Processes for the production of high molecular weight ethylene/alpha-olefin/non-conjugated interpolymers with low levels of long chain branching

Patent metadata

Field	Value
Publication number	US-10450394-B2
Application number	US-201615553356-A
Country	US
Kind code	B2
Filing date	Mar 1, 2016
Priority date	Mar 31, 2015
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

The invention provides a process to form a polymer composition comprising at least one ethylene/α-olefin/non-conjugated polyene interpolymer, and wherein the polymer composition has at least the following properties: a) a Mw/V0.1 ratio greater than, or equal to, 1.80 (g/mol)/(Pa·s); said process comprising polymerizing one or more mixture(s) comprising ethylene, an α-olefin and a non-conjugated polyene in the presence of a catalyst system comprising a metal-ligand complex of Formula (I), as described herein.

First claim

The invention claimed is:

1. A process to form a polymer composition comprising at least one ethylene/α-olefin/non-conjugated polyene interpolymer, and wherein the polymer composition has at least the following properties:
a) a Mw/V0.1 ratio greater than, or equal to, 1.80 (g/mol)/(Pa·s);
said process comprising polymerizing one or more monomer(s) comprising ethylene, an α-olefin and a non-conjugated polyene, in the presence of a catalyst system comprising a metal-ligand complex of Formula (I):

wherein:
M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; and n is an integer of from 0 to 3, and wherein when n is 0, X is absent; and
each X, independently, is a (C 1 -C 40 )hydrocarbyl, a (C 1 -C 40 )heterohydrocarbyl, or a halide, and wherein each X, independently, is a monodentate ligand that is neutral, monoanionic, or dianionic; or
wherein two X's are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; and
wherein X and n are chosen, in such a way, that the metal-ligand complex of Formula I is, overall, neutral; and
each Z independently is an oxygen atom, a sulfur atom, —N[(C 1 -C 40 )hydrocarbyl]-, or —P[(C 1 -C 40 )hydrocarbyl]-; and
L is a substituted or unsubstituted (C 1 -C 40 )hydrocarbylene, or a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbylene, and
wherein, for L, the (C 1 -C 40 )hydrocarbylene has a portion that comprises a 1-carbon atom to 10-carbon atom linker backbone, linking R 21 and R 22 in Formula I (to which L is bonded), or
wherein, for L, the (C 1 -C 40 )heterohydrocarbylene has a portion that comprises a 1-atom to 10-atom linker backbone linking R 21 and R 22 in Formula I, wherein each of the 1 to 10 atoms of the 1-atom to 10-atom linker backbone of the (C 1 -C 40 )heterohydrocarbylene, independently, is one of the following: i) a carbon atom, ii) a heteroatom, wherein each heteroatom independently is —O— or —S—, or iii) a substituent selected from —S(O)—, —S(O) 2 —, —Si(R C ) 2 —, —Ge(R C ) 2 —, —P(R C ), or —N(R C )—, and wherein each R C is, independently, a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarby; and
R 21 and R 22 are each, independently, C or Si; and
R 1 through R 20 are each, independently, selected from the group consisting of following: a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , a halogen atom, and a hydrogen atom; and wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; and
wherein, when R 17 is a hydrogen atom, then R 18 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , or a halogen atom; and

wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; or
wherein, when R 18 is a hydrogen atom, then R 17 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , or a halogen atom; and

wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; or
wherein, when R 19 is a hydrogen atom, then R 20 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , or a halogen atom; and

wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; or
wherein, when R 20 is a hydrogen atom, then R 19 is a substituted or unsubstituted (C 1 -C 40 )hydrocarbyl, a substituted or unsubstituted (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , or a halogen atom; and

wherein each R C is independently a substituted or unsubstituted (C 1 -C 30 )hydrocarbyl, or a substituted or unsubstituted (C 1 -C 30 ) heterohydrocarbyl; and
wherein, for Formula I, two or more of R 1 through R 22 , optionally, form one or more ring structures, and wherein each ring structure has from 3 to 50 atoms in the ring, excluding any hydrogen atoms.

2. The process of claim 1 , wherein the polymer composition has a tan delta (0.1 rad/sec, 190° C.) greater than, or equal to, 1.50.

3. The process of claim 1 , wherein the process comprises polymerizing the one or more mixture(s) in one or more reactor(s), and wherein the reactor temperature in at least one reactor is less than 150° C.

4. The process of claim 1 , wherein the polymer composition has molecular weight distribution (MWD) from 1.80 to 3.50.

5. The process of claim 1 , wherein the process comprises polymerizing the one or more mixture(s) in one reactor or in two reactors.

6. The process of claim 1 , wherein the polymer composition comprises two ethylene/α-olefin/non-conjugated polyene interpolymers.

7. The process of claim 1 , wherein for Formula I, each Z is an oxygen atom.

8. The process of claim 1 , wherein for Formula I, R 21 and R 22 are each C (carbon).

9. The process of claim 1 , wherein for Formula I, L is selected from the following: —CH2CH2CH2-, —CH2CH2- or —CH2-.

10. The process of claim 1 , wherein for Formula I, M is zirconium.

11. The process of claim 1 , wherein for Formula I, R 1 and R 16 are each independently selected from the following i) through vii):

12. The process of claim 1 , wherein Formula I is selected from the following I1 through I12:

Assignees

• Dow Global Technologies Llc

Inventors

• Fontaine Philip P
• Sun Lixin
• Li Pi Shan Colin
• Tuberquia Juan C
• Brown Susan G
• Madenjian Edward O
• Brennan Gregory J

Classifications

• C08F2/01

  characterised by special features of the polymerisation apparatus used · 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

• C08F4/659

  Component covered by group C08F4/64 containing a transition metal-carbon bond {(C08F4/64003 - C08F4/64196 take precedence)} · CPC title

• C08L23/16

  Ethylene-propylene or ethylene-propylene-diene copolymers · CPC title