Coumarin-functionalized polyolefin and associated cyclodimerization products, preparation methods, and electronic devices

Patent metadata

Field	Value
Publication number	US-9394390-B2
Application number	US-201414762835-A
Country	US
Kind code	B2
Filing date	Feb 6, 2014
Priority date	Feb 7, 2013
Publication date	Jul 19, 2016
Grant date	Jul 19, 2016

Abstract

A polyolefin is functionalized with two, three, or more terminal coumarin groups. When irradiated with longer wavelength ultraviolet light (e.g., 365 nanometers), the coumarin groups cyclodimerize to form a chain-extended or crosslinked polyolefin. The cyclodimerization can be reversed by irradiation with shorter wavelength ultraviolet light (e.g., 254 nanometers). When the crosslinked polyolefin is used to form a barrier layer in a light emitting diode or a photovoltaic device, scratches in the barrier layer cleave the cyclodimer groups and can be “healed” by irradiation to reduce or remove the scratches.

First claim

The invention claimed is:

1. A compound of the following formula:

wherein:
L is a multivalent initiator residue;
k is an integer greater than or equal to 2;
A for each occurrence independently is selected from —NR a —, —O—, or —OC(O)—, wherein R a is a H or a C 1 -C 4 alkyl;
R 3 , R 4 , R 5 for each occurrence independently is each independently selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, amino, C 1 -C 6 alkoxy, —C(O)OR a , hydroxy, or a halogen;
n for each occurrence independently is an integer not less than 2;
m for each occurrence independently is 0, 1, 2 or 3;
R 1 for each occurrence independently is H or a C 1 -C 4 alkyl, a C 1 -C 6 alkoxy or a substituted or unsubstituted aryl; and
R 2 for each occurrence independently is H, X 2 , CH 2 X 2 , CHX 2 2 , CX 2 3 , CN, or NO 2 , wherein X 2 , for each occurrence, is independently a halogen.

2. The compound of claim 1 , wherein
R 1 for each occasion is independently H or a C 1 -C 4 alkyl; and
R 2 for each occasion is independently H.

3. The compound of claim 1 , wherein
A for each occurrence independently is selected from —NR a — or —O—;
m is 0; and
R 3 and R 4 is each independently selected from H, C 1 -C 6 alkyl, or —C(O)OR a .

4. The compound of claim 1 , represented by the following structural formula:

5. The compound of claim 1 , represented by the following structural formula:

wherein

6. A method of synthesis of a compound of claim 1 , comprising a step of reacting a compound represented by the following structural formula

wherein X 1 is for each occurrence, independently, a halogen, with a compound of the following structural formula

7. The method of claim 6 , comprising the step of reacting the compound represented by the following structural formula

with the compound represented by the following structural formula:

8. A dendritic polymer including repeating unit represented by the following structure formula:
L-Y—Z 2 —Y-L,

wherein:
L is a multivalent initiator residue;
Y, for each occurrence independently, is represented by the following structural formula

Z 2 is a dimer selected from

and further wherein:
A for each occurrence independently is selected from —NR a —, —O—, or —OC(O)—, wherein R a is a H or a C 1 -C 4 alkyl;
R 3 , R 4 , R 5 for each occurrence independently is each independently selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, amino, C 1 -C 6 alkoxy, —C(O)OR a , hydroxy, or a halogen;
n for each occurrence independently is an integer not less than 2;
m for each occurrence independently is 0, 1, 2 or 3;
R 1 for each occurrence independently is H or a C 1 -C 4 alkyl, a C 1 -C 6 alkoxy or a substituted or unsubstituted aryl; and
R 2 for each occurrence independently is H, X 2 , CH 2 X 2 , CHX 2 2 , CX 2 3 , CN, or NO 2 , wherein X 2 , for each occurrence, is independently a halogen.

9. The dendritic polymer of claim 8 , wherein:
L is represented by the following structural formula:

Y is represented by the following structural formula:

 and
Z 2 is a dimer selected from

10. A method of synthesis of a dendritic polymer, the method comprising:
dimerizing a branched precursor represented by the following structural formula:
L-(Y—Z) k

 to produce a dendritic polymer including a repeating unit represented by the following structural formula:
L-Y—Z 2 —Y-L,

 wherein:
L is a multivalent initiator residue;
k is an integer greater than or equal to 2;
Y, for each occurrence independently, is represented by the following structural formula

Z is represented by the following structural formula:

Z 2 is a dimer selected from

 and further wherein:
A for each occurrence independently is selected from —NR a —, —O—, or —OC(O)—, wherein R a is a H or a C 1 -C 4 alkyl;
R 3 , R 4 , R 5 for each occurrence independently is each independently selected from H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, amino, C 1 -C 6 alkoxy, —C(O)OR a , hydroxy, or a halogen;
n for each occurrence independently is an integer not less than 2;
m for each occurrence independently is 0, 1, 2 or 3;
R 1 for each occurrence independently is H or a C 1 -C 4 alkyl, a C 1 -C 6 alkoxy or a substituted or unsubstituted aryl; and
R 2 for each occurrence independently is H, X 2 , CH 2 X 2 , CHX 2 2 , CX 2 3 , CN, or NO 2 , wherein X 2 , for each occurrence, is independently a halogen.

11. The method of claim 10 , wherein dimerizing the branched precursor includes exposing the branched precursor to the ultraviolet radiation.

12. The method of claim 10 , wherein:
L is represented by the following structural formula:

Y is represented by the following structural formula:

Z is represented by the following structural formula:

 and
Z 2 is a dimer selected from

13. An electronic device comprising an encapsulant or barrier layer comprising the compound of claim 1 or the dendritic polymer of claim 8 .

14. The electronic device of claim 13 , selected from a light emitting diode and a photovoltaic device.

Assignees

• Univ Massachusetts
• Univ Massachusetts

Inventors

• Faust Rudolf
• Tripathy Ranjan

Classifications

• C08F2/48

  by ultraviolet or visible light · CPC title

• C08F8/26

  Removing halogen atoms or halogen-containing groups from the molecule · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• C08F110/10 Primary

  Isobutene · CPC title

• C07D311/08 Primary

  not hydrogenated in the hetero ring · CPC title