Ethylene α-olefin non-conjugated polyene copolymer, use thereof, and manufacturing method thereof

Patent metadata

Field	Value
Publication number	US-11760819-B2
Application number	US-202017133280-A
Country	US
Kind code	B2
Filing date	Dec 23, 2020
Priority date	Feb 13, 2014
Publication date	Sep 19, 2023
Grant date	Sep 19, 2023

Abstract

The purpose of the present invention is to obtain an ethylene⋅α-olefin⋅non-conjugated polyene copolymer that has a low permanent compression set at low temperatures, is flexible, and has an excellent balance of rubber elasticity at low temperatures and tensile strength at normal temperatures. This ethylene-based polymer is an ethylene⋅α-olefin⋅non-conjugated polyene copolymer that includes units derived from ethylene (A), units derived from an α-olefin (B) containing 4-20 carbon atoms, and units derived from a non-conjugated polyene (C) and satisfies (1)-(4). (1) The molar ratio of (A) to (B) is 40/60-90/10, (2) the contained amount of the units derived from (C) is 0.1-6.0 mol %, (3) ML (1+4) 125° C. is 5-100, and (4) the B value is 1.20 or more.

First claim

The invention claimed is:

1. A method for manufacturing an ethylene⋅α-olefin⋅non-conjugated polyene copolymer,
wherein the ethylene⋅α-olefin⋅non-conjugated polyene copolymer comprises a structural unit derived from an ethylene [A], a structural unit derived from a C 4 -C 20 α-olefin [B] and a structural unit derived from a non-conjugated polyene [C], and satisfying the following (1) to (4):
(1) a molar ratio ([A]/[B]) of the structural units derived from the ethylene [A] to the structural units derived from the α-olefin [B] is 40/60 to 90/10;
(2) a content of the structural units derived from the non-conjugated polyene [C] is 0.1 to 6.0 mol % based on the total of the structural units of [A], [B] and [C] as 100 mol %;
(3) a Mooney viscosity ML (1+4) 125° C. at 125° C. is 5 to 100; and
(4) a B value represented by the following formula (i) is 1.20 or more:
B value=([ EX]+ 2[ Y ])/[2×[ E ]×([ X]+[Y ])]  (i),

wherein [E], [X] and [Y] represent a mole fraction of the ethylene [A], the C 4 -C 20 α-olefin [B] and the non-conjugated polyene [C] respectively, and [EX] represents an ethylene [A]-C 4 -C 20 α-olefin [B] diad chain fraction; and
wherein the ethylene, the C 4 -C 20 α-olefin and the non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst including:
(a) a transition metal compound represented by formula [VII]:

wherein M is a titanium atom, a zirconium atom, or a hafnium atom;
R 5 and R 6 are substituted aryl groups wherein one or more of the hydrogen atoms of an aryl group are substituted with an electron-donating substituent having a substituent constant σ of −0.2 or less in the Hammett's rule; wherein when the substituted aryl group has a plurality of the electron-donating substituents, each of the electron-donating substituents is the same or different; wherein the substituted aryl group optionally contains a substituent selected from the group consisting of C 1 -C 20 hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups other than the electron-donating substituents; and wherein when the substituted aryl group has a plurality of the substituents, each of the substituents is the same or different;
Q is selected in an identical or different combination from halogen atoms, C 1 -C 20 hydrocarbon groups, anionic ligands and neutral ligands capable of being coordinated with a lone electron pair; and
j is an integer of 1 to 4; and
(b) at least one compound selected from the group consisting of
(b-1) organometallic compounds,
(b-2) organoaluminum oxy compounds, and
(b-3) components which react with the transition metal compound (a) to form an ion pair.

2. A method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer, the method comprising copolymerizing an ethylene, an α-olefin having three or more carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing:
(a) a transition metal compound represented by formula [I]:

wherein Y is selected from the group consisting of a carbon atom, a silicon atom, a germanium atom and a tin atom;
M is a titanium atom, a zirconium atom or a hafnium atom;
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , each of which is the same or different, are atoms or substituents selected from the group consisting of hydrogen atoms, C 1 -C 20 hydrocarbon groups, aryl groups, substituted aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups;
adjacent substituents between R 1 and R 6 are optionally bound together to form a ring;
Q is selected in an identical or different combination from halogen atoms, C 1 -C 20 hydrocarbon groups, anionic ligands and neutral ligands capable of being coordinated with a lone electron pair;
n is an integer of 1 to 4; and
j is an integer of 1 to 4; and
(b) at least one compound selected from the group consisting of
(b-1) organometallic compounds,
(b-2) organoaluminum oxy-compounds, and
(b-3) components which react with the transition metal compound (a) to form an ion pair.

3. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 2 , wherein n in the general formula [I] is 1.

4. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 2 , wherein R 1 , R 2 , R 3 and R 4 in the general formula [I] are all hydrogen atoms.

5. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 2 , wherein Y in the general formula [I] is a carbon atom.

6. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 2 , wherein R 5 and R 6 in the general formula [I] are groups selected from the group consisting of aryl groups and substituted aryl groups.

7. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 6 , wherein R 5 and R 6 in the general formula [I] are substituted aryl groups wherein one or more of the hydrogen atoms of an aryl group are substituted with an electron-donating substituent having a substituent constant σ of −0.2 or less in the Hammett's rule; wherein when the substituted aryl group has a plurality of the electron-donating substituents, each of the electron-donating substituents is the same or different; wherein the substituted aryl groups optionally contain a substituent selected from the group consisting of C 1 -C 20 hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups other than the electron-donating substituents; and wherein when the substituted aryl group has a plurality of the substituents, each of the substituents is the same or different.

8. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 7 , wherein the electron-donating substituent is a group selected from the group consisting of nitrogen-containing groups and oxygen-containing groups.

9. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 8 , wherein R 5 and R 6 in the general formula [I] are substituted phenyl groups in which a group selected from the group consisting of the nitrogen-containing groups and the oxygen-containing groups is on the meta position and/or para position to the bond to Y.

10. The method for manufacturing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 9 , wherein R 5 and R 6 in the general formula [I] are substituted phenyl groups comprising a nitrogen-containing group represented by formula [II] as the electron-donating substituent:

wherein R 7 and R 8 , each of which is the same or different and is optionally bound together to form a ring, are atoms or substituents selected from the group consisting of hydrogen atoms, C 1 -C 20 hydrocarbon groups, silicon-containing groups, oxygen-containing groups and halogen-containing groups; and the line on the right of N represents a bond to a phenyl group.

11. The method for manufacturing an et

Assignees

• Mitsui Chemicals Inc

Inventors

• Endo Koji
• Hiwara Mayumi
• Matsuura Sadahiko
• Mizobuchi Yusuke
• Yamamura Yuichi
• Noguchi Yuji
• Ishii Yuji
• Sakai Tatsuya
• Shishido Keisuke
• Ichino Kotaro
• Inomata Kiyohide
• Takeuchi Fumito
• Ide Kenta

Classifications

• C08F210/18 Primary

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

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title

• C08F4/65912

  in combination with an organoaluminium compound · CPC title

• C08L23/08

  Copolymers of ethene (C08L23/16 takes precedence) · CPC title

• C09K3/10

  {Materials in mouldable or extrudable form} for sealing or packing joints or covers (filling pastes C09D5/34) · CPC title