Electrochrome polymer systems

• US 6,569,361 B1
• Filed: 02/01/2000
• Issued: 05/27/2003
• Est. Priority Date: 07/07/1997
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Heuer, Helmut Werner, Kostromine, Serguei, Claussen, Uwe, Berneth, Horst
• Primary Examiner(s): Tucker, Philip
• Application Number:
  US09/462,045
• Time in Patent Office: 1,211 Days
• Field of Search: 252/583, 359/265, 359/267, 359/272, 359/275
• US Class Current: 252/583
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: G02F 2001/15145 the electrochromic layer comprises a mixture of anodic and cathodic compounds

Abstract

Electrochromic systems containing soluble electrochromic polymers which are accessible by polymerization, polycondensation or polyaddition from electrochromic monomers are used in devices for variable transparency to electromagnetic radiation.

Claims

1. A process for preparing the polymer according to a polymer of the Formula I dissolved in at least one polar solvent

2. The process according to claim 1, wherein, in the monomers of the formulae XXVI, XXVII and XXVIII,

OX² is a radical has a formula selected from the formulae consisting of IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, and XVIII:

wherein R₁ to R₄, independently of one another, are hydrogen, (C₁-C₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₃-C₇)-cycloalkyl, (C₇-C₁₅)-aralkyl or (C₆-C₁₀)-aryl,

R₅ and R₆ or R₇ and R₈ are hydrogen or together are a —

(CH₂)₂—

or —

(CH₂)₃—

bridge,

R₉ and R₁₀, independently of one another, are hydrogen or in pairs are a —

(CH₂)₂—

, —

(CH₂)₃—

or —

CH═

CH—

bridge,

R₁₁, R₁₂, R₁₇ and R₁₈, independently of one another, are hydrogen, (C₁-C₄alkyl, (C₁-C₄)-alkoxy, halogen, cyano, nitro or (C₁-C₄)-alkoxycarbonyl,

R₁₃ and R₁₄, independently of one another, are O, N—

CN, C(CN)₂ or N-(C₆-C₁₀)aryl-,

R₁₅ and R₁₆ are a —

CH═

CH—

CH═

CH—

bridge,

E₁ is an O or S atom,

Z₁ is a direct bond, —

CH═

CH—

, —

C(CH₃)═

CH—

, —

C(CN)═

CH—

, —

CCl═

CCl—

, —

C(OH)═

CH—

, —

CCl═

CH—

, —

CH═

CH—

, —

CH═

N—

N═

CH—

, —

C(CH₃)═

N—

N═

C(CH₃)—

or —

CCl═

N—

N═

CCl—

,

Z₂ is —

(CH₂)_r—

, p- or m-CH₂—

C₆H₄—

CH₂—

,

r is an integer form 1 to 10, and

G⁻

is a colorless anion which is redox-inert under the conditions, and

RED¹ is a radical selected from the group consisting of compounds having the formulae XIX, XX, XXI, XXII, XXIII, XIV and XXV;

wherein R₂₁ and R₂₂ are (C₁-C₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₃-C₇)-cycloalkyl, (C₇-C₁₅)-aralkyl or (C₆-C₁₀)-aryl,

R₂₃ to R₂₈, independently of one another, are hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, cyano, nitro, (C₁-C₄)-alkoxycarbonyl or (C₆-C₁₀)-aryl, and

R₂₆ is additionally NR³⁷R₃₇,

R₂₉ to R₃₅, independently of one another, are hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, cyano, (C₁-C₄)-alkoxycarbonyl or (C₆-C₁₀)-aryl, or

R₂₉ and R₃₀, and R₃₄ and R₃₅, independently of one another, together are a —

(CH₂)₃—

, —

(CH₂)₄—

or —

CH═

CH—

CH═

CH—

bridge,

E₂ is an O or S atom or the groups N—

B₄, C(CH₃)₂, C═

O or SO₂,

E₃ and E₄ is an O or S atom or the group NR³⁶,

R³⁶ and R³⁷, independently of one another, are (C₁-C₁₂)-alkyl, (C₂-C₈) alkenyl, (C₃-C₇)cycloalkyl, (C₇-C₁₅)-aralkyl or (C₆-C₁₀)-aryl, and R³⁶ is additionally hydrogen,

R³⁷ in the meaning of NR³⁷R³⁷ together with the N atom to which they are bonded, form a five or six-membered, saturated ring, which may contain further heteroatoms,

v is an integer from 1 to 20,

if B₃ is identical to B₄, B₃ and B₄ are identical to B₁ or B₂,

if B₃ is not identical to B₄ or B₄ is absent, B₃ is —

[Y¹_s—

(CH₂)_m—

Y²—

(CH₂)_e—

Y³]_o—

Y⁴, wherein

Y¹ is O, NR¹⁹, COO, OCO, CONH, OCONH, NHCONH, C(═

O), OC(═

O)O, —

CH₂—

CH═

CH—

(trans- or cis-), —

CH₂—

C═

C—

, (C₄-C₇)-cycloalkanediyl, (C₆-C₁₂)-arylene or (C₇-C₁₄)-arylalkylene,

Y² is O, NR¹⁹, COO, OCO, CONH, —

CH═

CH—

(trans- or cis-), —

C═

C—

, (C₄-C₇)-cycloalkanediyl or (C₆-C₁₂)-arylene,

Y³ is O, NR¹⁹, COO, OCO, CONH or (C₆-C₁₂)-arylene, and

Y⁴ is

 

wherein

B₅ is B₁ or B₂, and

R₂₀ is hydrogen, (C₁-C₁₈)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxycarbonyl, (C₆-C₁₀)-aryl, halogen or cyano,

B₄ is absent or is hydrogen, (C₁-C₁₈)-alkyl, (C₂-C₁₂)-alkenyl, (C₁-C₄)-alkoxy, (C₃-C₇)-cycloalkyl, (C₁-C₄)-alkoxycarbonyl, (C₇-C₁₅)-aralkyl, (C₆-C₁₀)-aryl, halogen, cyano or nitro, and

B₁ and B₂ are identical or bridging units, or wherein B³ and B⁴ are replaced by the bridging units B⁶, B⁷ and B⁸,

X¹ and X² are halogen, —

OH, —

O⁻

, —

COOH, —

COO—

(C₁-C₄)-alkyl, —

O(═

O)—

(C₁-C₄)-alkyl, —

COO⁻

, —

NH₂, —

NH—

(C₁-C₄)-alkyl, —

N═

C═

O, or a tertiary nitrogen atom which carries three identical or different (C₁-C₁₂)-alkyl, (C₇-C₁₅)-aralkyl or (C₆-C₁₀)-aryl substituents or is a member of a 4- to 7-atom ring, which may also contain further heteroatoms, or

X¹ or X² is a C═

C—

double bond, an —

O—

C(═

O)—

CH═

CH₂ group or an —

O—

C(═

O)—

C(CH₃)═

CH₂—

group.

3. The process according to claim 1, wherein the electrochromic monomers of formulae XXVI to XXVIII, in which X¹ and X² are primary or secondary OH groups, are polycondensed with aliphatic or aromatic diisocyanates.

4. The process according to claim 1, wherein the electrochromic monomers of formulae XXVI to XXVIII, in which X¹ and X² are primary halogen groups, are subjected to a polyaddition reaction with aliphatic or aromatic compounds which have two tertiary nitrogen atoms which themselves carry three identical or different (C₁-C₁₂)-alkyl, (C₇-C₁₅)-aralkyl, or (C₆-C₁₀)-aryl substituents or are members of the 4- to 7-atom ring.

5. The process according to claim 1, wherein the electrochromic monomers of formulae XXVI to XXVIII, in which X¹ and X² or both, is or are, at least one C═

C double bond, are polymerized by free-radical polymerization.

6. The process according to claim 1, wherein the electrochromic monomers of formulae XXVI to XXVIII, in which X¹ and X² are two OH groups, are polycondensed with dicarboxylic acid dichlorides.