence of microspecks, ie. small irregularities on the surface of the films, is frequently observed. If such microspecks occur to a great extent, they impair the optical quality of the film.
It is an object of the present invention, starting from the catalyst systems described in US-A 48 57 613 and US-A 52 88 824, to develop an improved catalyst system of the Ziegler-Natta type which does not have the abovementioned disadvantages in respect of the formation of microspecks and additionally gives a high productivity and stereospecificity of the polymers thus obtained.
We have found that this object is achieved by means of the catalyst systems of the Ziegler-Natta type defined in the introduction.
The catalyst systems of the present invention contain, inter alia, a cocatalyst in addition to a titanium-containing solid component The cocatalyst may here be the aluminum compound Preferably, an additional electron donor compound c) is used as a further constituent of the cocatalyst together with this 30 aluminum compound b).
To produce the titanium-containing solid component titanium compounds used are generally halides or alkoxides of trivalent or tetravalent titanium, with the chlorides of titanium, in 35 particular titanium tetrachloride, being preferred. The titanium-containing solid component also contains silica gel as support.
In addition, compounds of magnesium are used, inter alia, in the production of the titanium-containing solid component. Suitable magnesium compounds are, in particular, magnesium halides, magnesium alkyls and magnesium aryls, and also magnesium alkoxy and magnesium aryloxy compounds, with preference being given to using magnesium dichloride, magnesium dibromide and di(Ci-Clo-alkyl)magnesium compounds. The titanium-containing solid t. BASF Aktiengesellschaft O.Z. 0050/46076 3 component can additionally contain halogen, preferably chlorine or bromine.
The titanium-containing solid component a) also contains electron donor compounds, for example monofunctional or polyfunctional carboxylic acids, carboxylic anhydrides and carboxylic esters, also ketones, ethers, alcohols, lactones, and organophosphorus and organosilicon compounds. As electron donor compounds within the titanium-containing solid component, preference is given to using phthalic acid derivatives of the general formula (II) CO- X CO- Y where X and Y are each a chlorine atom or a Ci-Clo-alkoxy radical or together are oxygen. Particularly preferred electron donor compounds are phthalic esters in which X and Y are each a
C
1
-C
8 -alkoxy radical, for example a methoxy, ethoxy, propyloxy or a butyloxy radical.
Further preferred electron donor compounds within the titanium-containing solid components are, inter alia, diesters of 3- or 4-membered, substituted or unsubstituted cycloalkyl-l,2-dicarboxylic acids, and also monoesters of substituted or unsubstituted benzophenone-2-carboxylic acids. The hydroxy compounds used for these esters are the alcohols 30 customary in esterification reactions, for example Cl-C s-alkanols and Cs-C 7 -cycloalkanols which may in turn bear C 1 -Clo-alkyl groups, also C 6 -Clo-phenols.
The titanium-containing solid component can be produced by 35 methods known per se. Examples of such methods are described, inter alia, in EP-A 45 975, EP-A 45 977, EP-A 86 473, EP-A 171 200, GB-A 2 111 066, US-A 48 57 613 and US-A 52 88 824.
9 For producing the titanium-containing solid component the following two-stage process is preferably employed: In the first stage, silica gel (SiO 2 generally having a mean particle diameter of from 5 to 200 mn, in particular from 20 to am, a pore volume of from 0.1 to 10 cm 3 in particular from 1.0 to 4.0 cm 3 and a specific surface area of from 10 to 1000 m 2 in particular from 100 to 500 m 2 as finely divided support is first admixed with a solution of the i. BASF Aktiengesellschaft 0.2. 0050/46076 4 magnesium-containing compound in a liquid alkane, after which this mixture is stirred for from 0.5 to 5 hours at from 10 to 120°C. Preference is given to using from 0.1 to 1 mol of the magnesium compound per mol of the support. Subsequently, while stirring continuously, a halogen or a hydrogen halide, in particular chlorine or hydrogen chloride, is added in an at least two-fold, preferably at least five-fold, molar excess, based on the magnesium-containing compound. After from about 30 to 120 minutes, this reaction product is, at from 10 to 150°C, admixed with a Ci-Cs-alkanol, in particular ethanol, a halide or an alkoxide of trivalent or tetravalent titanium, in particular titanium tetrachloride, and also an electron donor compound. In this procedure, from 1 to 5 mol of the trivalent or tetravalent titanium and from 0.01 to 1 mol, in particular from 0.1 to 0.5 mol, of the electron donor compound are used per mol of magnesium in the solid obtained from the first stage. This mixture is stirred for at least 1 hour at from 10 to 150 0 C, the solid thus obtained is subsequently filtered off and washed with a C 7 -Clo-alkylbenzene, preferably with ethylbenzene.
In the second stage, the solid obtained from the first stage isextracted for a few hours at from 100 to 150°C with excess titanium tetrachloride or an excess of a solution of titanium tetrachloride in an inert solvent, preferably an alkylbenzene, with the solvent containing at least 5% by weight of titanium tetrachloride. The product is then washed with a liquid alkane until the washings contain less than 2% by weight of titanium tetrachloride.
The titanium-containing solid component obtainable in this way is used together with a cocatalyst as Ziegler-Natta catalyst system.
A suitable cocatalyst is here, inter alia, an aluminum compound b).
35 Aluminum compounds b) suitable as cocatalysts are trialkylaluminums and also those compounds in which an alkyl group is replaced by an alkoxy group or by a halogen atom, for example by chlorine or bromine. Preference is given to using trialkylaluminum compounds whose alkyl groups each have from 1 to 8 carbon atoms, for example trimethylaluminum, triethylaluminum or methyldiethylaluminum.
Preference is given to using not only the aluminum compound b) but also electron donor compounds c) as further cocatalyst, for example monofunctional or polyfunctional carboxylic acids, carboxylic anhydrides and carboxylic esters, also ketones, ethers, alkohols, lactones, and organophosphorus and I BASF AJCe1enese.rcu. vru vv3vi~uv u organosilicon compounds. Preferred electron donor compounds are here organosilicon compounds of the general formula (I) R1nSi(OR 2 4-n
(I)
where
R
1 are identical or different and are each a C1-C 20 -alkyl group, a to 7-membered cycloalkyl group which in turn can bear a
C
1 -Clo-alkyl group, or a C 6
-C
20 -aryl or aralkyl group, R 2 are identical or different and are each a C 1
-C
20 -alkyl group and n. is 1, 2 or 3. Particular preference is here given to those compounds in which R 1 is a C 1 -Cs-alkyl group or a 5- to 7-membered cycloalkyl group, and R 2 is a C 1
-C
4 -alkyl group and n is 1 or 2.
Among these compounds, particular emphasis is given to dimethoxydiisopropylsilane, dimethoxyisobutylisopropylsilane, dimethoxydiisobutylsilane, dimethoxydicyclopentylsilane, dimethoxyisobutyl-sec-butylsilane, dimethoxyisopropyl-sec- S* butylsilane, diethoxydicyclopentylsilane and 20 diethoxyisobutylisopropylsilane.
The individual compounds b) and, if desired, c) can be used as cocatalyst in any order, either individually or as a mixture of two components.
According to the present invention, the silica gel used in the titanium-containing solid component a) is a finely divided silica gel which has a mean particle diameter of from 5 to 200 pm, in particular from 20 to 70 pm, and a mean particle diameter of the 30 primary particles of from 1 to 10 pm, in particular from 1 to 5 pm. For the purposes of the present inventionthe primary particles are porous, granular silica gel particles which are !obtained from an Sio 2 hydrogel by milling, if desired after appropriate sieving.
Furthermore, the finely divided silica gel to be used according to the present invention also has voids or channels having a mean diameter of from 1 to 10 pm, in particular from 1 to 5 pm, whose macroscopic proportion by volume in the total particle is in the range from 5 to 20%, in particular in the range from 5 to The finely divided silica gel additionally has, in particular, a pore volume of from 0.1 to 10 cm 3 preferably from 1.0 to cm 3 and a specific surface area of from 10 to 1000 m 2 /g, preferably from 100 to 500 m 2 /g.
"i l/o ^i I r i.
BASF Axi3egese.Lc.bxz %0 6 Owing to the voids or channels present in the finely divided silica gel, there is a significantly improved distribution of the catalytically active components in the support material.
Furthermore, a material pervaded in this way by voids and channels has a positive effect on the diffusion-controlled supply of monomers and cocatalysts and thus also on the polymerization kinetics. Such a finely divided silica gel is, inter alia, obtainable by spray drying milled, appropriately sieved SiO 2 hydrogel, which for this purpose is slurried with water or an aliphatic alcohol. However, such a finely divided silica gel is also commercially available.
The silica gel is/present within the titanium-containing solid component a) in such amounts that from 0.1 to 1.0 mol, in particular from 0.2 to 0.5 mol, of the magnesium compound is present per 1 mol of the silica gel.
The cocatalytically active compounds b) and, if desired, c) can be allowed to act either successively or together on the 20 titanium-containing solid component This is usually carried out at from 0 to 150'C, in particular from 20 to 90°C, and at pressures of from 1 to 100 bar, in particular from 1 to 40 bar.
The cocatalysts b) and, if used, c) are preferably used in such 25 an amount that the atomic ratio between aluminum from the aluminum compound and titanium from the titanium-containing solid component a) is from 10:1 to 800:1, in particular from 20:1 to 200:1, and the molar ratio between the aluminum compound and the electron donor compound c) used as cocatalyst is from 1:1 to 30 250:1, in particular from 10:1 to 80:1.
The catalyst systems of the present invention are particularly Sssuitable for preparing polymers of propylene, ie. homopolymers of propylene and copolymers of propylene together with other
C
2
-C
0 o-alk-l-enes.
The description C 2 -Clo-alk-l-enes here refers to, inter alia, ethylene, but-1-ene, pent-1-ene, hex-1-ene, hept-1-ene or oct-1-ene, with the comonomers ethylene and but-1-ene being particularly preferred.
However, the catalyst systems of the present invention can also be used for preparing polymers of other C 2 -Clo-alk-l-enes, for example for preparing homopolymers or copolymers of ethylene, but-l-ene, pent-1-ene, hex-1-ene, hept-1-ene or oct-1-ene.
'j y t BASF Aktiengesellschaft O.Z. 0050/46076 7 The preparation of such polymers of C 2 -Clo-alk-l-enes can be carried out in the customary reactors used for the polymerization of C 2
-C
10 -alk-l-enes, either batchwise or preferably continuously, for example as suspension polymerization or preferably as gas-phase polymerization. Suitable reactors include continuously operated stirred reactors containing a fixed bed of finely divided polymer which is usually kept in motion by means of suitable agitators. Of course, the reaction can also be carried out in a plurality of reactors connected in series. The reaction time, ie. the mean residence time, is determined by the reaction conditions selected in each case. It is usually from 0.2 to hours, mostly from 0.5 to 10 hours.
The polymerization reaction is advantageously carried out at from 20 to 150°C and at pressures of from 1 to 100 bar. Preference is given to temperatures of from 40 to 100 0 C and pressures of from to 50 bar. Specifically for the preparation of propylene homopolymers, the polymerization reaction is preferably carried out at from 50 to 100°C, in particular from 60 to 90"C, at pressures of from 15 to 40 bar, in particular from 20 to 35 bar, and at mean residence times of from 0.5 to 5 hours, in particular from 0.5 to 3 hours. The molecular weight of the polyalk-1-enes formed can be controlled by addition of regulators customary in polymerization technology, for example hydrogen, and adjusted over a wide range. It is also possible to make concomitant use of inert solvents such as toluene or hexane, inert gas such as nitrogen or argon and relatively small amounts of polypropylene powder.
30 The propylene homopolymers and copolymers obtained by means of the catalyst system of the present invention are obtainable in the molecular weights usual for polyalk-1-enes, with preference saf being given to polymers having molecular weights (weight average) of from 20,000 to 500,000. Their melt flow indices at 230'C and 35 under a load of 2.16 kg, in accordance with DIN 53 735, are in the range from 0.1 to 100 g/10 min, in particular in the range from 0.5 to 50 g/10 min.
The catalyst system of the present invention has, compared with e*o' 40 the catalyst systems known hitherto, a higher productivity and an improved stereospecificity, in particular in gas-phase polymerization. The polymers obtainable in this way also have a high bulk density and a low residual chlorine content.
Furthermore, the catalyst system of the present invention has the advantage of significantly reducing the microspeck formation in the polymers obtained therefrom.
II-- SBASF Aktiengesellschaft O.Z. 0050/46076 8 Owing to their good mechanical properties, the propylene polymers prepared using the catalyst system of the present invention are especially suitable for producing films, fibers and moldings.
Examples Example 1 a) Production of the titanium-containing solid component (1) In a first stage, finely divided silica gel (SiO 2 having a particle diameter of from 20 to 45 pm, a pore volume of cm 3 /g and a specific surface area of 260 m 2 /g was admixed with a solution of n-butyloctylmagnesium in n-heptane, with 0.3 mol of the magnesium compound being used per mol of SiO 2 The finely divided silica gel was additionally characterized by a mean particle size of the primary particles of 3-5 pm and by voids and channels having a diameter of 3-5 pm, with the macroscopic proportion by volume of the voids and channels in the total particle being about 15%. The solution was stirred for 45 minutes at 95°C, then cooled to 20 0
C,
after which the 10-fold molar amount, based on the organomagnesium compound, of hydrogen chloride was passed in.
After 60 minutes, the reaction product was admixed while 25 stirring continuously with 3 mol of ethanol per mol of magnesium. This mixture was stirred for 0.5 hour at 80°C and subsequently admixed with 7.2 mol of titanium tetrachloride and 0.3 mol of di-n-butyl phthalate, in each case based on 1 mol of magnesium. The mixture was subsequently stirred for 30 1 hour at 100 0 C, the solid thus obtained was filtered off and ~washed a number of times with ethylbenzene.
*a The solid product thus obtained was extracted for 3 hours at 125°C with a 10% strength by volume solution of titanium S. 35 tetrachloride in ethylbenzene. The solid product was then separated from the extractant by filtration and washed with n-heptane until the extractant contained only 0.3% by weight of titanium tetrachloride.
The titanium-containing solid component contained by weight of Ti 7.4% by weight of Mg 28.2% by weight of Cl.
BASF Aktiengesellschaft O.Z. 0050/46076 9 The particle diameter was determined by Coulter Counter analysis (particle size distribution of the silica gel particles), the pore volume and the specific surface area were determined by nitrogen adsorption in accordance with DIN 66131 or by mercury porosimetry in accordance with DIN 66133. The mean particle size of the primary particles, the diameter of the voids and channels and their macroscopic proportion by volume were determined by means of scanning electron microscopy or electron probe microanalysis, in each case on particle surfaces and on particle cross sections of the silica gel.
b) Polymerization of propylene The polymerization was carried out in a vertically stirred gas-phase reactor having a utilizable capacity of 800 1 in the presence of hydrogen as molecular weight regulator. The reactor contained an agitated fixed bed of finely divided polymer. The reactor output of polymer was 152 kg of polypropylene per hour.
Gaseous propylene was passed into the gas-phase reactor atand at a pressure of 32 bar. Polymerization was carried out continuously at a mean residence time of 1.5 hours with ^the aid of the titanium-containing solid component a) described in Example 1 a, with 6.6 g/h of the titanium-containing solid component 1384 mmol/h of triethylaluminum and 40 mmol/h of dimethoxyisobutylisopropylsilane being used as cocatalyst.
After completion of the gas-phase polymerization, a propylene homopolymer having a melt flow index of 12.2 g/10 min at 230 0 C and 2.16 kg (in accordance with DIN 53 735) was obtained.
Comparative Example A Propylene was polymerized using a method similar to the example according to the present invention with the same catalyst system and under the same conditions, but using a titanium-containing solid component a) containing a granular silica gel having the following properties: Particle diameter: 20 45 pun Pore volume: 1.8 cm 3 /g Specific surface area: 325 m 2 /g Proportion of voids and channels in the total particle: I- BASF Aktiengesellschaft O.Z. 0050/46076 After.completion of the gas-phase polymerization, a propylene.
homopolymer having a melt flow index of 12.5 g/10 min at 230°C and 2.16 kg (in accordance with DIN 53 735) was obtained.
Table I below shows, both for Example 1 according to the present invention and for Comparative Example A, the productivity of the catalyst system used and also the following properties of the propylene homopolymers obtained in each case: xylene-soluble proportion (measure of the stereospecificity of the polymer), heptane-soluble proportion (measure of the stereospecificity of the polymer), chlorine content, bulk density, shear modulus (G modulus), viscosity and number of microspecks.
S* I I r I II *9.
.c Table I Example 1 Comparative Example A Productivity 22880 14350 [g of polymer/g of titanium-containing solid Xylene-soluble proportion 1.3 by weight]__ Heptane-soluble proportion 2.6 by weight]__ Chlorine content 12.5 20.7 (ppm] Bulk density a) 426 344 [gte) G modulus b) 878 767 [N/mm 2 Number of microspecks C) 30-40 120-150 [per in 2 determined in accordance with DIN 53 466 determined in accordance with DIN 53 445 determined by on-line measurement by means of a Brabender apparatus of 40 pm.
on a film having a thickness BASF Aktiengesellschaft O.Z. 0050/46076 12 Comparison of Example 1 according to the present invention with Comparative Example A makes it clear that the catalyst system of the present invention has a higher productivity and leads to polymers of propylene having an increased stereospecificity (lower xylene- and heptane-soluble proportions), a reduced chlorine content and an increased bulk density. Furthermore, the polymers of propylene obtained with the aid of the catalyst system of the present invention also have a higher stiffness (higher G modulus) and a significantly reduced number of microspecks.
Example 2 a) Preparation of the titanium-containing solid components (1) In a first stage, finely divided silica gel (Si02) having a particle diameter of from 20 to 45 pm, a pore volume of cm 3 /g and a specific surface area of 260 m 2 /g was admixed with a solution of n-butyloctylmagnesium in n-heptane, with 0.3 mol of the magnesium compound being used per mole of Sio 2 The finely divided silica gel also had a mean particle size of the primary particles of 3-5 pm and had voids and channels having a diameter of 3-5 pm, with the macroscopic 25 proportion by volume of the voids and channels in the total particle being about 15%. The solution was stirred for 45 minutes at 95 0 C, then cooled to 20°C, after which the 10-fold molar amount, based on the organomagnesium compound, of hydrogen chloride was passed in. After 60 minutes, the reaction product was admixed while stirring continuously with 3 mol of ethanol per mole of magnesium. This mixture was Sstirred for 0.5 hour at 80°C and subsequently admixed with 7.2 mol of titanium tetrachloride and 0.5 mol of di-n-butyl phthalate, in each case based on 1 mol of magnesium. The mixture was subsequently stirred for 1 hour at 100'C, the solid thus obtained was filtered off and washed a number of times with ethylbenzene.
The solid product thus obtained was extracted for 3 hours at 125°C with a 10% strength by volume solution of titanium tetrachloride in ethylbenzene. The solid product was then separated from the extractant by filtration and washed with n-heptane until the extractant contained only 0.5% by weight of titanium tetrachloride.
The titanium-containing solid component contained r; BASF Aktiengesellschaft O.Z. 0050/46076 13 by weight of Ti 7.4% by weight of Mg 28.2% by weight of Cl.
The particle diameter was determined by Coulter Counter analysis (particle size distribution of the silica gel particles), the pore volume and the specific surface area were determined by nitrogen adsorption in accordance with DIN 66131 or by mercury porosimetry in accordance with DIN 66133. The mean particle size of the primary particles, the diameter of the voids and channels and their macroscopic proportion by volume were determined by means of scanning electron microscopy or electron probe microanalysis, in each case on particle surfaces and on particle cross sections of the silica gel.
b) Polymerization of propylene The polymerization was carried out in a vertically stirred gas-phase reactor having a utilizable capacity of 800 1 in the presence of hydrogen as molecular weight regulator. The reactor contained an agitated fixed bed of finely divided polymer.
25 Gaseous propylene was passed into the gas-phase reactor at 0: 25 80°C and at a pressure of 32 bar. Polymerization was carried out continuously at a mean residence time of 1.5 hours with the aid of the titanium-containing solid component a) described in Example 2 a, with 7.4 g/h of the titanium-containing solid component 450 mmol/h of triethylaluminum and 45 mmol/h of dimethoxyisobutylisopropylsilane being used as cocatalyst.
After completion of the gas-phase polymerization, a propylene homopolymer having a melt flow index of 11.9 g/10 min at 230°C and 35 2.16 kg (in accordance with DIN 53 735) was obtained.
Comparative Example B Propylene was polymerized using a method similar to Example 2 according to the present invention with the same catalyst system and under the same conditions, but using a titanium-containing solid component a) containing a granular silica gel having the following properties: Particle diameter: 20 45 mun Pore volume: 1.8 cm 3 /g Specific surface area: 325 m 2 /g I r BASF Aktiengesellschaft O.Z. 0050/46076 14 Proportion of voids and channels in the total particle: 1.0 After completion of the gas-phase polymerization, a propylene homopolymer having a melt flow index of 12.4 g/10 min at 230°C and 2.16 kg (in accordance with DIN 53 735) was obtained.
Example 3 The procedure of Example 2 according to the present invention was repeated. Propylene was passed into a vertically stirred 800 1 gas-phase reactor at a mean residence time of 1.5 hours.
Polymerization was carried out continuously at a mean residence time of 1.5 hours, with 6.6 g/h of the titanium-containing solid component described, 450 mmol/h of the aluminum component and mmol/h of dimethoxyisobutylisopropylsilane being used as catalyst constituents.
After completion of the gas-phase polymerization, a propylene homopolymer having a melt flow index of 12.3 g/10 min at 230°C and 2.16 kg (in accordance with DIN 53 735) was obtained.
Comparative Example C S 25 Propylene was polymerized using a method similar to Example 3 according to the present invention with the same catalyst system and under the same conditions, but using a titanium-containing solid component a) containing a granular silica gel having the following properties: Particle diameter: 20 45 pm Pore volume: 1.8 cm 3 /g Specific surface area: 325 m 2 /g Proportion of voids and channels 35 in the total particle: After completion of the gas-phase polymerization, a propylene homopolymer having a melt flow index of 13.0 g/10 min at 230°C and 2.16 kg (in accordance with DIN 53 735) was obtained.
Example 4 The procedure of Example 2 according to the present invention was repeated. Propylene was passed into a vertically stirred 800 1 gas-phase reactor at a mean residence time of 1.5 hours.
Polymerization was carried out continuously at a mean residence time of 1.5 hours, with 5.9 g/h of the titanium-containing solid rrl I I I BASF Aktiengesellschaft O.Z. 0050/46076 component described, 450 mmol/h of the aluminum component and 9 mmol/h of dimethoxyisobutylisopropylsilane being used as catalyst constituents.
After completion of the gas-phase polymerization, a propylene homopolymer having a melt flow index of 12.8 g/10 min at 230°C and 2.16 kg (in accordance with DIN 53 735) was obtained.
Comparative Example D Propylene was polymerized using a method similar to Example 4 according to the present invention with the same catalyst system and under the same conditions, but using a titanium-containing solid component a) containing a granular silica gel having the following properties: Particle diameter: 20 45 pm Pore volume: 1.8 cm 3 /g Specific surface area: 325 m 2 /g Proportion of voids and channels in the total particle: After completion of the gas-phase polymerization, a propylene :2homopolymer having a melt flow index of 12.1 g/10 min at 230'C and 25 2.16 kg (in accordance with DIN 53 735) was obtained.
Table II below shows, both for Examples 2 to 4 according to the present invention and for Comparative Examples A to C, the productivity of the catalyst system used and also the following properties of the propylene homopolymers obtained in each case: xylene-soluble proportion (measure of the stereospecificty of the polymer), chlorine content and stiffness (G modulus).
0
C
C C C C C C C
OCR.
C
C.
C C
C
C. C C
CC.
CC C. C CC CCC CC CCC. C CC C C CRC CCC CC CC Table II Example 2 Comparative Example 3 Comparative Example 4 Comparative Example B Example C Example D Productivity [g of 20100 12100 22800 13900 25400 15300 polymer/g of titanium-containing solid Chlorine content of the 14 23 12 20 11 18 polymer Xylene-soluble 1.0 1.9 1.3 3.0 2.2 3.8 proportion by weight] 780____ [G modulus [N/MM 2 1010 925 960 T_ 830 90078 *)determined in accordance with DIN 53 445 9' :T C _C
I-
BAS Aktigsmiischaft 0.Z. 0050/46076 Comparison of Examples 2 to 4 according to the present invention with Comparative Examples B to D makes it clear that the process of the present invention has a higher productivity and leads to polymers of propylene having an increased stereospecificity (lower xylene-soluble prdportions), a reduced chlorine content and an increased stiffness (higher G modulus).
0 0* U 0 0
U
0 0**0 0U*
I
111 18 THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A catalyst system of the Ziegler-Natta type, comprising as active constituents a) a titanium-containing solid component comprising a compound of titanium, a compound of magnesium, a halogen, finely divided silica gel as support and a carboxylic ester as electron donor compound, and also, as cocatalyst, b) an aluminum compound and c) if desired, a further electron donor compound, wherein the finely divided silica gel used has a mean particular diameter of from 5 to 200 gm, a mean particle diameter of the primary particles of from 1 to 10 lm and voids or channels having a mean diameter of from 1 to 10 im whose macroscopic proportion by volume in the total particle is in the range of 5 to 2. A catalyst system as claimed in claim 1, wherein the finely divided silica gel used has voids and channels having an average diameter of from 1 to Lm whose macroscopic proportion by volume in the total particle is in the range of from 5 to 3. A catalyst system as claimed in claim 1 or 2, wherein the finely divided silica gel used is spray dried.
4. A catalyst system as claimed in any of claims 1 to 3, wherein the further electron donor compound c) used is an organosilicon compound of the general formula (I) R1nSi(OR2) 4 .n where R1 are identical or different and are each a Ci-C20-alkyl group, a S 5- to 7-membered cycloalkyl group which in turn can bear a C1-Clo-alkyl group, or a C6-C20-aryl or arylalkyl group, R2 are identical or different and Sare each a C1-C20-alkyl group and n is 1, 2 or 3.
Claims (4)
- 6. A process for producing a catalyst system as claimed in any of claims 1 to wherein the titanium-containing solid component a) and the cocatalyst b) and, if used, c) are allowed to react together at from 0 to 1500 C and at pressures of from 1 to 100 bar.
- 7. A process for preparing polymers of propylene by polymerization of propylene and, if desired, added comonomers at from 20 to 1500 C and at pressures of from 1 to 100 bar in the presence of a Ziegler-Natta catalyst system, wherein a catalyst system as claimed in any of claims 1 to 5 is used. C
- 8. A polymer of propylene obtained by the process as claimed in claim 7.
- 9. A propylene homopolymer obtained by polymerizing propylene at from to 100 0 C, at pressures of from 15 to 40 bar and at mean residence times of from 0.5 to 5 hours in the presence of Ziegler-Natta catalyst systems as claimed in any of claims 1 to S 10. A film, fiber or molding comprising a polymer as claimed in claim 8 or 9. DATED this 28th day of May, 1999. BASF AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA LCG:CLR:JL VAX doc 027 AU6195896.WPC L. BASF Aktiengesellschaft O.Z. 0050/46076 Catalyst systems of the Ziegler-Natta type Abstract Catalyst systems of the Ziegler-Natta type comprise as active constituents a) a titanium-containing solid component comprising a compound of titanium, a compound of magnesium, a halogen, silica gel as support and a carboxylic ester as electron donor compound, and also, as cocatalyst, b) an aluminum compound and c) if desired, a further electron donor compound, wherein the silica gel used has a mean particle diameter of 20 from 5 to 200 pm, a mean particle diameter of the primary particles of from 1 to 10 pm and voids or channels having a mean diameter of from 1 to 10 pm whose macroscopic proportion by volume in the total particle is in the range from 5 to
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19529240A DE19529240A1 (en) | 1995-08-09 | 1995-08-09 | Improved Ziegler-Natta catalyst system for polymerisation of olefin(s)! - has titanium-contg. solid component based on special finely divided silica support in which particles contain cavities and channels |
| DE19529240 | 1995-08-09 | ||
| DE1995145497 DE19545497A1 (en) | 1995-12-06 | 1995-12-06 | Ziegler-Natta type catalyst system giving reduced micro:speck formation |
| DE19545497 | 1995-12-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU6195896A AU6195896A (en) | 1997-02-13 |
| AU708459B2 true AU708459B2 (en) | 1999-08-05 |
Family
ID=26017556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU61958/96A Ceased AU708459B2 (en) | 1995-08-09 | 1996-08-07 | Catalyst systems of the Ziegler-Natta type |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0761696B1 (en) |
| JP (1) | JPH09110916A (en) |
| CN (1) | CN1056155C (en) |
| AR (1) | AR003227A1 (en) |
| AT (1) | ATE164598T1 (en) |
| AU (1) | AU708459B2 (en) |
| DE (1) | DE59600133D1 (en) |
| ES (1) | ES2114335T3 (en) |
| TW (1) | TW367337B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19545499A1 (en) * | 1995-12-06 | 1997-06-12 | Basf Ag | Improved statistical propylene copolymers |
| US6329315B1 (en) | 1996-06-21 | 2001-12-11 | W. R. Grace & Co.-Conn. | Frangible, spray dried agglomerated supports, method of making such supports, and olefin polymerization catalysts supported thereon |
| DE19637367A1 (en) * | 1996-09-13 | 1998-03-19 | Basf Ag | Ziegler-Natta catalyst systems modified during their manufacture |
| DE19710761A1 (en) * | 1997-03-14 | 1998-09-17 | Basf Ag | Highly crystalline propylene homopolymers |
| DE19722569A1 (en) | 1997-05-28 | 1998-12-03 | Basf Ag | Statistical propylene copolymers |
| DE19728141A1 (en) * | 1997-07-02 | 1999-01-07 | Basf Ag | Process for the polymerization of C2-C8-Alk-1-enes using a Ziegler-Natta catalyst system |
| US7022795B1 (en) | 1998-03-13 | 2006-04-04 | Novolen Technology Holdings, C.V. | Highly crystalline propylene homopolymers |
| US6313061B1 (en) | 1998-12-22 | 2001-11-06 | W. R. Grace & Co.-Conn. | Method of making frangible spray dried agglomerated supports and olefin polymerization catalysts supported thereon |
| DE10002653A1 (en) * | 2000-01-21 | 2001-07-26 | Targor Gmbh | Novel catalyst systems of the Ziegler-Natta type |
| EP1336625A1 (en) | 2002-02-14 | 2003-08-20 | Novolen Technology Holdings C.V. | Solid catalytic component and catalytic system of the Ziegler-Natta type, process for their preparation and their use in the polymerisation of alk-1-enes |
| DE10306893A1 (en) | 2003-02-18 | 2004-08-26 | Basf Ag | Process for finishing textile material to impart water and soil repellence to e.g. natural, modified and/or synthetic fibers, yarn (precursor), thread or fabric, uses organic polymer and particulate (in)organic solid in aqueous medium |
| DE102004025368A1 (en) | 2004-05-19 | 2005-12-08 | Basf Ag | Process for producing structured surfaces |
| US7329626B2 (en) | 2004-09-07 | 2008-02-12 | Lummus Novolen Technology Gmbh | Ziegler-Natta catalyst, preparation, and use for the polymerization of alkenes |
| JP2007297371A (en) * | 2006-04-07 | 2007-11-15 | Colcoat Kk | Dialkoxymagnesium granular material and synthesis and use thereof |
| RU2737832C1 (en) | 2017-09-15 | 2020-12-03 | Базелл Полиолефин Италия С.Р.Л. | Method of producing catalyst components for olefin polymerization |
| CN114957519A (en) * | 2022-07-19 | 2022-08-30 | 吉化集团吉林市天龙催化剂有限公司 | Solid titanium catalyst, preparation method and catalyst component for propylene polymerization |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3201695A (en) * | 1994-08-12 | 1996-03-07 | Dow Chemical Company, The | Supported olefin polymerization catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7707960A (en) * | 1977-07-18 | 1979-01-22 | Stamicarbon | PROCESS FOR PREPARING POROUS, PURE SILICON DIOXIDE. |
| GB8610024D0 (en) * | 1986-04-24 | 1986-05-29 | Unilever Plc | Porous structures |
| JPH02293314A (en) * | 1989-05-01 | 1990-12-04 | Mitsubishi Kasei Corp | Aggregate of particle and production thereof |
-
1996
- 1996-08-01 EP EP96112429A patent/EP0761696B1/en not_active Revoked
- 1996-08-01 DE DE59600133T patent/DE59600133D1/en not_active Revoked
- 1996-08-01 AT AT96112429T patent/ATE164598T1/en not_active IP Right Cessation
- 1996-08-01 ES ES96112429T patent/ES2114335T3/en not_active Expired - Lifetime
- 1996-08-06 TW TW085109534A patent/TW367337B/en active
- 1996-08-07 AU AU61958/96A patent/AU708459B2/en not_active Ceased
- 1996-08-08 CN CN96113267A patent/CN1056155C/en not_active Expired - Fee Related
- 1996-08-09 JP JP8210863A patent/JPH09110916A/en active Pending
- 1996-09-08 AR ARP960103936A patent/AR003227A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3201695A (en) * | 1994-08-12 | 1996-03-07 | Dow Chemical Company, The | Supported olefin polymerization catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59600133D1 (en) | 1998-05-07 |
| CN1152580A (en) | 1997-06-25 |
| EP0761696A1 (en) | 1997-03-12 |
| AU6195896A (en) | 1997-02-13 |
| AR003227A1 (en) | 1998-07-08 |
| CN1056155C (en) | 2000-09-06 |
| EP0761696B1 (en) | 1998-04-01 |
| TW367337B (en) | 1999-08-21 |
| ES2114335T3 (en) | 1998-05-16 |
| ATE164598T1 (en) | 1998-04-15 |
| JPH09110916A (en) | 1997-04-28 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PC | Assignment registered |
Owner name: NOVOLEN TECHNOLOGY HOLDINGS C.V. Free format text: FORMER OWNER WAS: BASF AKTIENGESELLSCHAFT |