# US 8,772,523 B2 · Multifunctional chain shuttling agents

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- Number: US 8,772,523 B2
- Document ID: US8772523B2
- Status: Granted
- Kind: B2
- Application number: 13/667,119
- Filed: 2012-11-02
- Published: 2013-03-21
- Granted: 2014-07-08
- Earliest claimed: 2009-07-29
- Assignees: Dow Global Technologies LLC
- Applicants: Dow Global Technologies LLC
- Inventors: Thomas P. Clark; Nahrain E. Kamber; Sara B. Klamo; Phillip D. Hustad; David R. Wilson
- Web page: https://patentgrep.com/patent/US8772523B2

## CPC

- C08F 2/38: Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation}
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- H01M 50/417: Polyolefins
- C08F 10/14: Monomers containing five or more carbon atoms
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)}
- Y02E 60/10: Energy storage using batteries
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The invention generally relates to chain shuttling agents (CSAs), a process of preparing the CSAs, a composition comprising a CSA and a catalyst, a process of preparing the composition, a processes of preparing polyolefins, end functional polyolefins, and telechelic polyolefins with the composition, and the polyolefins, end functional polyolefins, and telechelic polyolefins prepared by the processes.

## Claims

### Claim 1

A process for preparing a multifunctional chain shuttling agent, the process comprising steps of: contacting a hydroxy-, thiol- (i.e., —SH), hydrocarbylamino-, amino- (i.e., —NH2), hydrocarbylphosphino-, or phosphino- (i.e., —PH2) and vinyl-containing polyvalent group to an alkylperhydrocarbylmetal to respectively prepare an organometallic intermediate that is a hydrocarbylmetal vinyl-alkoxide, hydrocarbylmetal vinyl-sulfide, hydrocarbylmetal vinyl-(hydrocarbyl)amine, hydrocarbylmetal vinyl-amine, hydrocarbylmetal vinyl-(hydrocarbyl)phosphine, or hydrocarbylmetal vinyl- phosphine; and contacting the organometallic intermediate to a hydrocarbylmetal monohydride, thereby preparing the multifunctional chain shuttling agent, each metal independently being a cation of tin or a metal of any one of Groups 2, 12, and 13 of the Periodic Table of the Elements.

### Claim 2 (depends on 1)

The process of claim 1 comprising:
(a) contacting together an alkylperhydrocarbylmetal of formula (1):
M2(C1-C20)alkyl(R2)z (1),
wherein M2 is tin or a metal of Group 12 or 13 of the Periodic Table of the Elements, the Group 12 metal being in a formal oxidation state of +2, the Group 13 metal being in a formal oxidation state of +3, and the tin being in a formal oxidation state of +2 or +4;
each R2 independently is a hydrogen, (C1-C20)hydrocarbyl or -D-(C1-C20)hydrocarbyl;
when z is 2 or 3, two R2 are taken together to form a (C2-C20)hydrocarbylene;
and z is an integer of 0, 1, 2, or 3;
and a compound containing a hydroxyl-, thiol-, amino-, hydrocarbylamino-, phosphino-, or hydrocarbylphosphino- and vinyl-containing polyvalent group of formula (2):
[H2C═C(R4)]r—RL1—[XH]p (2),
wherein R4 is hydrogen or a (C1-C5)alkyl and RL1 is absent or a polyvalent radical of a (C1-C18)hydrocarbon, the (C1-C18)hydrocarbon being saturated or mono- or di-unsaturated and R4 and RL1 being selected so that the number of C(R4) groups and RL1 have a total number of carbon atoms of from 1 to 19 carbon atoms; and
each X independently is O, S, N(H), N((C1-C20)hydrocarbyl), P(H), or P((C1 -C20)hydrocarbyl);
p is an integer of 1 or 2; and,
r is an integer of 1 or 2;
to give a hydrocarbylmetal vinyl-alkoxide/sulfide/amide/phosphide of formula (3):
[H2C═C(R4)]r—RL1—[X-M2(R2)z]p (3); and
(b) contacting the hydrocarbylmetal vinyl-alkoxide/sulfide/amide/phosphide of formula (3) to n mole equivalents of a hydrocarbylmetal monohydride of formula (4):
HM1(R1)y (4)
wherein y is an integer of 0, 1, or 2
each M1 is a metal of Group 2, 12, or 13 of the Periodic Table of the Elements, the Group 13 metal being in a formal oxidation state of +3 and the Group 2 or 12 metal being in a formal oxidation state of +2;
each R1 independently is a (C1-C20)hydrocarbyl; or, when y is 2, one R1 is (C1-C20)hydrocarbyl and one R1 is R3N(H)—, (R3)2N—, R3P(H)—, (R3)2P—, R3S—, or R3O—, or two R1 are taken together to form a (C2-C20)hydrocarbylene;
to give the multifunctional chain shuttling agent of formula (I):
{((R1)yM1[{(-CH2)r)t—RL—[(X-)s}q}mM2(R2)z]p]n (I),
or an exchange product thereof,
wherein
m is an integer of 1, 2, 3, or 4; r is an integer of 1 or 2; t is an integer of 1 or 2; each of n, p, q, and s is an integer of 1; and when r is 1, then each RL independently is a (C1-C19)alkylene or (C2-C19)alkenylene; or when (a) r is 1 and t is 2, or (b) r is 2 and t is 1, or (c) each of m and s is 2 and r and t are each 1, then each RL independently is a trivalent radical of a (C3-C19)alkane or (C3-C19)alkene; or
n is an integer of 1, 2, or 3; s is an integer of 1 or 2; p is an integer of 1 or 2; each of m, q, r, and t is an integer of 1; and when s and p are each 1, then each RL independently is a (C1-C19)alkylene or (C2-C19)alkenylene; or when (a) s is 1 and p is 2, or (b) s is 2 and p is 1, then each RL independently is a trivalent radical of a (C3-C19)alkane or (C3-C19)alkene; or
q is an integer of 2 or 3; each of m, n, p, r, s, and t is an integer of 1; and each RL independently is a (C1-C19)alkylene or (C2-C19)alkenylene; or
each of m, n, and q is an integer of 1; each of p, r, s, and t is an integer of 1 or 2; and RL is a tetravalent radical of a (C3-C19)alkane or (C3-C19)alkene, where one of r and t is 1 and the other of r and t is 2 and one of p and s is 1 and the other of p and s is 2;
y is an integer of 0, 1, or 2 and is chosen such that the sum of [y plus the multiplicative product of (n times q times r)] is equal to the formal oxidation state of M1, i.e., (the formal oxidation state of M1)=y +(n·q·r);
z is an integer of 0, 1, 2, or 3 and is chosen such that the sum of [z plus the multiplicative product of (m times q times s)] is equal to the formal oxidation state of M1, i.e., (the formal oxidation state of M1)=z +(m·q·s).

### Claim 3 (depends on 2)

The process of claim 2 wherein M1 is zinc and M2 is aluminum.

### Claim 4 (depends on 2)

The process of claim 2 wherein M1 and M2 are aluminum.

### Claim 5 (depends on 2)

The process of claim 2 wherein M1 and M2 each independently is zinc, aluminum, tin, gallium, boron or calcium.