IE65299B1 - Process for the preparation of a polyolefin - Google Patents

Process for the preparation of a polyolefin

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Publication number
IE65299B1
IE65299B1 IE216391A IE216391A IE65299B1 IE 65299 B1 IE65299 B1 IE 65299B1 IE 216391 A IE216391 A IE 216391A IE 216391 A IE216391 A IE 216391A IE 65299 B1 IE65299 B1 IE 65299B1
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compound
component
temperature
reaction
mol
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IE216391A
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IE912163A1 (en
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Gerhard Thum
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Hoechst Ag
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Publication of IE912163A1 publication Critical patent/IE912163A1/en
Publication of IE65299B1 publication Critical patent/IE65299B1/en

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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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Artificial Filaments (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Image Processing (AREA)
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Abstract

Prodn. of polyolefins (I) by polymerisation of alpha-olefins at 50-150 deg.C and 1-40 bar in the presence of a catalyst consisting of a transition metal component (A) and an organometallic cpd. (component B); the novelty is that (A) is prepd. without sepn. of intermediates, by (a) reaction of an organomagnesium cpd. of formula (n-Bu)x(n-octyl)yMg (II) (with x = 1.2-1.7; y = 0.3-0.8) with 0.5-2.5 mols. chlorinated hydrocarbon (III) (w.r.t. 1 mol. II) at 30-110 deg.C, (b) treatment of the suspension obtd. with 0.1-1 mol. electron donor (IV) (per g-atom Mg in the solid) at 0-100 deg.C and (c) reaction of the support material obtd. with 0.5-2 mols. (per g-atom Mg in the support) of a cpd. of formula TiXm(OR)4-m (V), at 30-120 deg.C (with R = 2-10C alkyl; X = Hal; m = 0-4). Pref. (IV) is diethyl sulphite (IVA) or Me2Si(OEt)2 (IVE), and (V) is TiCl4.

Description

The present invention relates to a process for the preparation of a polyethylene having spherical particles by means of a highly active, spherical Ziegler catalyst, with which considerable simplifications and advantages in the handling and processing of the products are achieved.
A multiplicity of catalysts of the Ziegler type for the polymerization of alpha-olefins are already known. Many of these catalysts are based on magnesium chloride as support material, which is obtained by reaction of an organomagnesium compound R2Mg, such as, for example, butylethylmagnesium, with a chlorinated hydrocarbon compound R'-Cl, such as, for example, carbon tetrachloride (cf. US-A-4 442 225, US-A-4 439 539, DE-A-30 10 202).
However, in this context it is not possible to obtain a magnesium chloride of spherical shape.
On the other hand, it is known that spherical magnesium chloride is formed on the reaction of an organomagnesium compound R2Mg with a chloro-organic compound R'-Cl in the presence of an organoaluminum compound, such as triethylaluminum, and an electron donor compound, such as diisoamyl ether (cf. EP-A-00 99284).
Restrictions which apply here are that R* must be a hydrocarbon radical having three or more carbon atoms and that the carbon atom adjacent to the chlorine must be either a secondary or tertiary carbon atom.
A process is known for the preparation of a polyolefin by polymerization of alpha-olefins in the presence of a catalyst, the transition metal component A of which has been formed by a) reaction of an organomagnesium compound of the formula RxMgR2 with an organoaluminum compound of the formula AlR3n(OR4) 3_n, or the reaction product of aluminum trialkyls or aluminum dialkylhydrides with diolefins, and an aliphatic primary chlorinated hydrocarbon, b) treatment of the resulting solid with an electron donor, and c) reaction of the support material thus obtained with a titanium or zirconium compound of the formula MeXn(OR5)4.m (cf. DE-A-36 20 060).
It has now been found that a highly active and at the same time spherical catalyst, with which spherical polymers of ethylene can be obtained which are distinguished by a narrow particle size distribution coupled with a large average particle diameter, can be obtained in a simple manner if a very specific magnesium compound is used.
The invention thus relates to a process for the preparation of a polyethylene having spherical particles by polymerization of ethylene or copolymerization of ethylene and an alpha-olefin having 4 to 10 carbon atoms and one or more double bonds at a temperature of 50 to 150°C and a pressure of 1 to 40 bar in the presence of a catalyst composed of a transition metal component (component A) and an organometallic compound (component B), component A of which has been formed by reaction of an organomagnesium compound with an electron donor, an organic chlorine compound and a transition metal compound, wherein the polymerization is carried out in the presence of a catalyst of which spherical component A, having an average particle diameter of 20 to 110 μιη and a ratio Dm/Dn of less than 1.5, has been prepared, without separating off intermediates, by a) reaction of an organomagnesium compound of the formula [ (n—C4Hg) 1,2-1.7 0.3-0.in 0.5 to 15 molar solution with an aliphatic chlorinated hydrocarbon in an amount of 0.5 to 2.5 mol of the chlorinated hydrocarbon, based on mol of the organomagnesium compound, at a temperature of 30 to 110°C, T i T b) treatment of the resulting suspension with an electron donor in an amount of 0.1 to 1 mol per gram atom of magnesium contained in the solid at a temperature of 0 to 100°C, for 0.5 to 3 hours, c) reaction of the support material thus obtained with a compound of the formula Ti^(OR1)in which R1 is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atom and m is an integer from 0 to 4.· in an amount of 0.5 to 2 mol per gram atom of magnesium contained in the support material, at a temperature of 30 to 120°C, and d) washing with an inert hydrocarbon at a temperature of 0 to 100°C.
Initially a spherical solid is formed. For this purpose an organomagnesium compound is reacted with an aliphatic primary chlorinated hydrocarbon.
The organomagnesium compound is a magnesium dialkyl of the formula [ (n-C4H9)3..2-1.7 (n-C8H17) 0.3-0.eMStf · in particular [(n-C4HsH)x 5 (n-C8H17 >ο.5Μ9Ϊ · A suitable aliphatic primary chlorinated hydrocarbon is, for example, carbon tetrachloride, chloroform, methylene chloride, 1 - chloropropane or 1,1,1-trichloroethane, it also being possible for mixtures to be employed. Chloroform and carbon tetrachloride are preferably used.
In order to prepare the spherical solid, the organomagnesium compound is dissolved in an inert, liquid hydrocarbon under nitrogen or argon atmosphere. This solution is brought into contact, with uniform stirring at a temperature of 30 to 110°C, preferably of 40 to 80°C, with a solution of the chlorinated hydrocarbon. The reaction can be carried out by adding the chlorinated hydrocarbon to the solution of the organomagnesium compound in the liquid hydrocarbon, or vice versa.
In the case of this reaction, both the reaction time and the degree of dilution of the reactants can be varied within wide limits. The reaction time is 30 min to several hours, preferably 1 hour to 5 hours. The reactants are employed in the form of 0.5 to up to 15 molar solutions.
The batch contains up to 2.5 mol, preferably up to 2.0 mol, of the chlorinated hydrocarbon, based on 1 mol of organomagnesium compound.
The suspended solid formed essentially consists of spherical magnesium chloride.
An electron donor is now added to this suspension of the spherical solid. Suitable electron donors are oxygencontaining silicon, phosphorue or sulfur compounds, nitrogen compounds or silicon compounds containing alkyl or aryl radicals having 1 to 8 carbon atoms, such as, for example, triethylamine or hexamethyldisilane, or aliphatic or aromatic ethers containing identical or different organic radicals.
Diethyl sulfite and di ethoxydimethyl silane are preferably used.
The electron donor is added to the spherical solid in a molar ratio of 0.1 to 1, preferably 0.1 to 0.6, based on one gram attim of magnesium, at a temperature of 0 to 100°C, preferably of 60 to 90°C.
The reaction time is 0.5 to 3 hours, preferably up to 1 h, depending on the reactivity of the reactants.
The spherical support material obtained in this way is immediately reacted under nitrogen or argon atmosphere with a compound of the formula TiXgjOR1)4_n, in which R is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atom, preferably chlorine, and m is an integer T~T — T..... from 0 to 4, but preferably is 2 or 4. A mixture of several of these compounds can be employed.
Preferred compounds are, for example, TiCl4, TiCl3(OEt), TiCl3(O-iPr), TiCl2(OEt)2, TiCl2(O-iPr)2 and TiCl2 (O-CH2C6H5)2.
TiCl4 is very particularly preferred.
In the reaction described above, the titanium compound is employed in an amount of 0.5 to 2 mol, preferably 0.8 to 1.8 mol and in particular 1 mol, based on one gram atom of magnesium in the spherical support material.
The reaction temperature is 30 to 120°C, preferably 60 to 95°C, and the reaction time is 30 min to several hours, preferably 1 to 2 hours, depending on the titanium coverage required.
The catalyst component A prepared in this way is finally freed from soluble impurities, such as metal or halogen compounds, at a temperature of 0 to 100°C, preferably of 10 to 50°C, by repeated washing with an inert hydrocarbon.
The catalyst component A prepared according to the invention is in the form of spherical particles, the average diameter of which is 20 to 110 μα, preferably 40 to 80 μη., and which have a ratio of mass-average diameter Da to number-average diameter Da of less than 1.5, preferably 1.01 to 1.2.
The component A is employed in the form of a suspension in an inert hydrocarbon, or alternatively, after separating off the suspending agent, dry for the polymerization of ethylene or the copolymerization of ethylene with an alpha-olefin having 4 to 10 carbon atoms and one or more double bonds, such as, for example, but-l-ene, isobutene, hex-l-ene or buta-1,3-diene, is preferred.
The polymerization can be carried out either continuously or discontinuously in the gas phase or in saturated hydrocarbons having 3 to 15 carbon atoms, such as, for example, propane, butanes, pentanes, hexanes, heptanes, cyclohexenes or mixtures of such compounds.
In general, hydrogen, as molar mass regulator, and, as component B (cocatalyst), an aluminum compound of the formula AlR2pY3_p, in which p is 1, 2 or 3 and R2 is an alkyl or aryl radical having 1 to 20 carbon atoms and Y is hydrogen, a halogen atom or an alkoxy or aryl oxy group having, in each case, 1 to 20 carbon atoms, are additionally also employed.
Examples are halogen-containing organoaluminum compounds, such as dialkylaluminum halides, alkylaluminum dihalides or alkylaluminum sesquichlorides, and also aluminum trialkyls or aluminum alkylhydrides, which can be employed on their own or as a mixture.
Aluminum trialkyls, such as, for example, aluminum triethyl or aluminum triisobutyl, are preferably used.
The polymerization temperature is 50 to 150°C, preferably 50 to 100°C, and the pressure 1 to 40 bar, preferably 3 to 12 bar.
The polymers and copolymers prepared in the process according to the invention are distinguished by a compact, uniform spherical shape with a very narrow particle size distribution. The ratio of mass-average diameter Dn to number-average diameter Dn is less than 1.5, preferably from 1.02 to 1.3. The D/d ratio is in the range from 1.05 to 1.2. The diameter of the polymer particle ie in the range from 100 to 1,000 μη, preferably 300 to 800 μη. The polymers have a high bulk density and an excellent processability.
A further advantage of the catalyst according to the invention lies in the high contact activity, so that only very small amounts of the catalyst are necessary for the polymerization. Consequently, the polymers also do not have to be subjected to an additional after-treatment, such as, for example, laborious washing or purification operations. Furthermore, there are no unwanted discolorations of the product due to catalyst residues, which frequently can lead to an impairment of the stability of the polymers to light.
The residual titanium or zirconium content in the polymers prepared according to the invention is less than 5 ppm, frequently less than 3 ppm.
In particular, however, considerable simplifications and advantages in the handling, drying and processing are achieved as a result of the spherical shape and the associated very good flowability of the polymers and copolymers.
The invention is illustrated in more detail below by the examples.
The MFI (190/5) melt index was determined in accordance with DIN 53735 at 190»C and at a load of 5 kg.
The Da to Dn ratio was determined in accordance with NF X 11-630 of June 1981: Db - [Σ ni (Di)3 Di]/[E ni (Di)3] Dn » [Σ ni Di]/Σ ni ni number i of the samples of the same diameter Di diameter of the i-th sample The particle size distribution Dn/Dn of the component λ was determined by means of image analysis.
The particle size distribution Da/Dn of the polymer was determined by means of screen analysis in accordance with DIN 4188.
Example 1 55.3 cm3 (- 570 mmol) of CC14 together with 500 cm3 of benzine (b.p. 100-120*0 were added in the course of 90 min at 70-80*C to 621 cm3 of a solution of a magnesium compound having the approximate composition [ (n-C4H5) (n-C8H17) Q.sMg] , which is commercially under the name BOMAG-A, (. 570 mmol of Mg) . The batch was then 120 min at 85*C. The bright, red-brown, spherical solid had am Mg/Cl ratio of 1 to 2.08 and could be employed as catalyst support without further working up. available in heptane stirred for Example 2 656 cm3 of a solution of the Mg compound named in Example 1 in heptauie (- 570 mmol of Mg) were added in the course of 90 min to 200 cm3 of benzine (b.p. 100-120*0 and 98 cm3 of CHC13 (- 1,210 mmol) at 70-75*C auxd the mixture was then stirred for a further 120 min at 75-77*C. The pale brown, spherical solid had an Mg/Cl ratio of 1:1.97.
Example 3 17.2 cm3 (- 135 mmol) of diethyl sulfite were added at 82-84®C in the course of 10 min to a portion of the MgCl2 suspension prepared in Example 2 (- 306 mmol of Mg) and the mixture was then stirred for 60 min at 84-85*C. 33.7 cm3 ( 306 mmol) of TiCl4 were then added dropwise in the course of 20 min at 85 ®C auid the batch was stirred for a further 120 min at 85-88*C. The violet, spherical catalyst solid was washed 8 times with in total 1,300 cm3 of benzine (b.p. 100-120*0 at 55*C.
Mg:Ti:Cl - 1:0.085:2.10 d50 55 /xm? Da/Dn - 1.18.
Example 4 31.9 cm3 250 mmol) of diethyl sulfite were added at 85*C in the course of 5 min to the MgCl2 suspension obtained in Example 1 (- 570 mmol of Mg) auid the mixture was then stirred for 60 min at 85*C. 62.8 cm3 (> 570 mmol) of TiCl4 were added in the course of 20 min to the dark brown suspension at 85°C and the batch was stirred for 120 min at 95°C. The dark violet catalyst solid was then washed at 60°C 6 times with, in each case, 150 cm3 of benzine (b.p. 100-120*0 until titanium-free.
Mg:Ti:Cl « 1:0.130:2.28 d50 « 60 μιη; Da/Dn - 1.12.
Example 5 The procedure was analogous to Example 3 - except that 92 mmol of di-n-butyl ether were employed in place of 135 mmol of diethyl sulfite.
Mg:Ti:Cl 1:0.008:1.95 d50 = 50 μη; Dtt/Dn 1.15.
Example 6 The procedure was analogous to Example 4 except that di ethoxydimethyl si lane was employed in place of diethyl sulfite.
Mg:Ti:Cl « 1:0.06:2.11 d50 - 45 /tm; Da/Dn - 1.17.
Examples 7-14 The ethylene polymerization was carried out in accordance with the table in a 1.5 dm3 steel autoclave at a temperature of 85*C and a pressure of 7 bar in 800 cm3 of benzine (b.p. 100-120*0. Zn each case 3.0 mmol of triethylaluminum (TEA) or triisobutylaluminum (TIBA) were added as component B. The spherical polyethylene particle had a D/d ratio of between 1.1 and 1.3. The proportion of fines < 100 /tm was < 0.1%.
Table: Ethylene polymerization Ex. Comp.A Ex. No. Comp.B h2 t by vol. Yield g PE/mmol Ti MFI 190/5 g/10 min dso /zm Bulk density 9/1 7 3 TEA 55 14,580 22.5 520 395 8 3 TIBA 45 18,980 6.8 585 360 9 3 TIBA 55 10,110 22.0 475 390 10 4 TIBA 45 14,040 4.3 380 330 11 4 TEA 55 17,320 20.0 360 335 12 4 TEA 45 20,425 5.5 430 345 13 5 TIBA 45 41,435 7.0 390 340 14 6 TEA 55 23,890 26.1 435 355 T

Claims (5)

1. A process for the preparation of a polyethylene having spherical particles by polymerization of ethylene or copolymerization of ethylene and an alpha-olefin having 4 to 10 carbon atoms and one or more double bonds at a temperature of 50 to 150°C and a pressure of 1 to 40 bar in the presence of a catalyst composed of a transition metal component (component A) and an organometallic compound (component B), component A of which has been formed by reaction of an organomagnesium compound with an electron donor, an organic chlorine compound and a transition metal compound, wherein the polymerization is carried out in the presence of a catalyst of which spherical component A, having an average particle diameter of 20 to 110 /xm and a ratio D a /D n of less than 1.5, has been prepared, without separating off intermediates, by a) reaction of an organomagnesium compound of the formula [(n-C 4 H 3 ) 1.2-1.70.3-0.0.5 to 15 molar solution with an aliphatic chlorinated hydrocarbon in an amount of 0.5 to 2.5 mol of the chlorinated hydrocarbon, based on 1 mol of the organomagnesium compound, at a temperature of 30 to 110°C, b) treatment of the resulting suspension with an electron donor in an amount of 0.1 to 1 mol per gram atom of magnesium contained in the solid at a temperature of 0 to 100*C, for 0.5 to 3 hours, c) reaction of the support material thus obtained with a compound of the formula TiX^OR 1 ) 4 _ B , in which R 1 is an alkyl radical having 2 to 10 carbon atoms, X is a halogen atom and m is an integer from 0 to 4, in an amount of 0.5 to 2 mol per gram atom of magnesium contained in the support material, at a temperature of 30 to 120°C, and d) washing with an inert hydrocarbon at a temperature of 0 to 100°C.
2. The process as claimed in claim 1, wherein the electron donor employed is diethyl sulfite or 5 die thoxydime thy 1 s i 1 ane.
3. The process as claimed in claim 1, wherein TiCl 4 has been employed.
4. A process as claimed in claim 1, substantially as hereinbefore described and exemplified. 10
5. A polyethylene whenever prepared by a process claimed in a preceding claim.
IE216391A 1990-06-22 1991-06-21 Process for the preparation of a polyolefin IE65299B1 (en)

Applications Claiming Priority (1)

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DE4019925A DE4019925A1 (en) 1990-06-22 1990-06-22 Polyolefin prodn. with high bulk density and good processability

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IE912163A1 IE912163A1 (en) 1992-01-01
IE65299B1 true IE65299B1 (en) 1995-10-18

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JP (1) JPH07107084B2 (en)
KR (1) KR950009109B1 (en)
AT (1) ATE109800T1 (en)
AU (1) AU640488B2 (en)
BR (1) BR9106583A (en)
DE (2) DE4019925A1 (en)
DK (1) DK0535023T3 (en)
ES (1) ES2061250T3 (en)
IE (1) IE65299B1 (en)
PT (1) PT98069B (en)
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4017661A1 (en) * 1990-06-01 1991-12-05 Hoechst Ag METHOD FOR PRODUCING A POLY-1 OLEFIN
CA2092769A1 (en) * 1992-03-28 1993-09-29 Gerhard Thum Process for the preparation of a spherical catalyst component
DE4306382A1 (en) * 1993-03-02 1994-09-08 Hoechst Ag Process for the preparation of a poly-1-olefin
EP0622379B1 (en) * 1993-04-29 1998-07-08 Ticona GmbH Process for the production of a catalyst system for the (co)polymerisation of ethylene into ultra-high molecular weight ethylene (co)polymers
DE4337985A1 (en) * 1993-11-06 1995-05-11 Hoechst Ag Process for the preparation of a poly-1-olefin
DE4417475A1 (en) * 1994-05-19 1995-11-23 Hoechst Ag Process for the preparation of a catalyst component for the polymerization of ethylene and 1-olefins to form ultra-high molecular weight ethylene polymers
WO2005097322A1 (en) * 2004-04-08 2005-10-20 Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Method for preparing a catalyst and process for polymerising ethylene and copolymerising ethylene with alpha-olefins
RU2320410C1 (en) * 2006-11-16 2008-03-27 Институт Катализа Имени Г.К. Борескова Сибирского Отделения Российской Академии Наук Method of preparing catalyst and ethylene polymerization process utilizing this catalyst
US9714302B2 (en) 2014-10-10 2017-07-25 W. R. Grace & Co.—Conn. Process for preparing spherical polymerization catalyst components for use in olefin polymerizations

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252670A (en) * 1979-01-10 1981-02-24 Imperial Chemical Industries Limited Olefine polymerization catalyst
DE3620060A1 (en) * 1986-06-14 1987-12-17 Hoechst Ag METHOD FOR PRODUCING A POLYOLEFIN

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PT98069A (en) 1992-03-31
IE912163A1 (en) 1992-01-01
DE59102518D1 (en) 1994-09-15
DK0535023T3 (en) 1995-01-09
AU7908291A (en) 1992-01-23
ATE109800T1 (en) 1994-08-15
JPH05502053A (en) 1993-04-15
AU640488B2 (en) 1993-08-26
DE4019925A1 (en) 1992-01-02
JPH07107084B2 (en) 1995-11-15
WO1992000332A1 (en) 1992-01-09
BR9106583A (en) 1993-06-01
PT98069B (en) 1998-12-31
KR930701492A (en) 1993-06-11
KR950009109B1 (en) 1995-08-14
ZA914789B (en) 1992-03-25
ES2061250T3 (en) 1994-12-01
EP0535023A1 (en) 1993-04-07

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