Patent EA-000615-B1 (EA)
Title: Process and catalyst component for homo- andcopolymerization of olefins
Inventor: KARBASI AMIR K
IPC: C08F4/658
Filed: 1996-05-06
Abstract: 1. A process for the homo- or copolyroerization of olefins by contacting one or more polymerizable olefins having the general formula CH2 = CR1R2 (I) where R1 and R2 are the same or different and are hydrogen or a C1-C10 alkyl, with a polymerization catalyst system obtained by contacting at least the following components: 1) a solid procatalyst which contains titanium (Ti), chlorine and magnesium; 2) a cocatalyst which contains aluminum (Al) and a C1-C10 alkyl; and possibly 3) an external electron donor (ED), characterized in that it comprises steps wherein a) in the absence of polymerizable olefin, a first amount of cocatalyst and at least one-half of the total amount of procatalyst are contacted in such a way that the cocatalyst is added in the form of a solution, the concentration of which is from 0.001 to 2.0 mol/dm<3>; b) the precontact product, a second amount of cocatalyst, and one or more polymerizable olefins according to Formula (I) presented above are contacted in order to produce a first homo-or copolymerization product; c) the homo- or copolymerization product is recovered. 2. A process for the homo- or copolyroerization of olefins by contacting one or more polymerizable olefins having the general formula CH2 = CR1R2 (I) where R1 and R2 are the same or different and are hydrogen or a C1-C10 alkyl, with a polymerization catalyst system obtained by contacting at least the following components: 1) a solid procatalyst which contains titanium (Ti), chlorine and magnesium; 2) a cocatalyst which contains aluminum (Al) and a C1-C10 alkyl; and possibly 3) an external electron donor (ED), characterized in that it comprises steps wherein a) in the absence of polymerizable olefin, a first amount of cocatalyst and at least one-half of the total amount of procatalyst are contacted in such a way that the cocatalyst is added in the form of a solution, the concentration of which is from 0.001 to 2.0 mol/dm<3>; b) the precontact product, a second amount of cocatalyst, and one or more polymerizable olefins according to formula (I) presented above are contacted in order to produce a prepolymerization product. c) the prepolymerization product, a third amount of cocatalyst, and one or more polymerizable olefins according to formula (I) are contacted in order to produce a second homo- or copolymerization product; and d) the prepolymerization product, and the the homo- or copolymerization product is recovered. 3. A process according to Claim 1 or2, characterized in that, independently of one another, i) only one type of procatalyst is used; ii) only one type of cocatalyat is used; iii) substantially the entire amount of procatalyst is used in step a). 4. A process according to Claim 1, 2 or 3, characterized in that in step a), in the absence of polymerizable olefin, the first amount of cocatalyst and at least one-half of the entire amount of procatalyst are contacted so that the molar ratio Al/Ti is within a range of 0.5-16, preferably within a range of 1.0-8.0, most preferably within a range of 1.5-5.0. 5. A process according to Claim 1, 2, 3 or 4, characterized in that the first amount of cocatalyst, used in step a), is introduced in the form of a solution having a cocatalyst concentration within a range of 0.001-1.0 mol/dm<3>, preferably within a range of 0.05-0.5 mol/dm<3>. 6. A process according to any of the above Claims, characterized in that the first amount of cocatalyst, used in step a), constitutes 0.1-30 % by weight, preferably 0.5-10 % by weight, and most preferably 1.0-5.0 % by weight, of the combined weight of the first amount of cocatalyst and the second amount of cocatalyst, used in step b). 7. A process according to any of the above Claims, characterized in that in step a), in the absence of polymerizable olefin, a first amount of cocatalyst, at least one-half of the total amount of procatalyst, and a first amount of external electron donor (ED) are contacted, preferably so that the molar ratio Al/ED is within a range of 0.5-100, in order to produce a precontact product, and in step b) this precontact product, a second amount of cocatalyst, a second amount of external electron donor (ED) and one of more polymerizable olefins according to formula (I) are contacted in order to produce a first homo- or copolymerization product and c) the homo- or copolyraerization product is recovered. 8. A process according to Claim 6, characterized in that in step a), in the absence of polymerizable olefin, a first amount of cocatalyst, at least one-half of the total amount of procat-alyst, and a first amount of external electron donor (ED) are contacted so that the molar ratio Al/ED is within a range of 1.0-50, preferably approx 1.0-20. 9. A process according to Claim 6 or 7, characterized in that in step a) the first amount of external electron donor (ED) is introduced in a solution, preferably in the said cocatalyst solution, the electron donor concentration in the solution being preferably within a range of 0.0002-0.4 mol/dm, more preferably 0.0002-0.2 mol/dm, most preferably within a range of 0.01-0.1 mol/dm. 10. A process according to any of the above Claims, characterized in that the temperature used in step a) is between -50 and +100 degree C, preferably between -20 and +50 degree C, and most preferably between -5 and +30 degree C. 11. A process according to any of the above Claims, characterized in that the solvent used in step a) is a C6-C12 hydrocarbon, preferably a hydrocarbon having a density within a range of 0.6-0.9 g/cm<3> such as n-heptane. 12. A process according to any of the above Claims, characterized in that the contact time used in step a) is within a range of 10 min.-5 hr, preferably within a range of 10 min - 2 hr. 13. A process according to any of the above Claims, characterized in that the procatalyst used in step a) is a procatalyst not coated with a prepolymer. 14. A process according to any of the above Claims, characterized in that in step b) the precontact product, a second amount of cocatalyst, possibly a second amount of electron donor, and one or more olefins according to Formula (I) are contacted so that the total molar ratio Al/Ti is within a range of 50-1500. 15. A process according to any of the above Claims, characterized in that the polymerizable olefin according to formula (I) is propylene. 16. A process according to any of the above Claims, characterized in that hydrogen, H2, is introduced into step b) in order to control the molar mass of the homopolymerization, copolymerization product. 17. A process according to any of the above Claims, characterized in that the procatalyst comprises a titanium compound, containing at least one Ti-halide bond, O supported on an active g-halide, preferably a reaction product of a MgCl2 support and TiCl4. 18. A process according to any of the above Claims, characterized in that the cocatalyst is a tri-C1-C10-alkyl aluminum, preferably triethyl aluminum. 19. A process according to any of the above Claims, characterized in that the external electron donor is an alkoxy silane, preferably dialkyl dialkoxy silane, such as cyclohexyl methyl dimethoxy silane (CHMMS) and dicyclopentyl dimethoxy silane (DCPDMS). 20. A catalyst component intended for the polymerization of one or more polymerizable olefins having the general formula CH2 = CR1R2 (I) where R1 and R2 are the same or different and are hydrogen or a C1-C10 alkyl, with a polymerization catalyst system obtained by contacting at least the following components: 1) a solid procatalyst which contains titanium (Ti), chlorine and magnesium; 2) a cocatalyst which contains aluminum (Al) and a C1-C10 alkyl; and possibly; 3) an external electron donor (ED); characterized in that in its preparation the cocatalyst and the procatalyst are contacted in the absence of polymerizable olefin so that the molar ratio Al/Ti is within a range of 0.1-20. 21. The use of a catalyst component according to Claim 19 for the homo- or copolymerization of one or more polymerizable olefins according to Formula (I), characterized in that (α) the said catalyst component, an additional amount of cocatalyst, and one or more polymerizable olefins according to Formula (I) are contacted in order to produce a first homo- or copolymerization product or, alternatively, a prepolymerization product; (β) alternatively, the prepolymerization product, a second additional amount of cocatalyst, and one or more polymerizable olefins according to Formula (I) are contacted in order to produce a second homo- or copolyroerization product; and (γ) the first homo- or copolymerization product, the prepolymerization product, or the second homo- or copolymerization product is recovered.