RU96115290A - PROCESS (CO) POLYMERIZATION OF OLEFINS - Google Patents

Claims (24)

1. A multistage polymerization process of one or more olefins of the formula CH ₂ = CHR, where R is hydrogen or an alkyl, cycloalkyl or aryl group with 1-10 carbon atoms, characterized in that it includes:
(A) a first polymerization stage, in which, in order to obtain an olefinic homo or copolymer, one or more of these olefins is polymerized in one or more reactors in the presence of a catalyst containing a reaction product between an aluminum alkyl compound and a solid component comprising a transition metal compound Mi selected from Ti and V, not containing M - π bonds, and magnesium halide in active form;
(B) the stage of processing, in which the product obtained in the first stage of polymerization (A), in any way
a) is brought into contact with a compound capable of deactivating the catalyst present in this step (A); and
b) is brought into contact with a transition metal compound M selected from Ti, Zr, V or Hf containing at least one M - π bond and, optionally, with an alkyl aluminum compound;
(C) a second polymerization stage in which one or more of said olefins is polymerized in one or more reactors in the presence of the product obtained in said processing stage (B).  2. The process of claim 1, wherein said homo or copolymer obtained in step (A) has a porosity expressed as a percentage of voids greater than 5%.  3. The process of claim 2, wherein said homo or copolymer obtained in step (A) has a porosity expressed as a percentage of voids higher than 10%. 4. The process of claim 1, wherein said magnesium halide in active form is MgCl ₂ , and said transition metal compound M ^{I is} selected from the group consisting of: titanium halides, halogen-alcoholates of titanium, VCl ₃ , VCl ₄ , VOCl ₃ , halogen-alcoholate vanadium. 5. The process according to claim 4, wherein said titanium compound is selected from the group comprising: TiCl ₄ , TiCl ₃ and halogen-alcoholates of the formula Ti (OR ^I ) _m X _n , in which R ^I is a hydrocarbon radical of 1-12 carbon atoms or a group —COR ^I , X is halogen, and (m + n) is the valence of titanium.  6. The process of claim 1, wherein the solid component used in the first polymerization stage (A) is in the form of spheroidal particles with an average diameter of from 10 to 150 microns.  7. The process of claim 1, wherein said transition metal compound M contains at least one ligand L coordinated by this metal, wherein said ligand has a monocyclic or polycyclic structure containing conjugated π electrons. 8. The process of Claim 7, wherein said transition metal compound M is selected from:
Cp ^I MR $\genfrac{}{}{0ex}{}{\text{one}}{\text{a}}$ R $\genfrac{}{}{0ex}{}{\text{2}}{\text{b}}$ R $\genfrac{}{}{0ex}{}{\text{3}}{\text{c}}$ ,
Cp ^I Cp ^II MR $\genfrac{}{}{0ex}{}{\text{one}}{\text{a}}$ R $\genfrac{}{}{0ex}{}{\text{2}}{\text{b}}$ ,
(Cp ^I - Ae - Cp ^II ) MR $\genfrac{}{}{0ex}{}{\text{one}}{\text{a}}$ R $\genfrac{}{}{0ex}{}{\text{2}}{\text{b}}$ ,
in which M represents Ti, V, Zr or Hf; Cp ^I and Cp ^II , the same or different, are cyclopentadienyl groups or substituted cyclopentadienyl groups; two or more substituents of said cyclopentadienyl groups may form one or more cycles containing from 4 to 6 carbon atoms; R ¹ , R ² , R ³ identical or different, represent hydrogen atoms, halogen, alkyl or alkoxy group with 1-20 carbon atoms, aryl, alkylaryl or arylalkyl with 6-20 carbon atoms, acyloxy group with 1-20 atoms carbon, allyl group, substituent containing a silicon atom; A is an alkenyl bridge or a bridge with a structure selected from:

= AlR ₁ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , = NR ₁ , = PR ₁ and = P (O) R ₁ , in which M ₁ is Si Ge or Sn; R ₁ , R ₂ , which are the same or different, are alkyl groups with 1-4 carbon atoms or aryl groups with 6-10 carbon atoms; a, b and c independently of one another are integers from 0 to 4; e is an integer from 0 to 6, and two or more of the radicals R ¹ , R ² and R ³ can form a cycle. 9. The process of claim 7, wherein said transition metal compound is selected from compounds having the following structure:
(Me ₅ Cp) MMe ₃ , (Me ₅ Cp) M (OMe) ₃ , (Me ₅ Cp) MCl ₃ , (Cp) MCl ₃ , (Cp) MMe ₃ , (MeCp) MMe ₃ , (Me ₃ Cp) MMe ₃ , (Me ₄ Cp) MCl ₃ , (Ind) MBenz ₃ , (H ₄ Ind) MBenz ₃ , (Cp) MBu ₃ . 10. The process of claim 7, wherein said transition metal compound is selected from compounds having the following structure:
(Cp) ₂ MMe ₂ , (Cp) ₂ MPh ₂ , (Cp) ₂ MEt ₂ , (Cp) ₂ MCl ₂ , (Cp) ₂ M (OMe) ₂ , (Cp) ₂ M (OMe) Cl, (MeCp ) ₂ MCl ₂ , (Me ₅ Cp) ₂ MCl ₂ , (Me ₅ Cp) ₂ MMe ₂ , (Me ₅ Cp) ₂ MMeCl, (Cp) (Me ₅ Cp) MCl ₂ ,
(1-MeFlu) ₂ MCl ₂ , (BuCp) ₂ MCl ₂ , (Me ₃ Cp) ₂ MCl ₂ , (Me ₄ Cp) ₂ MCl ₂ , (Me ₅ Cp) ₂ M (OMe) ₂ , (Me ₅ Cp ) ₂ M (OH) Cl, (Me ₅ Cp) ₂ M (OH) ₂ , (Me ₅ Cp) ₂ M (C ₆ H ₅ ) ₂ , (Me ₅ Cp) ₂ M (CH ₃ ) Cl, (EtMe ₄ Cp) ₂ MCl _2, [(C ₆ H ₅₎ Me ₄ Cp] ₂ MCl _2, (Et ₅ Cp) ₂ MCl _2, (Me ₅ Cp) ₂ M (C ₆ H ₅₎ Cl, (Ind) ₂ MCl ₂ , (Ind) ₂ MMe ₂ , (H ₄ Ind) ₂ MCl ₂ , (H ₄ Ind) ₂ MMe ₂ , {[(Si (CH ₃ ) ₃ ] ₂ Cp} ₂ MCl ₂ , {[(Si ( CH ₃ ) ₃ ] Cp} ₂ MCl ₂ , (Me ₄ Cp) (Me ₅ Cp) MCl ₂ . 11. The process of claim 7, wherein said transition metal compound is selected from compounds having the following structure:
C ₂ H ₄ (Ind) ₂ MCl ₂ , C ₂ H ₄ (Ind) ₂ MMe ₂ , C ₂ H ₄ (H ₄ Ind) ₂ MCl ₂ , C ₂ H ₄ (H ₄ Ind) ₂ MMe ₂ ,
Me ₂ Si (Me ₄ Cp) ₂ MCl ₂ , Me ₂ Si (Me ₄ Cp) ₂ MMe ₂ , Me ₂ SiCp ₂ MCl ₂ , Me ₂ SiCp ₂ MMe ₂ ,
Me ₂ Si (Me ₄ Cp) ₂ MMeOMe, Me ₂ Si (Flu) ₂ MCl ₂ , Me ₂ Si (2-Et-5-iPrCp) ₂ MCl ₂ , Me ₂ Si (H ₄ Ind) ₂ MCl ₂ , Me ₂ Si (H ₄ Flu) ₂ MCl ₂ , Me ₂ SiCH ₂ (Ind) ₂ MCl ₂ , Me ₂ Si (2-MeH ₄ Ind) ₂ MCl ₂ , Me ₂ Si (2-MeInd) ₂ MCl ₂ , Me ₂ Si (2-Et-5-iPrCp) ₂ MCl ₂ , Me ₂ Si (2-Me-5-EtCp) ₂ MCl ₂ , Me ₂ Si (2-Me-5-MeCp) ₂ MCl ₂ , Me ₂ Si ( 2-Me-4,5-benzoindenyl) ₂ MCl ₂ ,
Me ₂ Si (4,5-benzoindenyl) ₂ MCl ₂ , Me ₂ Si (2-EtInd) ₂ MCl ₂ , Me ₂ Si (2-iPrInd) ₂ MCl ₂ ,
Me ₂ Si (2-tert-butyl-Ind) ₂ MCl ₂ , Me ₂ Si (3-tert-butyl-5-MeCp) ₂ MCl ₂ , Me ₂ Si (3-tert-butyl-5-MeCp) ₂ MMe ₂ , Me ₂ Si (2-MeInd) ₂ MCl ₂ , C ₂ H ₄ (2-Me-4,5-benzoindenyl) ₂ MCl ₂ , Me ₂ C (Flu) CpMCl ₂ , Ph ₂ Si (Ind) ₂ MCl ₂ , Ph (Me) Si (Ind) ₂ MCl ₂ , C ₂ H ₄ (H ₄ Ind) M (NMe ₂ ) OMe, isopropylidene- (3-tert-butyl-Cp) (Flu) MCl ₂ , Me ₂ C (Me ₄ Cp) (MeCp) MCl ₂ , Me ₂ Si (Ind) ₂ MCl ₂ , Me ₂ Si (Ind) ₂ MMe ₂ , Me ₂ Si (Me ₄ Cp) ₂ MCl (OEt), C ₂ H ₄ ( Ind) ₂ M (NMe ₂ ) ₂ , C ₂ H ₄ (Me ₄ Cp) ₂ MCl ₂ ,
C ₂ Me ₄ (Ind) ₂ MCl ₂ , MeSi (3-MeInd) ₂ MCl ₂ , C ₂ H ₄ (2-MeInd) ₂ MCl ₂ , C ₂ H ₄ (3-MeInd) ₂ MCl ₂ , C ₂ H ₄ (4.7-Me ₂ Ind) ₂ MCl ₂ , C ₂ H ₄ (5.6-Me ₂ Ind) ₂ MCl ₂ , C ₂ H ₄ (2,4,7-Me ₃ Ind) ₂ MCl ₂ , C ₂ H ₄ (3,4,7-Me ₃ Ind) ₂ MCl ₂ , C ₂ H ₄ (2-MeH ₄ Ind) ₂ MCl ₂ ,
C ₂ H ₄ (4.7-Me ₂ H ₄ Ind) ₂ MCl ₂ , C ₂ H ₄ (2,4,7-Me ₃ H ₄ Ind) ₂ MCl ₂ , Me ₂ Si (4,7-Me ₂ Ind) ₂ MCl ₂ ,
Me ₂ Si (5,6-Me ₂ Ind) ₂ MCl ₂ , Me ₂ Si (2,4,7-Me ₃ H ₄ Ind) ₂ MCl ₂ . 12. The process of claim 1, wherein said catalyst used in the first polymerization stage (A) contains a reaction product between an alkyl aluminum compound, an electron donor compound (external donor) and a solid component containing at least one transition metal compound M ^I , selected from Ti and V and not containing bonds M ^I - π, and magnesium halide in active form and electron-donor compound (internal donor). 13. The process of claim 12, wherein said electron donor compound (external donor) is selected from silicon compounds of the formula R ₁ R ₂ Si (OR) ₂ , where R ₁ and R ₂ , which may be the same or different, are alkyl, cycloalkyl or aryl groups with 1-18 carbon atoms, and R is an alkyl radical with 1-4 carbon atoms. 14. The process of claim 1, wherein said compound capable of deactivating the catalyst and used in step (A) is selected from the group consisting of: CO, COS, CS ₂ , CO ₂ , O ₂ , acetylene compounds, allene compounds and compounds General formula R _y-1 XH, where R represents hydrogen or a hydrocarbon group with 1-10 carbon atoms, X represents O, N or S, and y is the valency of X.  15. The process of claim 1, wherein said compound capable of deactivating the catalyst present in step (A) is water. 16. The process of claim 1, wherein in step (B) the product obtained in the first polymerization stage (A), (a) is brought into contact with aliphatic hydrocarbons in solution, suspension or dispersion, the amount of said deactivating compound being such that the molar ratio of this compound and M ^{I is} greater than 50; and b) is treated with solutions containing the compound of the transition metal M and an aluminum alkyl compound selected from aluminum trialkyls in which the alkyl groups contain from 1 to 12 carbon atoms, and linear or cyclic alumoxane compounds with repeating monomeric units - (R ₄ ) AlO -, where R ₄ is an alkyl group with 1-12 carbon atoms or a cycloalkyl or aryl group with 6-10 carbon atoms, and these alumoxane compounds contain from 1 to 50 repeating monomeric units. 17. The process according to claim 1, wherein at the polymerization stage (C) at least one reactor is charged with the reaction product obtained in the processing step (B) and, simultaneously or separately, with an alkyl aluminum compound selected from aluminum trialkyls in which the alkyl groups contain from 1 to 12 carbon atoms, and linear or cyclic alumoxane compounds containing a repeating monomer unit - (R ₄ ) AlO-, where R ₄ is an alkyl group with 1-12 carbon atoms or a cycloalkyl or aryl group with 6-10 carbon atoms These alumoxane compounds contain from 1 to 50 repeating monomeric units. 18. The process of claim 1, wherein the polymerization stage (A) is carried out in a liquid phase, wherein said liquid phase contains a hydrocarbon solvent or one or more olefins CH ₂ = CHR, and in which the polymerization stage (C) is carried out at least one fluidized bed reactor or mechanically stirred bed.  19. The process of claim 1, wherein in both stages, (A) and (C), the polymerization is carried out in gas-phase fluidized bed or mechanically stirred bed reactors.  20. The process of claim 1, wherein the processing step (B) is carried out in a gas-phase loop reactor.  21. The process of claim 1, wherein the amount of polymer obtained in step (A) is, by weight, from 10 to 90% of the total amount of polymer obtained in steps (A) and (C).  22. The process of claim 1, wherein the amount of polymer obtained in step (A) is from 20 to 80% by weight of the total amount of polymer obtained in steps (A) and (C). 23. A multistage process for producing heterophasic propylene copolymers, characterized in that it includes: (A) a first polymerization stage in which propylene is polymerized in one or more reactors, and possibly ethylene and / or one or more CH ₂ = CHR ^II olefins, where R ^II is a hydrocarbon radical with 2-10 carbon atoms in the presence of a catalyst containing a reaction product between an aluminum alkyl compound, optionally an electron donor compound (external donor) and a solid component comprising the compound a transition metal M ^I , selected from Ti and V, free of M ^I - π bonds, and magnesium halide in active form and, optionally, an electron-donor compound (internal donor). An olefin polymer is obtained, the porosity of which, expressed as a percentage of voids, is above 10%, the content of monomer units, derivatives of ethylene and / or olefin CH ₂ = CHR ^II is less than 20% by weight, the content of monomer units, derivatives of propylene is more weight by weight 80%, and insolubility in xylene - above 60%;
(B) the stage of processing, in which the specified product obtained in the first stage (A), in any way
a) is brought into contact with a compound capable of deactivating the catalyst present in this step (A); and
b) is brought into contact with a transition metal compound M selected from Ti, Zr, V or Hf, containing at least one M - π bond and possibly with an alkyl aluminum compound. (C) a second polymerization stage in which one or more olefins CH ₂ = CHR are polymerized (where R is hydrogen, alkyl, cycloalkyl or aryl radicals with 1-10 carbon atoms) in one or more reactors in the presence of the product obtained on said processing stages (B). A substantially amorphous olefinic (co) polymer is obtained, its amount is by weight from 20 to 80% of the total amount of polymer obtained in steps (A) and (C).  24. Olefinic homo-or copolymers obtained by the process of claim 1 or 23.