Ethylene/alpha-olefin/non-conjugated polyene copolymer, method for producing the same, and use thereof

Patent metadata

Field	Value
Publication number	US-11905348-B2
Application number	US-201816979998-A
Country	US
Kind code	B2
Filing date	Mar 20, 2018
Priority date	Mar 20, 2018
Publication date	Feb 20, 2024
Grant date	Feb 20, 2024

Abstract

An object of the present invention is to provide a novel ethylene/α-olefin/non-conjugated polyene copolymer containing a certain non-conjugated polyene such as VNB as a copolymerization component, having a low long-chain branching content, excellent in cure characteristics in the case of crosslinking by using peroxide, and having good processability. The ethylene/α-olefin/non-conjugated polyene copolymer according to the present invention has constitutional units derived from ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a non-conjugated polyene (C) having a total of two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in a molecule, and satisfies certain requirements.

First claim

The invention claimed is:

1. An ethylene/α-olefin/non-conjugated polyene copolymer (S) having constitutional units derived from ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a non-conjugated polyene (C) having a total of two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in a molecule, and
satisfying the following requirements (i) to (vii):

(i) a molar ratio of ethylene/α-olefin is 40/60 to 99.9/0.1;
(ii) a weight fraction of the constitutional unit derived from the non-conjugated polyene (C) is 0.07 wt % to 10 wt % per 100 wt % of the ethylene/α-olefin/non-conjugated polyene copolymer (S);
(iii) a weight average molecular weight (Mw) of the ethylene/α-olefin/non-conjugated polyene copolymer (S), a weight fraction of the constitutional unit derived from the non-conjugated polyene (C) (weight fraction of (C) wt %), and a molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following expression (1);
4.5≤Mw×Weight fraction of (C)/100/Molecular weight of (C)≤40   Expression (1)

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

(v) a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) molecular weight distribution; Mw/Mn measured by gel permeation chromatography (GPC) is in the range of 8 to 30;
(vi) the number average molecular weight (Mn) is 30,000 or less;
(vii) two or more peaks are shown in a chart obtained by GPC measurement and an area of the peak appearing on the side having the smallest molecular weight is in the range of 1 to 20% of the total peak area.

2. The ethylene/α-olefin/non-conjugated polyene copolymer (S) according to claim 1 , wherein the intrinsic viscosity [η] is 0.1 to 5 dL/g and the weight average molecular weight (Mw) is 10,000 to 600,000.

3. The ethylene/α-olefin/non-conjugated polyene copolymer (S) 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 (S) according to claim 1 , further comprising a constitutional unit derived from a non-conjugated polyene (D) having only one partial structure selected from the group consisting of the general formulas (I) and (II) in a molecule in a weight fraction of 0 to 20 wt % (provided that the sum of the weight fractions of (A), (B), (C), and (D) is 100 wt %, and satisfying the following requirement (viii):
(viii) the weight average molecular weight (Mw), the weight fraction of the constitutional unit derived from the non-conjugated polyene (C) (weight fraction of (C) (wt %)), the weight fraction of the constitutional unit derived from the non-conjugated polyene (D) (weight fraction of (D) (wt %)), 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 the following expression (4):
4.5≤ Mw ×{(Weight fraction of( C )/100/Molecular weight of( C ))+(Weight fraction of( D )/100/Molecular weight of( D ))}≤45  Expression (4),

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

6. A method for producing the ethylene/α-olefin/non-conjugated polyene IS) copolymer according to claim 1 , comprising:
(1) a step of carrying out the copolymerization in the presence of a polymerization catalyst containing at least one metallocene compound represented by the following general formula [A1] and (2) a step of adding an alcohol as a catalyst deactivator to deactivate the polymerization catalyst;

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 the silicon-containing group, and any two adjacent groups of R 1 to R 4 may be bonded to each other to 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 the silicon-containing group, and R 7 and R 10 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 the silicon-containing group, and R 6 and R 7 ay be bonded to each other to form a ring, and R 10 and R 11 may be bonded to each other to form a ring, provided that all of R 6 , R 7 , R 10 , and R 11 are not a hydrogen atom;
R 13 and R 14 ach 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 having 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair, j represents an integer of 1 to 4, and when j is an integer of 2 or more, each Q may be the same or different from each other.

7. The method for producing the ethylene/α-olefin/non-conjugated polyene copolymer (S) according to claim 6 , wherein the copolymerization in the step (1) is carried out in the presence of a polymerization catalyst constituted by:
(a) a metallocene compound represented by the general formula [A1],
(b) at least one compound selected from
(b-1) an organometallic compound,
(b-2) an organoaluminum oxy-compound, and
(b-3) a compound which react with the metallocene compound (a) to form an ion pair,

and if necessary,
(c) a particulate carrier,
wherein the polymerization catalyst comprises at least the organometallic compound (b-1) as the compound (b).

8. The method for producing the ethylene/α-olefin/non-conjugated polyene copolymer (S) according to claim 6 , wherein the ethylene (A), the α-olefin (B) having 3 to 20 carbon atoms, the non-conjugated polyene (C) having a total of two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in a molecule, and if necessary, a non-conjugated polyene (D) having only one partial structure selected from the group consisting of the general formulas (I) and (II) in a molecule are continuously fed into a reactor to carry out the copolymerization;

9. The method for producing the ethylene/α-olefin/non-conjugated polyene copolymer (S) according to claim 8 , wherein the non-conjugated polyene (C) is 5-vinyl-2-norbornene (VNB) and the non-conjugated polyene (D) is 5-ethylidene-2-norbornene (ENB).

10. The method for producing the ethylene/α-olefin/non-conjugated polyene copolymer (S) according to claim 6 , wherein the catalyst deactivator is methanol or ethanol and the organometallic compound (b-1) is trimethylaluminum or triisobutylaluminum.

Assignees

• Mitsui Chemicals Inc

Inventors

• Ichino Kotaro
• Kikuchi Yoshiharu
• Shishido Keisuke
• Tanaka Junpei
• Arino Mitsunao

Classifications

• C08F210/18 Primary

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

• B60C1/0008

  Compositions of the inner liner · CPC title

• B60C1/0016

  Compositions of the tread · CPC title

• B60C1/0025

  Compositions of the sidewalls · CPC title

• C08F4/6592

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