Classifications

• • 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
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • 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
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

• the present invention relates to a procatalyst composition which is suitable for homo- and co-polymerization of ole ⁇ fins.
• the invention also relates to a method for preparation of such a procatalyst composition and its use together with an organometallic co-catalyst compound for polymerization of olefins.
• a Ziegler-Natta-catalyst system In the polymerization of olefins a Ziegler-Natta-catalyst system generally is used consisting of a so called procata ⁇ lyst and a co-catalyst.
• the procatalyst is a component based on a compound of a transition metal belonging to some of the groups IVA-VIII (Hubbard, IUPAC 1970) of the periodic system of the elements.
• the co-catalyst again is a component based on an organic metal compound of a metal belonging to ' some of the groups IA-IIIA of the periodic system of the el ⁇ ements.
• the catalyst system usually also contains electron donating compounds which improve and modify the catalytical properties.
• heterogenic polymerization catalysts it is conventional to use in the preparation of heterogenic polymerization catalysts as a component enhancing the poly ⁇ merization activity of the procatalysts a support compound, on which the transition metal compound is superposed.
• the usual carrier compounds are based on silica, aluminum oxide, magnesium oxide, titanium oxide, a mixture thereof, carbon in different forms, and different types of polymers.
• a more modern method to provide a deformed crystal form of magnesium compounds such as a magnesium halide and thereby enhance its ability to become activated with a transition metal compound is to modify it chemically.
• a mag ⁇ nesium compound, optionally an electron donor and a tran ⁇ sition metal compound are reacted, often in a solution, to an easily isolated procatalyst composition.
• Enough amorphous procatalyst is anyhow not formed in the process since the composition is more or less spontaneously crystallized in the preparation whereafter its morphology is not essentially changed.
• U.S. Patents No. 4,124,532 and 4,174,429 describe the prep ⁇ aration of this kind of catalytically active complexes by reacting a magnesium halide and a transition metal compound at a suitable ratio in a electron donor solvent.
• the fin- ished complex can be separated through crystallization by evaporation of said solvent, or by mixing the complex with a solvent in which it isn't soluble. Because such complex coiripouiius are lor- ⁇ e as a result of . spontaneous crystal ⁇ lization, their crystall structure is very regular and activity rather limited.
• U.S. Patent 4,302,566 and EP Patent Application 6,110 de ⁇ scribe a precursor formed by a magnesium halide, a transit!- on metal compound and an electron donor.
• the precursor is formed by precipitation from an electron donor solution whereafter it is separated and mixed with an aluminumalkyl which is activating it and a separate inert carrier.
• an essentially amorphous procatalyst compo ⁇ sition is not formed either, because the precursor in ques ⁇ tion is crystallized in the preparation spontaneously and its morphology is not essentially changed after that.
• EP Patent Application No. 166,970 describes the treatment of magnesium chloride with titanium tetrabutoxide in hep ⁇ tane, the treatment of the surfaces of the particles ob- tained with an organic hydroxy compound such as an alcohol, a silanol or a phenol, the treatment of the product with a titanium halide and a polymeric silicon compound.
• US Patent No. 4,833,111 describes suspending of a silica activated at 600°C into hexane, reacting of the surface hydroxyl groups of the silica with dibutylmagnesium, reac ⁇ ting of the magnesium with ethanol whereby the butyl group is substituted by a ethoxy group, and activating of the catalyst with titanium tetrachloride and ethyl aluminum dichloride.
• the purpose of the present invention is to provide a solid procatalyst composition which is as active as possible, and which has a suitable particle form, particle size and particle size distribution.
• a useful procatalyst composition is easily obtainable by impregnating a separate, inert carrier with a magnesium halide, a transition metal compound dissolving said mag ⁇ nesium compound and containing no chlorine, and an elec ⁇ tron donor, and by chlorinating with a chlorine compound containing no transition metal, or with a mixture of said chlorine compound and an organometallic compound.
• a procata ⁇ lyst is thus obtained which has its chlorine/metal ratio at an optimal level in respect of the polymerization result.
• the invention has as compared with the solutions of the prior art as an advantage the controlled morphology of the catalyst thanks to the carrier, in particular the silica. Additionally the catalyst according to the invention has both a high activity and good hydrogen sensitivity and a good co-monomer sensitivity and the polymers obtainable with it have a narrow molecular weight distribution.
• a method for the production of a solid procatalyst composition wherein a solid carrier is impregnated with a mixture of a Mg compound and a transition metal compound dissolving this Mg compound, and the resulting composition is chlorinated with a compound containing no titanium.
• the Mg/Ti ratio used in this process is usually of the order 0.5 and it can be of at most about 1, and the obtained polymerization activity as calculated in relation to ti- tanium is typically 100-130 kg PE/g Ti. The remaining ti ⁇ tanium in the polymer is over 10 ppm.
• I lXXS U ⁇ I.OXJT _> b C ⁇ iu OO b U-l UU UJ. l.ij mim- b-iC Xll V Cll .XUll typically are 200-500 kg PE/g Ti and then the titanium remainders are less than 5 ppm.
• the carrier to be used according to the invention can be of whatever porous inorganic or organic material.
• the organic carriers the polymers can be mentioned.
• Especially preferable inorganic materials are based on oxides of sili ⁇ con, aluminum, titanium, magnesium and/or chromium. Such materials are e.g. silica, aluminum oxide, magnesium oxide, magnesium silicate, titanium oxide, etc.
• Especially pre ⁇ ferred carriers are silica, aluminum oxide and magnesium silicate or a mixture thereof. Most preferable is silica.
• the physically bound water can optionally be removed ther- mally from the surface of the inert carrier by drying at a temperature under 200°C.
• the surface hydroxyl groups of the carrier can optionally be removed thermally at a temperature above 200°C or chemi- cally by using agents reacting with the hydroxyl groups.
• the removal of the surface hydroxyl groups is, however, not necessary for the performance of the catalyst as is shown in the examples of the specification.
• Agents suitable for the chemical removal of the surface hydroxyl groups of the carrier are organic silicon, alumi ⁇ num, zinc, phosphorus and/or fluorine compounds.
• organic silicon compounds as the preferred ones may be mentioned the compounds of formula (R ⁇ Si ⁇ NH or formula R n SiX4_ n , wherein R is a hydrogen and/or an alkyl group, X is a group reacting with the H of a hydroxyl group such as a halogen, and n is 1, 2 or 3.
• R is a hydrogen and/or a hydrocarbon group containing 1-20 carbon atoms, preferably a lower alkyl group
• X is a halogen
• n is 1, 2 or most preferably 3
• m is 1 or 2.
• Typical aluminum compounds are ._. -c u-L ffiin ⁇ ___ns such as tr -t-sobuty alut ⁇ inuiu, diaikyl aluminum halides such as diethyl aluminum chloride and di- alkyl aluminum hydrides such as diisobutyl aluminum hydride.
• Preferred phosphorus compounds removing hydroxyl groups are phosphorustrihalides, phosphorusoxytrihalides, diaikyl phosphorus halides, monoalkyl phosphorus halides and diamino phosphorus oxyhalides.
• Suitable fluorine compounds removing hydroxyl groups are gaseous fluorine, hydrogenfluoride, borontrifluoride, silicon tetrafluoride and sulphuroxydi- fluoride.
• the most preferred agents removing hydroxyl groups are organic silicon compounds and organic aluminum compounds and of these the most preferred hexamethyldisilazane respectively.
• a magnesium halide compound with one or several com ⁇ pounds of the transition metals belonging to the groups IVB or VB of the periodic system of the elements, which compouds dissolve the said magnesium compound and contain no chlorine, and with an electron donor compound which is dissolving/suspending the Mg compound.
• It can according to one embodiment be carried out by contacting the carrier with a mixture which has been formed from a magnesium halide compound, from one or several transition metal compounds of the groups IVB and VB of the periodic system of the elements containing no chlorine, and from an electron donor compound.
• the mixture is preferably in the form of a sol- ution, especially in the form of a hydrocarbon or electron donor solution, wherein the dissolved material can be a complex formed by a magnesium compound, a transition metal compound and an electron donor compound.
• the impregnation is carried out by adding a magnesium halide compound, a transition metal compound containing no chlorine and an electron donor compound to the carrier without separate dissolution.
• the impregnation of the carrier can be carried out by first contacting the carrier with a mixture formed from a magnesium compound and an electron donor compound and then with a mixture formed from a magnesium compound and a transition metal compound.
• Suitable magnesium compounds are the Mg halides, especially magnesium dichloride.
• Suitable transition metal compounds are liquid compounds dissolving the magnesium compounds. Such compounds are e.g.
• transition metal alkoxides such as the tetraalkyltitanates (titanium tetraalkoxides) titanium tetraethoxide, titanium tetrapropoxide and titanium tetra- butoxide.
• Suitable electron donor compounds are liquid organic com- pounds dissolving the magnesium compounds. Such compounds are e.g. alkylesters of carboxylic acids, aliphatic ethers, cyclic ethers, aliphatic ketones and aliphatic alcohols. Preferred electron donor compounds are ethyl acetate and tetrahydrofuran and the most preferable are aliphatic al- cohols such as ethanol, propanol and butanol.
• Suitable organometallic compounds are e.g. organic aluminum compounds such as trialkyl aluminums, other metal alkyls such as butyllithium, and organic silicon compounds such as hexamethyldisilazane.
• organic aluminum compounds such as trialkyl aluminums, other metal alkyls such as butyllithium
• organic silicon compounds such as hexamethyldisilazane.
• the most preferred organometallic compounds are the organic silicon compounds and organic aluminum compounds, and from these hexamethyldisilazane and triethylaluminum, respectively.
• the chlorine compound containing no transition metal is preferably HC1, CCI4, silicon chloride or especially a compound of formula [ n A lCl3_ n ] m , wherein R is a hydrocarbon group with 1-20 carbon atoms, preferably a lower alkyl group, n is 1 or 2 and m is 1 or 2.
• Typical aluminum com ⁇ pounds suitable for chlorination are alkyl aluminum chlor- ides such as diethyl aluminum chloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride.
• the carrier is in that case first impregnated with a solution/sludge of the magnesium compound and the electron donor, then reacted with the organometallic compound and thereafter impregnated with a mixture of the magnesium compound and the transition metal compound in a liquid form. The product obtained is finally chlorinated with a chlorine compound containing no transition metal.
• the invention also relates to a method for preparing a procatalyst composition of the type described above, wherein one or several inert, solid carriers are treated, from which carriers hydroxyl groups of the surface have optionally been removed thermally or chemically by reacting the carrier with a compound removing hydroxyl groups, by impregnating the carrier with a magnesium halide compound, with one or several compounds of transition metals of groups IVA and VA of the periodic system of the elements (Hubbard, IUPAC 1970), dissolving said magnesium compound and containing no chlorine, and an electron donor compound dissolving/ suspending said Mg-compound, and treated with a chlorine compound containing no transition metal, or with a mixture of said chlorine compound and an organometallic compound.
• T__e ai ⁇ tiiOu is y ic3.-_.j-y csms ⁇ __ cut e.g. by removing fro one or several inorganic oxides only physically bound water by drying at a temperature under 200°C, or also the hydroxyl groups of the surface by calcination at a temperature above 200°C and/or chemically with an organosilicon compound, preferably hexamethyldisilazane.
• a pre-mixture is prepared by dissolving a magnesium com ⁇ pound, most preferably anhydrous magnesium chloride, into a transition metal compound dissolving it, such as a ti ⁇ tanium alkoxide, preferably titanium tetrabutoxide, and into an electron donor compound dissolving/suspending it, prefer ⁇ ably n-butanol, at a temperature above 20 C C.
• the solution is preferably in the form of a hydrocarbon or an electron donor solution.
• the Mg/Ti mole ratio can be as high as or higher than 1, preferably between 1-4.
• the Cl/Ti mole ratio can be about 1-10, preferably 3-5.
• the ED/Ti mole ratio can be between 1-100.
• the pre-mixture is added to the carrier while stirring and stirring is optionally continued for 1-100 hrs at a tempera ⁇ ture above 20°C.
• the hydrocarbon and/or electron donor solution is evaporated at a temperature above 20°C until a dry, free flowing powder is obtained.
• the components of the pre-mixture can also be added to the carrier without a separate dissolution so that a magnesium compound, a transition metal compound, an electron donor and optionally a hydrocarbon solvent are mixed into the car ⁇ rier, whereafter the stirring of the procatalyst can be continued at a temperature above 20°C for 1-100 hrs, and the hydrocarbon and/or electron donor solution is evaporated at a temperature above 20"C until a dry, free flowing powder is obtained.
• the impregnation of the carrier can also be carried out in two stages so that first a pre— ixture 1 is added which is prepared by dissolving a part of the magnesium compound into the electron donor compound either in a hydrocarbon solvent or without a hydrocarbon solvent, and then by adding either to the dried or undried, impregnated carrier, a pre-mixture 2, which is prepared by dissolving a part of the magnesium compound to the transition metal compound in a hydrocarbon solvent or without a hydrocarbon solvent.
• a pre— ixture 1 which is prepared by dissolving a part of the magnesium compound into the electron donor compound either in a hydrocarbon solvent or without a hydrocarbon solvent
• a pre-mixture 2 which is prepared by dissolving a part of the magnesium compound to the transition metal compound in a hydrocarbon solvent or without a hydrocarbon solvent.
• the obtaibed precursor is stirred and the stirring can be continued for 1-100 hrs at a temperature above 20°C, and finally the precursor is dried at a temperature above 20 Q
• the obtained precursor is thereafter treated with a chlorine compound containing no transition metal, or with a mixture of the chlorine compound in question and an organometallic compound. It is also possible to treat the carrier with an organometallic compound before the treatment with the tran ⁇ sition metal compound containing no chlorine. Examples of the chlorine compounds containing no transition metal as also of the organometallic compounds have been given above.
• the present invention also related to the use of a procata ⁇ lyst composition according to the invention in homo- and co-polymerization of olefins, wherein the polymerization is carried out by the aid of the said procatalyst compo ⁇ sition and some organometallic co-catalyst compound of a metal belonging to the groups IA-IIIA of the periodic table of the elements.
• the co-catalyst compound is preferably an organometallic compound of aluminum such as a trialkylalumi- num, most preferably triethylaluminum.
• step A The product of step A was suspended in 5 mL of n-pentane.
• the yield was 2.621 g containing 2.4 wt% Ti, 2.8 wt% Mg,
• the composition of the catalyst was: Ti 3.5 %, Mg 4.1 %, Al 2.2 %, Cl 15.9 %.
• step B The product of step B was suspended in 5 mL of n-pentane.
• the composition of the catalyst was: Ti 3.3 %, Mg 4.7 %, Al 2.8 %, Cl 18.5 %.
• 1.527 g of the above obtained product were suspended in 5 L of n-pentane. 5.5 mL of a 10 wt% solution of TEA in pentane and 3.0 mL of a 10 wt% solution of EADC in pentane were added to the slurry. The mixture was stirred for 20 min at room temperature and dried in a stream of gaseous nitrogen for 45 min. The dried procatalyst was stirred for further 15 hrs at room temperature, washed 3 times with
• the composition of the catalyst was: Ti 3.1 %, Mg 4.6 %, Al 2.2 %, Cl 19.6 %.
• the pre-mixture solution was transferred by siphonation into 3.0 g of silica which had been dried at 150°C for 4 hrs, while stirring well.
• the mixture was dried in a flow of gaseous nitrogen at 125°C for 15 min, whereby 4.4 g of a free flowing powder was obtained, containing 18.5 wt% of butanol, 1.7 wt% of titanium and 2.0 wt% of magnesium.
• the composition of the catalyst was: Ti 1.2 %, Mg 1.5 %, Al 5.5 %, Cl 9.7 %.
• the pre-mixture solution was transferred by siphonation into hexamethyldisilazane-treated carrier while stirring well.
• the mixture was dried in a flow of gaseous nitrogen at 80°C in a bath for 30 min, whereby a dry, free flowing powder was obtained containing 20.3 wt% of butanol, 1.1 wt% of titanium and 1.8 wt% of magnesium.
• Tu cG-ttpcsxticn ⁇ the cataxyst was: T 1.3 %, Mg 1.5 %, Al 7.9 %, Cl 8.2 %.
• 1,0 g of the procatalyst prepared in step C were suspended in 3 mL of n-pentane.
• 4,1 mL of a 10 wt% solution of TEA in pentane and 2,1 mL of a 10 wt% solution of diethyl alu ⁇ minum chloride (DEAC) in pentane were added to the slurry.
• the mixture was stirred at room temperature for 20 min, dried in a flow of gaseous nitrogen for 20 min and stirred further as dry at room temperature for 16 hrs.
• the composition of the catalyst was: Ti 1.2 %, Mg 1.5 %, Al 7.1 %, Cl 7.5 %.
• Example 7 A Treatment of the carrier with hexamethyldisilazane
• Impregnation of the carrier with the pre-mixture was transferred by siphonation into the carrier while stirring well.
• the mixture was dried in a flow of gaseous nitrogen at 80"C in a bath for 45 min, whereby a free flowing powder was obtained containing 18.1 wt% of butanol, 1.2 wt% of titanium and 1.7 wt% of mag- nesium.
• 0.5 g of the above prepared procatalyst were suspended in 1.5 mL of n-pentane. 2.17 mL of a 10 wt% solution of TEA in pentane and 0.5 mL od a 10 wt% solution of EADC in pen ⁇ tane were added to the slurry. The mixture was stirred at room temperature for 20 min, dried in a flow of gaseous nitrogen for 20 min and stirred further as dry for 16 hrs.
• the composition of the catalyst was: Ti 0.98 %, Mg 1.5 %, Al 6.6 %, Cl 8.4 %.
• the pre-mixture solution was transferred by siphonation into the carrier while stirring well.
• the mixture was dried in a flow of gaseous nitrogen at 80°C in a bath for ⁇ _ hr, whereby a free flowing powder was obtained containing 16.5 wt% of butanol, 1.5 wt% of titanium and 1.5 wt% of mag ⁇ nesium.
• 1,0 g of the above prepared procatalyst were suspended in 3 mL of n-pentane. 3,96 mL of a 10 wt% solution of TEA in pentane and 1.16 mL of a 10 wt% solution of EADC in pentane were added to the slurry. The mixture was stirred at room temperature for 20 min, dried in a flow of gaseous nitrogen for 20 min and stirred as dry for further 16 hrs.
• the composition of the catalyst was: Ti 1.6 %, Mg 1.3 %, Al 5.8 %, Cl 7.3 %.
• the composition of the catalyst was: Ti 2.8 %, Mg 4.1 %, Al 2.9 %, Cl 18.9 %.
• Impregnation of the carrier with the pre-mixture was transferred by siphonation into 2.505 g of the above prepared HMDS-treated silica.
• the mixture was stirred at 110°C in a bath for 1 hr and dried in a stream of gaseous argon at the same temperature for 3 hrs 45 min, whereby a free flowing powder was obtained containing 12.9 wt% of butanol, 1.3 wt% of titanium and 2.4 wt% of magnesium.
• the composition of the catalyst was: Ti 1.3 %, Mg 2.0 %, Al 4.8 %, Cl 9.6 %.
• Impregnation of the carrier with the pre-mixture was transferred by siphonation into 1.2 g of the above prepared HMDS-treated silica.
• the mixture was stirred at 110°C in a bath for 1 hr and dried in a stream of nitrogen at 100°C in a bath for 1 hr, whereby a free flowing powder was obtained containing 15.1 wt% of ethanol, 3.3 wt% of titanium and 4.0 wt% of magnesium.
• the composition of the catalyst was: Ti 2.6 %, Mg 3.1 %, Al 7.8 %, Cl 20.3 %.
• TiPT titanium tetraisopropoxide
• the pre-mixture solution was transferred by siphonation into 4.0 g of the above prepared carrier.
• the mixture was stirred 85°C in a bath for 1 hr and dried at the same temperature for 6 hrs 45 min.
• the dry, free flowing procatalyst powder contained 2.6 % of titanium and 15.9 % of tetrahydrofuran.
• step D Treatment with DEAC
• the treatment was carried out in the same way as in step D of example 12 except that 680 mg of the procatalyst and 2.52 mL of a 10 wt% solution of DEAC in pentane were used.
• the composition of the catalyst was: Ti 2.3 %, Mg 3.3 %, Al 5.3 %, Cl 16.6 %.
• the catalysts prepared according to examples 1-10 were polymerized in pentane as follows:
• n-pentane treated with oxygen and moisture scavengers were added. Then 30-50 mg of proca- talyst dissolved in a small amount of pentane were added to the reactor through a feeding funnel and the temperature was raised to 80°C.
• the catalysts prepared according to examples 11-13 were polymerized in isobutane as follows:
• Co-polymerization of ethene was carried out in the same way as for the homo-polymerization except that the co-monomer (180 g of 1-butene) was added to the reaction medium (1.8 L of isobutane) immideately after the addition of co-catalyst.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=8530276

Family Applications (1)

Country Status (7)

Cited By (5)

Families Citing this family (2)

Citations (6)

Family Cites Families (1)

• 1990
  • 1990-04-12 FI FI901895A patent/FI91767C/fi not_active IP Right Cessation
• 1991
  • 1991-04-12 DE DE69122502T patent/DE69122502T2/de not_active Expired - Fee Related
  • 1991-04-12 EP EP91907558A patent/EP0525003B1/en not_active Expired - Lifetime
  • 1991-04-12 WO PCT/FI1991/000111 patent/WO1991016361A1/en active IP Right Grant
  • 1991-04-12 AT AT91907558T patent/ATE143674T1/de not_active IP Right Cessation
  • 1991-04-12 JP JP3506914A patent/JP2681310B2/ja not_active Expired - Lifetime
  • 1991-04-12 ES ES91907558T patent/ES2094810T3/es not_active Expired - Lifetime

Patent Citations (6)

Also Published As

Similar Documents

Legal Events