KR940011560A - Ethylene / α-olefin copolymer composition, graft modified ethylene / α-olefin copolymer composition, ethylene copolymer composition and multistage olefin polymerization method - Google Patents

Abstract

Ethylene / α-olefin copolymer composition composed of ethylene / α-olefin copolymer and another ethylene / α-olefin copolymer [B1], wherein the former ethylene / α-olefin copolymer is at least an organoaluminumoxy compound (a) and The latter can be produced in the presence of a catalyst for olefin polymerization of two specific metallocene compounds (b). The latter ethylene / α-olefin copolymer [B1] is composed of an organoaluminum oxy compound (a) and a specific metallocene. A graft modified ethylene / α-olefin copolymer composition obtained by graft copolymerization of an ethylene / α-olefin copolymer composition with a polar monomer, which may be prepared in the presence of a catalyst for olefin polymerization of compound (b ′), The / α-olefin copolymer composition is an ethylene / α-olefin copolymer prepared in the presence of an olefin polymerization catalyst made of an organoaluminum oxy compound (a) and a specific metallocene compound (b ') and the ethylene / α-olefin. Copolymer [B 1]. The graft-modified ethylene / α-olefin copolymer composition and the ethylene / α-olefin copolymer composition comprising polyolefin, an organoaluminum oxy compound (a), a specific metallocene compound (bI) and a specific metallocene compound (b In the presence of a catalyst for olefin polymerization containing III), an ethylene / α-olefin copolymer [Al] production step, an olefin polymerization containing an organoaluminum oxy compound (a) and a specific metallocene compound (b ') It is a multi-stage olefin polymerization method comprising the step of preparing an ethylene / alpha -olefin copolymer [B1] in a polymerizer different from the copolymerization polymerizer of the above step in the presence of a solvent catalyst. The ethylene / α-olefin copolymer composition of the present invention is excellent in heat safety and moldability. From this composition, a film with high transparency, high mechanical strength and high blocking resistance can be produced. The graft modified ethylene / α-olefin copolymer composition of the present invention is excellent in moldability. From this composition, the film which has transparency and favorable adhesiveness with respect to a high polar material can be manufactured. The ethylene / α-olefin copolymer composition of the present invention is excellent in moldability. From this composition, the film which has high transparency and favorable adhesiveness with respect to a high polar material can be manufactured. In the multistage olefin polymerization method of the present invention, an ethylene / α-olefin copolymer composition having high thermal stability and moldability can be prepared, and a film having high transparency and high mechanical strength can be produced from this composition.

Description

Ethylene / α-olefin copolymer composition, graft modified ethylene / α-olefin copolymer composition, ethylene copolymer composition and multistage olefin polymerization method

As this is a public information case, the full text was not included.

1 is an explanatory diagram of a method for producing a catalyst for olefin polymerization used in the multistage olefin polymerization method according to the present invention.

Claims (16)

[A1] A periodic table containing a ligand having a (a) organic aluminum oxy compound and (b) a cyclopentadienyl skeleton. Group IV transition metal compound having 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization of at least two kinds. obtained by copolymerizing α-olefin and ethylene, and further having the following characteristics; (Ai) Ethylene / α-olefin copolymer having a density in the range of 0.850 to 0.980 g / cm 3 and (A-ii) intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g. Carbon atoms in the presence of a catalyst for olefin polymerization of 20 to 90% by weight of a periodic table of Group IV transition metal compounds containing a ligand having a [B1] (a) organic aluminum oxy compound and a (b ') cyclopentadienyl skeleton It is obtained by copolymerizing ethylene and alpha-olefin of -20, and is different from the said ethylene / alpha-olefin copolymer (A1), and has the following characteristics; (Bi) Ethylene / α-olefin copolymer 10 having a density in the range of 0.850 to 0.980 g / cm 3 and an intrinsic viscosity [η] in the range of (B-ii) 135 deg. Ethylene / α-olefin copolymer composition composed of -80% by weight. The ethylene / α-olefin copolymer composition according to claim 1, wherein at least two kinds of transition metal compounds of the periodic table IV copolymer group having a ligand having a cyclopentadienyl skeleton are as follows. At least one kind of transition metal compound represented by the following formula [b-I]; In formula [bI], M is a transition metal atom selected from group IVB of the periodic table, and L ¹ is a ligand coordinated to this transition metal atom. At least two L ¹ are groups selected from a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a substituted cyclopentadienyl group having at least one substituent selected from a hydrocarbon group having 3 to 10 carbon atoms, Ligand other than cyclopentadienyl (L ² ) is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, or a hydrogen atom, and X is a transition metal atom (M). At least one kind of transition metal compound represented by the following formula [b-II]; In the formula [b-II], M is a transition metal atom selected from group IVB of the periodic table, L²Is a ligand that coordinates this transition metal atom and is at least two L²end A substituted cyclopentadienyl group having a 2-5 substituent group selected from a methyl group and an ethyl group, and L other than this substituted cyclopentadienyl group^OneIs a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, or a hydrogen atom. X is the valence of the transition metal atom (M). [A2] A copolymer of α-olefin having 3 to 20 carbon atoms and ethylene, and further having the following characteristics; (Ai) Density ranges from 0.85 to 0.980 g / cm 3, (A-ii) Intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.4 to 8 μg / g, and (A- °) at 190 ° C. The melt tension (MT (g)) and melt flow rate (MFR) satisfy the following relationship, and the shear stress of the melt copolymer is 2.4 × 10 ⁶ dyne at 190 ° C. in MT> 2.2 × MFR ^-0.84 (A-ⅳ). The flow index (FI (1 / sec)) and the melt flow rate (MFR), defined by the shear rate when reaching / cm 3, satisfy the following relationship and are measured by FR <150 × MFR (Av) GPC. One molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4 and satisfies the following relationship between (A-vi) MT / (Mw / Mn) and FI / MFR, MT / (Mw / Mn)> 0.03 × FI / MFR-3.0 However, when the value of 0.03 × FI / MFR-3.0 is 0 or less, 0 is taken, and 20 to 90% by weight of an ethylene / α-olefin copolymer polymer having [Bl] (a) organic aluminum Olefin with an oxy compound and a transition metal compound of group IV of the periodic table containing a ligand having a (b ′) cyclopentadienyl skeleton Obtained by copolymerizing ethylene and α- olefin of 3 to 20 carbon atoms in the presence of a catalyst hapyong the ethylene / α- olefin copolymer [A2] and different and also the following properties; (Bi) Ethylene / α-olefin copolymer having a density in the range of 0.850 to 0.980 g / cm 3 and an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g. Ethylene / α-olefin copolymer composition composed of 10 to 80% by weight. [A3] α-olefins having 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization of a periodic table Group IV transition metal compound comprising a ligand having an organic aluminum oxy compound and a (b ') cyclopentadienyl skeleton Obtained by copolymerizing with ethylene, and further having the following characteristics; (Ai) Ethylene / α-olefin air having a density in the range of 0.850 to 0.980 g / cm 3 and an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g. Number of carbon atoms in the presence of a catalyst for olefin polymerization of 20 to 90% by weight of a compound of the periodic table of Group IV having a ligand having a [B1] (a) organic aluminumoxy compound and a (b ') cyclopentadienyl skeleton Obtained by copolymerizing 3-20 alpha-olefin and ethylene, it is different from the said ethylene / alpha-olefin copolymer [A3], and also has the following characteristics; (Bi) Ethylene / α-olefin copolymer having a density in the range of 0.850 to 0.980 g / cm 3 and an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g. A graft modified ethylene / α-olefin copolymer composition obtained by graft copolymerization of an ethylene / α-olefin copolymer composition and a polar monomer composed of 10 to 80% by weight. [I] [A3] (a) Organic carbon atoms in the presence of a catalyst for olefin polymerization of a transition metal compound of group IV of the periodic table containing an organic aluminum oxy compound and a ligand having a (b ') cyclopentadienyl skeleton Obtained by copolymerizing ethylene with α-olefin and further having the following properties; (Ai) Ethylene / α-olefin air having a density in the range of 0.850 to 0.980 g / cm 3 and an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g. Number of carbon atoms in the presence of a catalyst for olefin polymerization of 20 to 90% by weight of a compound of the periodic table of Group IV having a ligand having a [B1] (a) organic aluminumoxy compound and a (b ') cyclopentadienyl skeleton Obtained by copolymerizing 3-20 alpha-olefin and ethylene, it is different from the said ethylene / alpha-olefin copolymer [A3], and also has the following characteristics; (Bi) Ethylene / α-olefin air having a density in the range of 0.850 to 0.980 g / cm 3 and (B-ii) an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.4 to 8 dl / g. Graft-modified ethylene / α-olefin copolymer composition obtained by graft copolymerization of an ethylene / α-olefin copolymer composition composed of 10 to 80% by weight of a copolymer and a polar monomer, and a [II] polyolefin. Ethylene copolymer composition in which the weight ratio ([I]: [II]) between the / α-olefin copolymer composition [I] and the polyolefin [II] is in the range of 1:99 to 99: 1. (a) an organic aluminum oxy compound, (b-I) at least one transition metal compound represented by the following formula [b-I], In the formula [bI], M is a transition metal atom selected from group IVB of the periodic table, and L ¹ is a ligand coordinated to this transition metal atom. At least two L ¹ are groups selected from a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a substituted cyclopentadienyl group having at least one substituent selected from a hydrocarbon group having 3 to 10 carbon atoms, Ligand other than cyclopentadienyl (L ¹ ) is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, or a hydrogen atom, and X is a transition metal atom (M). At least one kind of transition metal compound represented by the following formula [b-II]; In formula [b-II], M is a transition metal atom selected from group IVB of the periodic table, L ² is a ligand coordinated to this transition metal atom, and at least two L ² are substituted cyclos having 2-5 substituents selected from methyl and ethyl groups L ² other than the substituted cyclopentadienyl from a pentadienyl group is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, or a hydrogen atom, and X is a transition metal atom (M Step (1) of preparing an ethylene / α-olefin copolymer [A1] by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization (C1) (a) the polymerization reaction of step (1) in the presence of a catalyst for olefin polymerization (C2) of a group IV transition metal compound of the periodic table comprising a ligand having an organic aluminum oxy compound (b ') cyclopentadylyl skeleton In a polymerizer different from the group Multi-stage olefin polymerization process by copolymerizing ethylene and α- olefin of 3 to 20 carbon atoms consisting of step (2) for producing a [B1] an ethylene / α- olefin copolymer. The olefin polymerization catalyst (Cl) further contains an organoaluminum compound (c) in addition to the organoaluminum oxy compound (a), the transition metal compound (b-I) and the transition metal compound (b-II). Multistage olefin polymerization method characterized in that. The olefin polymerization catalyst (Cl) is a solid catalyst in which an organoaluminum oxy compound (a), a transition metal compound (bI), and a transition metal compound (b-II) are supported on a carrier. Phosphorus multistage olefin polymerization process. The catalyst for olefin polymerization (Cl) is a catalyst comprising a solid catalyst component and an organoaluminum compound (C), wherein the organoaluminum oxy compound (a), transition metal compound (bI) and A multistage olefin polymerization method characterized in that a transition metal compound (b-II) is supported on a carrier. The catalyst for olefin polymerization (Cl) is a prepolymerized catalyst obtained by prepolymerizing an olefin on a solid catalyst component. The solid catalyst component is an organoaluminum oxy compound (a) or a transition metal compound (bI). And the transition metal compound (b-II) is supported on a carrier. The catalyst for olefin polymerization (Cl) is a catalyst comprising a prepolymerization catalyst obtained by prepolymerizing an olefin on a solid catalyst component and an organoaluminum component (C), and the solid catalyst component is an organoaluminum oxy compound. (a) A multistage olefin polymerization method wherein a transition metal compound (bI) and a transition metal compound (b-II) are supported on a carrier. The olefin polymerization catalyst (C2) is a catalyst which further contains an organoaluminum compound (c) in addition to the organoaluminum oxy compound (a) and the transition metal compound (b '). Multistage olefin polymerization process. The multistage olefin polymerization method according to any one of claims 6 to 11, wherein the catalyst for olefin polymerization (C2) is a solid catalyst in which an organoaluminum oxy compound (a) and a transition metal compound (b ') are supported on a carrier. . The catalyst for olefin polymerization (C2) according to any one of claims 6 to 11, wherein the solid catalyst component and the organoaluminum compound (C) in which the organoaluminum oxy compound (a) and the transition metal compound (b ') are supported on a carrier. Multistage olefin polymerization method characterized in that the catalyst. The catalyst for olFP fin polymerization (C2) according to any one of claims 6 to 11, wherein the catalyst for preparing the olFP fin (C2) is prepared by preliminary olefins on the solid catalyst component supported on the carrier by the organoaluminumoxy compound (a) and the transition metal compound (b '). A multistage olefin polymerization process characterized by being a prepolymerized catalyst obtained by combining. The catalyst for olefin polymerization (C2) is composed of a prepolymerized catalyst component and an organoaluminum component (C), and the prepolymerized catalyst component is prepared by prepolymerizing olefins on a solid catalyst component. And the solid catalyst component is an organoaluminum oxy compound (a) and a transition metal compound (b ') supported on a carrier. ※ Note: The disclosure is based on the initial application.