Photochromic articles containing polyoxometalate derivatives and methods of making same

Patent metadata

Field	Value
Publication number	US-9976077-B2
Application number	US-201515320495-A
Country	US
Kind code	B2
Filing date	Jun 22, 2015
Priority date	Jun 30, 2014
Publication date	May 22, 2018
Grant date	May 22, 2018

Abstract

A photochromic article is provided, containing a polymer and a polyoxometalate derivative anion and counter cation complex distributed in the polymer. A method of forming a photochromic film is also provided, including forming a composition containing a polymer or a precursor of the polymer and a polyoxometalate derivative and counter cation complex and preparing a film from the composition, the film containing the polyoxometalate derivative and counter cation complex distributed in the polymer. Further, a precursor composition is provided, including a polymer or a precursor of the polymer and a polyoxometalate derivative anion and a counter cation.

First claim

What is claimed is:

1. A photochromic article comprising:
a polymer; and
a polyoxometalate derivative and counter cation complex comprising a polyoxometalate derivative anion and a counter cation distributed in the polymer;
wherein the polyoxometalate derivative anion is of the general formula (I):
[XM 11 O 39 (X′L y )] z−   (I)

wherein:
X is a heteroatom selected from the group consisting of Si, B, P, Ge, and As;
z is from 3 to 6;
M is W, Ta, Nb, or Mo;
X′ is a heteroatom or group containing a heteroatom, selected from the group consisting of Si—O—Si, P, Ge, Ti, Sn, and As;
y is from 1 to 2, wherein when X′ is Si—O—Si, y is 2 and one L is bound to each Si atom;
L is of formula (II), an alkylguanidine group, an alicyclic group, an aliphatic group, or an aryl group;

wherein:
R 1 is an alkylene group and R 2 and R 3 are independently selected from the group consisting of H, an alkyl group, an alkenyl group, an alkylamine group, an amide group, an imine group, a heterocyclic group, an aryl group, and an alicyclic group; and
the counter cation is selected from the group consisting of formula (III), of formula (IV), of formula (V), a phenylalanine cation, an alanine cation, an arginine cation, a glycine cation, a histidine cation, a proline cation, an aniline cation, a N,N-dimethylaminopyridine cation, a morpholine cation, a piperazine cation, a monatomic cation, and combinations thereof; with the proviso that when the counter cation is a monatomic cation L is an alkylamine group or an alkylguanidine group;

wherein:
R 4 through R 8 are independently selected from the group consisting of H, an alkyl group, an alicyclic group, an alkenyl group, and an aryl group, with the proviso that fewer than all of R 4 through R 8 are H; or R 4 through R 6 are independently selected from the group consisting of H, an alkyl group, an alicyclic group, an alkenyl group, and an aryl group, and R 7 and R 8 taken together with the N to which they are both bonded form a heterocyclic ring;

wherein:
R 9 is H, an alkyl group, an alkylamine group, or an alicyclic group; R 10 is an alkyl group or an alkylamine group; R 11 and R 12 are independently selected from the group consisting of H and an alkyl group; and

wherein R 13 is C≡N, an alkoxy group, an alkyl group, an alkenyl group, or an aryl group;
with the proviso that if L is an alicyclic group, an aliphatic group, or an aryl group then the counter cation contains a protonated amine group, wherein L is bonded to X′ through a carbon atom;
wherein the counter cation is not covalently bonded to the polymer, and wherein the article is photochromic.

2. The photochromic article of claim 1 , wherein the polymer does not participate stoichiometrically in a photochromic redox reaction of the polyoxometalate derivative and counter cation complex.

3. The photochromic article of claim 1 , wherein the polymer comprises polymethylmethacrylate (PMMA), poly(butyl acrylate), poly(tetrahydrofurfural acrylate), poly(iso-octyl acrylate), poly(isobornyl acrylate), poly(hydroxyethyl acrylate), polymethylmethacrylate copolymer, or a combination thereof.

4. The photochromic article of claim 1 , wherein L is propylguanidine hydrochloride, the cation is tetrabutylammonium, z is 3, X′ is Si—O—Si, and X is P.

5. The photochromic article of claim 1 , wherein the polyoxometalate-guanidinium salt complex is homogeneously distributed in the polymer.

6. A method of forming a photochromic film comprising:
forming a composition comprising a polymer or a precursor of the polymer and a polyoxometalate derivative and counter cation complex comprising a polyoxometalate derivative anion and a counter cation distributed in the polymer; and
preparing a film from the composition, the film comprising the polyoxometalate derivative and counter cation complex distributed in the polymer wherein the counter cation is not covalently bonded to the polymer;
wherein the polyoxometalate derivative anion is of formula (I):
([XM 11 O 39 (x′L y )] z−   (I)

wherein:
X is a heteroatom selected from the group consisting of Si, B, P, Ge, and As;
z is from 3 to 6;
M is W, Ta, Nb, or Mo;
X′ is a heteroatom or group containing a heteroatom, selected from the group consisting of Si—O—Si, P, Ge, Ti, Sn, and As;
y is from 1 to 2, wherein when X′ is Si—O—Si, y is 2 and one L is bound to each Si atom;
L is of formula (II), an alkylamine group, an alkylguanidine group, an alicyclic group, an aliphatic group, or an aryl group;

wherein:
R 1 is an alkylene group and R 2 and R 3 are independently selected from the group consisting of H, an alkyl group, an alkenyl group, an alkylamine group, an amide group, an imine group, a heterocyclic group, an aryl group, and an alicyclic group; and
the counter cation is selected from the group consisting of formula (III), of formula (IV), of formula (V), a phenylalanine cation, an alanine cation, an arginine cation, a glycine cation, a histidine cation, a proline cation, an aniline cation, a N,N-dimethylaminopyridine cation, a morpholine cation, a piperazine cation, a monatomic cation, and combinations thereof; with the proviso that when the counter cation is a monatomic cation L is an alkylamine group or an alkylguanidine group;

wherein:
R 4 through R 8 are independently selected from the group consisting of H, an alkyl group, an alicyclic group, an alkenyl group, and an aryl group, with the proviso that fewer than all of R 4 through R 8 are H; or R 4 through R 6 are independently selected from the group consisting of H, an alkyl group, an alicyclic group, an alkenyl group, and an aryl group, and R 7 and R 8 taken together with the N to which they are both bonded form a heterocyclic ring;

wherein:
R 9 is H, an alkyl group, an alkylamine group, or an alicyclic group; R 10 is an alkyl group or an alkylamine group; R 11 and R 12 are independently selected from the group consisting of H and an alkyl group; and

wherein R 13 is C≡N, an alkoxy group, an alkyl group, an alkenyl group, or an aryl group;
with the proviso that if L is an alicyclic group, an aliphatic group, or an aryl group then the counter cation contains a protonated amine group, wherein L is bonded to X′ through a carbon atom;
wherein the film is photochromic.

7. The method of claim 6 , wherein the polyoxometalate derivative and counter cation complex is dissolved in the composition.

8. The method of claim 6 , wherein the polyoxometalate derivative and counter cation complex is dispersed in the composition.

9. The method of claim 6 , wherein preparing the film comprises drying the composition in an atmosphere comprising less than 50% relative humidity.

10. A precursor composition for forming a photochromic article, the precursor composition comprising:
a polymer or a precursor of the polymer;

Assignees

• 3M Innovative Properties Co

Inventors

• Miller Adam D
• Frey Matthew H
• Isaacson Daniel E
• Janoski Jonathan E

Classifications

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08J2485/00

  Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers · CPC title

• C09K9/02 Primary

  Organic tenebrescent materials · CPC title

• C08L2203/16

  used for films · CPC title

• C09D5/29

  for multicolour effects · CPC title