	US 7,459,505 B2
	Block copolymers with acidic groups
Gerhard Maier, Munich (Germany); Markus Gross, Kaufbeuren (Germany); and Hans-Georg Herz, Marktoberdorf (Germany)
Assigned to General Motors Corporation, Detroit, Mich. (US)
Filed on May 03, 2005, as Appl. No. 11/120,790.
Prior Publication US 2006/0251969 A1, Nov. 09, 2006
Int. Cl. C08F 283/00 (2006.01)

U.S. Cl. 525—535 [524/68; 521/27; 429/303]

21 Claims

1. A block copolymer for use as a solid polymer electrolyte, the block copolymer comprising a polymer having formula 1:

(A_mB_n)_p 1

wherein

A is a first polymer segment that is repeated m times to form first polymer block A_m;

B is a second polymer segment that is repeated n times to form second polymer block B_n, B being described by formula 2:

Y¹is —O—, —S—, —CO—, —SO₂—, —C(CH₃)₂—, —C(CF₃)₂—, —P(O)(T′¹)—, —C(CH₃)(T′¹)—, —P(O)(R⁴)—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next aromatic ring, or

R¹, R², and R³are each independently H, C_1-10alkyl, C_6-18aryl, C_6-18aralkyl, SO₃H, —SO₃⁻M⁺, —COOH, —COO⁻M⁺, —PO₃H₂, —PO₃H⁻M⁺, —PO₃²⁻M₂⁺, or —PO₃²⁻M²⁺;

R⁴is H, C_1-10alkyl, C_6-18aryl, or C_6-18aralkyl;

T′¹is H or a moiety having at least one substituent for proton transfer;

i is an integer from 1 to 6; and

T¹is described by formula 3;

Y²is —O—, —S—, —CO—, —SO₂—, —C(CH₃)₂—, —C(CF₃)₂—, —P(O)(R⁴)—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, or a bond directly to the next aromatic ring;

R⁴is H, C_1-10alkyl, C_6-18aryl, or C_6-18aralkyl;

R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³are each independently H, C_1-10alkyl, C_6-18aryl, C_6-18aralkyl, SO₃H, —COOH, —COO⁻M⁺, —PO₃H₂, —PO₃H⁻M⁺, —PO₃²⁻M₂⁺, or —PO₃²⁻M²⁺;

M is a metal, ammonium, or alkylamonium; and

j is an integer from 1 to 30;

with the proviso that when j>1, the Y²between sequential aromatic rings are the same or different: the R⁵, R⁶, R⁷, R⁸, and R⁹on sequential aromatic rings are the same or different, wherein at least one of R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³is —SO₃H, —SO₃⁻M⁺, —COOH, —COO⁻M⁺, —PO₃H₂, —PO₃H⁻M⁺, —PO₃²⁻M₂⁺, or —PO₃²⁻M²⁺;

m, n are each independently an integer from 1 to 200; and

p is an integer from 1 to 20;

wherein first polymer block A_mis bonded to second polymer block B_nand the block copolymer is formable into an ion-conductive membrane with the proviso that when i>1, the Y¹between sequential aromatic rings are the same or different: the T¹and T′¹on sequential aromatic rings are the same or different; the R¹, R², and R³on sequential aromatic rings are the same or different.