Ethylene-based polymers and methods for producing the same

Abstract

To provide an ethylene-based polymer few in vinylene group and internal unsaturated bonds and many in a long-chained branched structure, and excellent in heat stability.SOLUTION: An ethylene-based polymer satisfies the following conditions (1) to (5). (1) MFR (190°C, 21.18 N load) is 0.001 g / 10 minutes or more and 100 g / 10 minutes or less. (2) Density is 0.895 g / cm3 to 0.970 g / cm3. (3) The sum (V1+V2) of the number of vinyl groups per 1000 carbon atoms (V1) and the number of vinylidene groups per 1000 carbon atoms (V2) is more than 0.13 and 3 or less. (4) The sum (V3+V4) of the number of vinylene groups per 1000 carbon atoms (V3) and the number of trisubstituted unsaturations per 1000 carbon atoms (V4) is less than 0.39. (5) In the branching index g' measured by a GPC measurement device combining a differential refractometer, a viscosity detector, and a light scattering detector, the lowest value (gL) in the molecular weight range of 100,000 to 1,000,000 is 0.20 or more and 0.75 or less.SELECTED DRAWING: None

Claims

1. An ethylene polymer that satisfies the following conditions (1) to (5), and further satisfies the following condition (9). (1) The MFR (at 190°C, with a load of 21.18 N) is 0.001 g / 10 min or more and 100 g / 10 min or less. (2) Density is 0.895 g / cm³ ３ ~0.970g / cm ３ That is the case. (3) Number of vinyl groups per 1000 carbon atoms (V １ ) and the number of vinylidene groups per 1000 carbon atoms (V ２ ) sum (V １ +V ２ ) is greater than 0.13 and less than or equal to 3. (4) The sum (V ３ + V ４ ) of the vinylene group number per 1000 carbon atoms (V ３ ) and the trisubstituted unsaturation number per 1000 carbon atoms (V ４ ) is less than 0.39.​​​​​​​​ (5) The lowest value (g) of the branching index g' between 100,000 and 1,000,000 molecular weight, measured by a GPC measuring device combining a differential refractometer, a viscosity detector, and a light scattering detector. Ｌ The value is between 0.20 and 0.

75. (9) The sum of the proportion of components whose molecular weight is equal to or greater than the weight-average molecular weight among components that elute at or below the temperature at which the amount of elution determined from the integral elution curve measured by cross-fractional chromatography (CFC) becomes 50% by weight (W2) and the proportion of components whose molecular weight is less than the weight-average molecular weight among components that elute at temperatures above the temperature at which the amount of elution determined from the integral elution curve becomes 50% by weight (W3) (W2 + W3) is 45% by weight or more and less than 80% by weight.

2. Furthermore, the ethylene polymer according to claim 1 satisfies the following condition (6a). (6a) Number of vinyl groups per 1000 carbon atoms (V １ The value is greater than 0.05 and less than or equal to 2.

3. Furthermore, the ethylene polymer according to claim 1 or 2 satisfies the following condition (7b). (7b) Number of trisubstituted unsaturated compounds per 1000 carbon atoms (V ４ ) is less than 0.

21.

4. Furthermore, the ethylene polymer according to any one of claims 1 to 3 satisfies the following condition (6b). (6b) Number of vinylidene groups per 1000 carbon atoms (V ２ ) is 1 or less.

5. Furthermore, the ethylene polymer according to any one of claims 1 to 4 satisfies the following condition (7a). (7a) Number of vinylene groups per 1000 carbon atoms (V ３ ) is less than 0.

18.

6. Furthermore, the ethylene polymer according to any one of claims 1 to 5 satisfies the following condition (8). (8) The molecular weight distribution (Mw / Mn) determined by weight-average molecular weight (Mw) and number-average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 2.5 or greater and 10.0 or less.

7. Furthermore, the ethylene polymer according to any one of claims 1 to 6 satisfies the following condition (10). (10) Of the components that elute at a temperature below which the amount of eluted determined from the integral elution curve measured by cross-fractional chromatography (CFC) is 50% by weight, the proportion of components whose molecular weight is equal to or greater than the weight-average molecular weight (W ２ The proportion of components whose molecular weight is equal to or greater than the weight-average molecular weight (W) among the components that dissolve at temperatures above the temperature at which the amount of eluted obtained from the integral dissolution curve measured by CFC is 50% by weight (W) ４ The value obtained by subtracting (W) ２ -W ４ ) is greater than -4% by weight and less than 30% by weight.

8. Furthermore, the ethylene polymer according to any one of claims 1 to 7 satisfies the following condition (11). (11) The number of long-chain branches (LCBs) per 1000 carbon atoms is greater than 0.2 and less than 2.

0.

9. The ethylene-based polymer according to any one of claims 1 to 8, which is an ethylene homopolymer or a copolymer of ethylene and an olefin having 3 to 10 carbon atoms.

10. A method for producing an ethylene polymer according to any one of claims 1 to 9, comprising polymerizing at least ethylene in the presence of an olefin polymerization catalyst containing the following components (A1), (B), and (C). Component (A1): A crosslinked cyclopentadienylindenyl compound containing a transition metal element, wherein the cyclopentadienyl ring has at least one substituent selected from the group consisting of a halogen atom, a C1-C20 hydrocarbon group, a C1-C18 silicon-containing hydrocarbon group containing 1-6 silicon atoms, a C1-C20 halogen-containing hydrocarbon group, a C1-C20 hydrocarbon group containing an oxygen atom, a C1-C20 hydrocarbon group containing a sulfur atom, a C1-C20 hydrocarbon group containing a nitrogen atom, a C1-C20 hydrocarbon group containing a phosphorus atom, a C1-C20 alkoxy group, a C6-C20 aryloxy group, a C1-C20 hydrocarbon group-substituted amino group, and a C1-C20 hydrocarbon group-substituted silyl group. Component (B): A compound that reacts with component (A1) to produce a cationic metallocene compound. Component (C): Inorganic compound carrier

11. A method for producing an ethylene polymer according to any one of claims 1 to 9, comprising polymerizing at least ethylene in the presence of an olefin polymerization catalyst containing the following components (A2), (B), and (C). Component (A2): A crosslinked cyclopentadienylindenyl compound containing a transition metal element, having a five-membered ring structure substituent on the indenyl ring. Component (B): A compound that reacts with component (A2) to produce a cationic metallocene compound. Component (C): Inorganic compound carrier

12. The method for producing an ethylene polymer according to claim 10, wherein the component (A1) has a five-membered ring structure substituent on the indenyl ring.

13. A method for producing an ethylene-based polymer according to any one of claims 10 to 12, comprising polymerizing at least ethylene in a gas-phase continuous polymerization apparatus or a slurry continuous polymerization apparatus.

14. A method for producing an ethylene-based polymer according to any one of claims 10 to 13, wherein polymerization is carried out at a polymerization temperature of 60°C to 110°C and an ethylene partial pressure in the range of 0.2 MPa to 1.9 MPa.

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