Ethylene/alpha-olefin/non-conjugated polyene copolymer, and production process and use thereof

Patent metadata

Field	Value
Publication number	US-2016355622-A1
Application number	US-201515117635-A
Country	US
Kind code	A1
Filing date	Feb 13, 2015
Priority date	Feb 14, 2014
Publication date	Dec 8, 2016
Grant date	—

Abstract

A novel ethylene/α-olefin/non-conjugated polyene copolymer comprising structural units derived from ethylene (A), an α-olefin (B) of 3 to 20 carbon atoms, and a non-conjugated polyene (C) containing intramolecularly two or more partial structures in total selected from the group consisting of structures of Formulae (I) and (II), and having a small number of long-chain branches,

The novel ethylene/α-olefin/non-conjugated polyene copolymer contains a non-conjugated polyene such as VNB as a copolymerization component and a small long-chain branch content and is excellent in curing properties in the case of crosslinking using peroxide; and a process for producing the ethylene/α-olefin/non-conjugated polyene copolymer, and a use thereof are provided.

First claim

1 . An ethylene/α-olefin/non-conjugated polyene copolymer comprising structural units derived from ethylene (A), an α-olefin (B) of 3 to 20 carbon atoms, and a non-conjugated polyene (C) containing intramolecularly two or more partial structures in total selected from the group consisting of structures represented by Formulae (I) and (II),

and satisfying the following requirements of from (i) to (v):
a molar ratio of the ethylene/α-olefin is from 40/60 to 99.9/0.1;
(ii) a weight fraction of the structural unit derived from the non-conjugated polyene (C) is from 0.07% by weight to 10% by weight in 100% by weight of the ethylene/α-olefin/non-conjugated polyene copolymer;
(iii) a weight-average molecular weight (Mw) of the ethylene/α-olefin/non-conjugated polyene copolymer, the weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C) (% by weight)), and a molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy Formula (1),
4.5≦Mw×weight fraction of ( C )/100/molecular weight of ( C )≦40   Formula (1);

(iv) a ratio of a complex viscosity η* (ω=0.1) (Pa·sec) at a frequency of w=0.1 rad/s to a complex viscosity η* (ω=100) (Pa·sec) at a frequency of w=100 rad/s, both obtained by linear viscoelastic measurement (190° C.) by using a rheometer, represented by P (η* (ω=0.1) /η* (ω=100) ), an intrinsic viscosity represented by [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C)) satisfy Formula (2),
P /([η] 2.9 )≦weight fraction of ( C )×6  Formula (2); and

(v) number of long-chain branches per 1000 carbon atoms represented by (LCB 1000C ) and a natural logarithmic number of the weight-average molecular weight (Mw) represented by [Ln(Mw)], obtained by using 3D-GPC, satisfy Formula (3),
LCB 1000C ≦1−0.07×Ln(Mw)  Formula (3).

2 . The ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1 , wherein the intrinsic viscosity [η] is from 0.1 to 5 dL/g, and the weight-average molecular weight (Mw) is from 10000 to 600000.

3 . The ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1 , wherein the non-conjugated polyene (C) is 5-vinyl-2-norbornene (VNB).

4 . The ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1 , further comprising a structural unit derived from a non-conjugated polyene (D) containing intramolecularly only one partial structure selected from the group consisting of structures represented by Formulae (I) and (II), at a weight fraction of from 0% by weight to 20% by weight (with the proviso that a sum of weight fractions of (A), (B), (C), and (D) is 100% by weight), and satisfying the following requirement (vi);
(vi) the weight-average molecular weight (Mw) of the ethylene/α-olefin/non-conjugated polyene copolymer, the weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C) (% by weight)), the weight fraction of the structural unit derived from a non-conjugated polyene (D) (weight fraction of D (% by weight)), the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)), and a molecular weight of the non-conjugated polyene (D) (molecular weight of (D)) satisfy Formula (4),
4.5≦Mw×[(weight fraction of ( C )/100/molecular weight of ( C ))+(weight fraction of ( D )/100/molecular weight of ( D ))]≦45   Formula (4)

5 . The ethylene/α-olefin/non-conjugated polyene copolymer according to claim 4 , wherein the non-conjugated polyene (D) is 5-ethylidene-2-norbornene (ENB).

6 . The ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1 , obtained by copolymerizing monomers in the presence of at least one kind of metallocene compound represented by Formula [A1],

[wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , and R 12 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than any silicon-containing group, and adjacent two groups among R 1 to R 4 may together form a ring;
R 6 and R 11 are the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than any silicon-containing group, R 7 and R 10 are the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than any silicon-containing group, R 6 and R 7 may together form a ring, and R 10 and R 11 may together form a ring, with the proviso that all of R 6 , R 7 , R 10 , and R 11 are not a hydrogen atom simultaneously;
R 13 and R 14 each independently represent an aryl group;
M 1 represents a zirconium atom;
Y 1 represents a carbon atom or a silicon atom;
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene of 4 to 20 carbon atoms, or a neutral ligand coordinatable by an anionic ligand or a lone pair, and j represents an integer from 1 to 4, and when j is an integer from 2 or more, a plurality of Qs may be the same or different from each other].

7 . A process for producing the ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1 , the process comprising performing copolymerization in the presence of at least one kind of metallocene compound represented by Formula [A1] below to produce the ethylene/α-olefin/non-conjugated polyene copolymer,

[wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , and R 12 each independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than any silicon-containing group, and adjacent two groups among R 1 to R 4 may together form a ring;
R 6 and R 11 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than any silicon-containing group, R 7 and R 10 are the same atom or the same group selected from hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than any silicon-containing group, R 6 and R 7 may together form a ring, and R 10 and R 11 may together form a ring, with the proviso that all of R 6 , R 7 , R 10 , and R 11 are not a hydrogen atom simultaneously;
R 13 and R 14 each independently represent an aryl group;
M 1 represents a zirconium atom;
Y 1 represents a carbon atom or a silicon atom;
Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene of 4 to 20 carbon atoms, or a neutral ligand coordinatable by an anionic ligand or a lone pair, and j represents an integer from 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different from each other].

8 . The process for producing the ethylene/α-olefin/non-conjugated polyene copolymer according to claim 7 , wherein the process comprises continuously feeding to a reactor and copolymerizing ethylene (A), an α-olefin (B) of 3 to 20 carbon atoms, a non-conjugated polyene (C) containing intramolecularly two or more partial structures in total selected from the group consisting of structures represented by Form

Assignees

• Mitsui Chemicals Inc

Inventors

• Ichino Kotaro
• Kikuchi Yoshiharu
• Tohi Yasushi
• Matsugi Tomoaki
• Yanagimoto Yasushi
• Arino Mitsunao
• Shishido Keisuke
• Hosoya Mikio

Classifications

• C08F210/18 Primary

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• B60C1/00

  Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition · CPC title

• C08F4/6592

  containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring · CPC title

• C08K5/14

  Peroxides · CPC title

• C08L23/22

  Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins · CPC title