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Title:
BIS-PHENYL-PHENOXY POLYOLEFIN CATALYSTS HAVING AN ALKOXY- OR AMIDO-LIGAND ON THE METAL FOR IMPROVED SOLUBILITY
Document Type and Number:
WIPO Patent Application WO/2019/067280
Kind Code:
A4
Abstract:
Embodiments are directed to a catalyst system comprising metal ligand complexes and processes for polyolefin polymerization using the metal ligand complex having the following structure : where X is selected from the group consisting of -ORX or NRX 2.

Inventors:
KRASOVSKIY ARKADY L (US)
WILSON DAVID R (US)
VAIDYA TULAZA (US)
CARNAHAN EDMUND M (US)
FONTAINE PHILIP P (US)
IVERSON CARL N (US)
Application Number:
PCT/US2018/051680
Publication Date:
May 23, 2019
Filing Date:
September 19, 2018
Export Citation:
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Assignee:
DOW GLOBAL TECHNOLOGIES LLC (US)
International Classes:
C08F4/659; C08F210/16; C08F4/64
Attorney, Agent or Firm:
LUNN, Jennifer H. et al. (US)
Download PDF:
Claims:
AMENDED CLAIMS

received by the International Bureau on 5 April 2019 (05.04.2019)

40

CLAIMS

1. A procatalyst comprising a metal-ligand complex according to formula (I):

M is a metal chosen from titanium, zirconium, or hafnium, the metal being in a formal oxidation state of +2, +3, or +4;

X is selected from the group consisting of -OR or -NR 2; wherein each R is

independently a (Ci-C5o)hydrocarbyl, (Ci-C5o)heterohydrocarbyl, or -H and at least one R is (Ci-C5o)hydrocarbyl, (Ci-C5o)heterohydrocarbyl, and, when X is -NR 2, optionally two R are covalently linked;

the metal-ligand complex is overall charge-neutral;

each Z is independently chosen from -0-, -S-, -N(Rn)-, or -P(Rp)-;

R1 and R16 are independently selected from the group consisting of -H,

(Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(Rn)2, -ORc, -SRc, -N02, -CN, -CF3, RCS(0)-, RCS(0)2- (RC)2C=N-, RCC(0)0-, RC0C(0)-, RCC(0)N(R)-, (RC)2NC(0)-, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV): 41

H, (Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(R )3, -Ge(Rc)3, -P(Rp)2, -N(Rn)2, -N=CHRc, -ORc, -SRc, -N02, -CN, -CF3, RCS(0)-, RCS(0)2- (RC)2C=N-, RCC(0)0-, RC0C(0)-, RCC(0)N(Rn)-, (RC)2NC(0)-, or halogen,

provided that at least one of R1 or R16 is a radical having formula (II), a radical having formula (III), or a radical having formula (IV);

each of R2 4, R5-8, R9-12, and R13 15 S independently selected from -H,

(Ci-C4o)hydrocarbyl, (Ci-C4o)heterohydrocarbyl, -Si(Rc)3, -Ge(Rc)3, -P(Rp)2, -N(Rn)2, -ORc, -SRc, -N02, -CN, -CF3, RCS(0)-, RCS(0)2-, (RC)2C=N-, RCC(0)0-, RC0C(0)-, RCC(0)N(R)-, (RC)2NC(0)-, and halogen;

L is (C2-C4o)hydrocarbylene or (C2-C4o)heterohydrocarbylene; and

each Rc, Rp, and RN in formula (I) is independently a (Ci-C3o)hydrocarbyl,

(Ci-C3o)heterohydrocarbyl, or -H.

2. The procatalyst according to claim 1, wherein R is chosen from (C5-Cso)alkyl or -H.

3. The procatalyst according to claims 1 or 2, wherein R is linear.

4. The procatalyst according to claims 1 or 2, wherein R is branched.

5. The procatalyst according to claims 1 or 2, wherein X is chosen from a linear alkyl having the formula -OCxHx+i or -NHCxHx+i, where x is an integer from 10 to 40.

6. The procatalyst according to claim 1, wherein:

M is zirconium or hafnium;

each X is -OC22H45; and

each Z is oxygen.

7. The procatalyst according to any one of claims 1 - 3,

M is zirconium or hafnium;

each X is -OCi8H37; and

each Z is oxygen.

8. The procatalyst according to claim 1,

M is zirconium or hafnium;

each X is -N(CI8H37)Rx; and

each Z is oxygen.

9. The procatalyst according to claim 1, wherein

M is zirconium or hafnium;

at least one X is -N(C22H45)2; and

each Z is oxygen.

10. The procatalyst according to any one of claims 1 to 10, wherein the metal-ligand complex according to formula (I) has a wt.% solubility ratio W/Y of at least 1.5, wherein W is the wt. % solubility of the metal-ligand complex of formula (I) in MCH at STP; wherein Y is the wt. % of a corresponding comparative metal-ligand complex of formula (la) in MCH at STP; and wherein the corresponding comparative complex has a structure according to formula (la):

in which M, each Z, each R1 16 and L, all are identical to corresponding groups of the metal- ligand complex according to formula (I)