RU96105711A - ETHYLENE COPOLYMERS, ETHYLENE-BASED PREPARATION OF POLYMERS AND THE CATALYST SYSTEM USED IN IT - Google Patents

Claims (17)

1. A copolymer of ethylene with at least one comonomer selected from α-olefins of the formula
CH ₂ = CH - CH ₂ R,
where R is hydrogen or a linear, branched or cyclic alkyl having 1 to 20 carbon atoms, cycloolefins and polyenes with an ethylene content of 80 to 99 mol.%, a content of units derived from comonomers of α-olefin, cycloolefin and / or polyene 1 - 20 mol.%, Characterized in that in the FTPE analysis (fractionation by temperature increasing elution), an amount equal to at least 90 wt.% Of the copolymer is eluted in the temperature range of less than 50 ^o C and M _w / M _n > 3, where M _w - weight average molecular weight and M _n - number average molecular weight , both determined by gel permeation chromatography.  2. The copolymer according to claim 1, in which the ratio value of the melting index F / E, where condition F includes a load of 21.6 kg, and condition E includes a load of 2.16 kg exceeds 100. 3. The copolymer according to claim 1 or 2, having a density of less than 0.94 g / cm ³ . 4. The copolymer according to claim 1 or 2, having a solubility of less than 10% by weight in xylene at 25 ^o C.  5. The copolymer according to claim 1 or 2, in which the comonomer is 1-butene. 6. Ethylene copolymer with 1-butene containing units derived from 1-butene in the range from 1 to 20 mol.%, Characterized in that the percentage by weight of 1-butene (% B), determined by analysis of nuclear magnetic resonance carbon-13, and the density (D) of the copolymer correspond to the following relationship:
% B + 285D ≤ 272,
M _w / M _n > 3, where M _w is the weight average molecular weight and M _n is the number average molecular weight, both determined by gel permeation chromatography. 7. The process of preparation of ethylene polymers, including the reaction of polymerization of ethylene in the presence of a catalyst consisting of the reaction product:
(A) mixtures of racemic and meso-isomers of the compound of a stereo-hard metallocene transition metal belonging to groups III, IV or V or lanthanides in the Periodic Table of Elements, with two cyclopentadienyl ligands bound to one another by a chemical linkage,
(B) at least one cocatalyst capable of activating both the racemic form and the meso form of a metallocene compound selected from alumoxanes and compounds capable of forming the alkyl metallocene cation. 8. The process according to claim 7, in which the reaction of polymerization of ethylene is carried out in the presence of a comonomer selected from α-olefins of the formula
CH ₂ = CH - CH ₂ R,
where R is a linear, branched or cyclic alkyl having 1 to 20 carbon atoms, cycloolefins and / or polyenes.  9. The process of Claim 7 or 8, in which the racemic form and the meso form of the metallocene compound are present in a mass ratio of 99: 1 and 1: 99, respectively. 10. The process of claim 7, wherein the metallocene compound is represented by Formula I

where M is a metal selected from T; Zr and Hf;
R ¹ - C ₁ - C ₂₀ -alkyl, C ₃ - C ₂₀ -cycloalkyl, C ₂ - C ₂₀ -alkenyl, C ₆ - C ₂₀ -aryl, C ₇ - C ₂₀ -alkylaryl or C ₇ - C _20- arylalkyl may contain Si or Ge atoms;
R ² and R ³ - hydrogen atoms, C ₁ - C ₂₀ -alkyl, C ₃ - C ₂₀ -cycloalkyl, C ₂ - C ₂₀ -alkenyl, C ₆ - C ₂₀ -aryl, C ₇ - C ₂₀ -alkylaryl or C ₇ - C ₂₀ arylalkyl, may contain Si or Ge atoms;
if the substituent R ² atoms differ from hydrogen, the substituent R ¹ and R ² atoms on the same cyclopentadienyl can form a ring containing from 5 to 20 carbon atoms;
R ⁴ - divalent group selected from (CR $\genfrac{}{}{0ex}{}{\text{five}}{\text{2}}$ ) _n , (SiR $\genfrac{}{}{0ex}{}{\text{five}}{\text{2}}$ ) _n , (CeR $\genfrac{}{}{0ex}{}{\text{five}}{\text{2}}$ ) _n , NR ⁵ or PR ⁵ , where the substituent R ⁵ atoms, which may be identical or different, are C ₁ - C ₂₀ alkyl, C ₃ - C ₂₀ cycloalkyl, C ₂ - C ₂₀ alkenyl, C ₆ - C ₂₀ -aryl, C ₇ - C ₂₀ -alkylaryl or C ₇ - C ₂₀ -arylalkyl, if R ⁴ - (CR $\genfrac{}{}{0ex}{}{\text{five}}{\text{2}}$ ) _n , (SiR $\genfrac{}{}{0ex}{}{\text{five}}{\text{2}}$ ) _n , or (GeR $\genfrac{}{}{0ex}{}{\text{five}}{\text{2}}$ ₂ ) two substituent R ⁵ atoms on the same carbon, silicon or germanium atom can form a ring containing from 3 to 8 atoms, with n being an integer from 1 and 4, preferably from 1 to 2;
substituents X ¹ and X ² - halogen atoms, R ⁶ , OR ⁶ , SR ⁶ , NR $\genfrac{}{}{0ex}{}{\text{6}}{\text{2}}$ or PR $\genfrac{}{}{0ex}{}{\text{6}}{\text{2}}$ where the substituent R ⁶ atoms which may be identical or different are C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₂ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, C ₇ - C ₂₀ -alkylaryl or C ₇ - C ₂₀ -arylalkyl and may contain Si or Ge atoms. 11. The process of claim 10, in which the metallocene compound is represented by formula II

where M, R ³ , R ⁴ , X ¹ and X ² have the values indicated in paragraph 10;
R ⁷ is hydrogen, C ₁ - C ₁₀ -alkyl, C ₃ - C ₁₀ -cycloalkyl, C ₂ - C ₁₀ -alkenyl, C ₆ - C ₁₀ -aryl, C ₇ - C ₁₀ -alkylaryl or C ₇ - C ₁₀ is arylalkyl and may contain Si or Ge atoms and, in addition, two adjacent substituent R ⁷ atoms may form a ring having 5-8 carbon atoms.  12. The process of claim 11, wherein the metallocene compound is ethylene bis (4,7-dimethyl-1-indenyl) zirconium dichloride. 13. The process according to claim 10, wherein the metallocene compound is represented by formula III

where M, R ³ , R ⁴ , X ¹ and X ² have the values indicated in paragraph 10;
R ⁷ substituents are hydrogen, C ₁ –C ₁₀ alkyl, C ₃ –C ₁₀ cycloalkyl, C ₂ –C ₁₀ alkenyl, C ₆ –C ₁₀ aryl, C ₇ –C ₁₀ alkylaryl, or C ₇ - C ₁₀ -arylalkyl and may contain Si or Ge atoms and, in addition, two adjacent substituent R ⁷ atoms may form a ring having 5 to 8 carbon atoms.  14. The process according to claim 7, in which the alumoxane is methylalumoxane.  15. The process according to claim 7, in which the catalyst has an inert carrier.  16. The process of claim 15, wherein the carrier is a porous organic carrier with functional groups having active hydrogen atoms.  17. The process of claim 15, wherein the organic carrier is a styrene polymer with partial intermolecular bonds.