Spirofluorene-based polymer and organic electroluminescent device using the same
View Patent ↗A spirofluorene-based polymer which contains a spirofluorene structure as a basic unit and which is end-capped with functional moieties substituted by fluorine, and an organic electroluminescent device using an organic layer using the spirofluorene-based polymer. The organic electroluminescent device has improved efficiency, reduced driving voltage, and excellent thermal, optical and electrical stability.
1. A spirofluorene-based polymer having Formula 3:
wherein each of R 1 to R 4 is a mono-substituted or multi-substituted substituent, and is independently selected from the group consisting of a hydrogen, a hydroxy group, an amino group, a substituted or unsubstituted C 1-30 alkylamino group, a substituted or unsubstituted C 6-30 arylamino group, a substituted or unsubstituted C 2-30 heteroarylamino group, a cyano group, a halogen atom, a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 1-30 alkoxy group, a substituted or unsubstituted C 6-30 aryl group, a substituted or unsubstituted C 6-30 aryloxy group, a substituted or unsubstituted C 6-30 aryl alkyl group, a substituted or unsubstituted C 2-30 heteroaryl group and a substituted or unsubstituted C 2-30 heterocyclic group,
at least one of R 1 and R 2 , and R 3 and R 4 may be linked to each other to form a saturated or unsaturated ring,
Ec 1 and Ec 2 are independently selected from the group consisting of the moieties having Formulae 2a through 2w:
wherein R 5 to R 10 are mono-substituted or multi-substituted functional groups and are independently selected from the group consisting of at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 6-30 aryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 2-30 heteroaryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 2-30 heterocyclic group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 3-30 cycloalkyl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, and a substituted or unsubstituted C 6-30 fused aryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12;
Ar is selected from the group consisting of a substituted or unsubstituted C 6-30 arylene group, a substituted or unsubstituted C 2-30 heteroarylene group, and a substituted or unsubstituted C 2-30 heterocyclic group;
x is a real number of 1 or 0.01 to 0.99;
y is a real number of 0 or 0.01 to 0.99; and
z represents the degree of polymerization and is a real number of 10 to 150.
2. The polymer of claim 1 , wherein
x is a real number of 0.01 to 0.99; and
y is a real number of 0.01 to 0.99.
3. The polymer of claim 1 , wherein the polymer has a number average molecular weight ranging from 10,000 to 200,000.
4. The polymer of claim 1 , wherein x is 1, and Y is 0.
5. The polymer of claim 2 , wherein the polymer has Formula 4:
wherein each of R′ and R″ is independently a C 1-12 alkyl group;
m and n are independent real numbers of 0 to 2;
x is 0.01 to 0.99;
y is 0.01 to 0.99; and
z is a real number of 10 to 150.
6. The polymer of claim 5 , wherein the polymer has Formula 5:
7. An organic electroluminescent device comprising an organic layer between a pair of electrodes, the organic layer containing the spirofluorene-based polymer of claim 1 .
8. An organic electroluminescent device, comprising:
a pair of electrodes; and
an organic layer between said pair of electrodes, the organic layer containing a spirofluorene-based polymer represented by Formula 3:
wherein each of R 1 to R 1 is a mono-substituted or multi-substituted substituent, and is independently selected from the group consisting of a hydrogen, a hydroxy group, an amino group, a substituted or unsubstituted C 1-30 alkylamino group, a substituted or unsubstituted C 6-30 arylamino group, a substituted or unsubstituted C 2-30 heteroarylamino group, a cyano group, a halogen atom, a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 1-30 alkoxy group, a substituted or unsubstituted C 6-30 aryl group, a substituted or unsubstituted C 6-30 aryloxy group, a substituted or unsubstituted C 6-30 aryl alkyl group, a substituted or unsubstituted C 2-30 heteroaryl group and a substituted or unsubstituted C 2-30 heterocyclic group;
at least one of R 1 and R 2 , and R 3 and R 4 may be linked to each other to form a saturated or unsaturated ring;
Ec 1 and Ec 2 are independently selected from the group consisting of the moieties having Formulae 2a through 2w:
wherein R 5 to R 10 are mono-substituted or multi-substituted functional groups and are independently selected from the group consisting of at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 6-30 aryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 2-30 heteroaryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 2-30 heterocyclic group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 3-30 cycloalkyl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, and a substituted or unsubstituted C 6-30 fused aryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12;
Ar is selected from the group consisting of a substituted or unsubstituted C 6-30 arylene group, a substituted or unsubstituted C 2-30 heteroarylene group, and a substituted or unsubstituted C 2-30 heterocyclic group;
x is a real number of 1 or 0.01 to 0.99;
y is a real number of 0 or 0.01 to 0.99; and
z represents the degree of polymerization and is a real number of 10 to 150.
9. The organic electroluminescent device of claim 8 , wherein the organic layer is an electroluminescent layer.
10. The organic electroluminescent device of claim 8 , wherein
x is a real number of 0.01 to 0.99; and
y is a real number of 0.01 to 0.99.
11. The organic electroluminescent device of claim 8 , wherein the polymer has a number average molecular weight ranging from 10,000 to 200,000.
12. The organic electroluminescent device of claim 8 , wherein x is 1, and y is 0.
13. The organic electroluminescent device of claim 10 , wherein the polymer has Formula 4:
wherein each of R′ and R″ is independently a C 1-12 alkyl group;
m and n are independent real numbers of 0 to 2;
x is 0.01 to 0.99;
y is 0.01 to 0.99; and
z is a real number of 10 to 150.
14. The organic electroluminescent device of claim 12 , wherein the polymer has Formula 5:
15. The organic electroluminescent device of claim 8 , wherein the molecular weight distribution of the spirofluorene-based polymer ranges from 1.5 to 5.
16. An organic electroluminescent device, comprising:
a pair of electrodes; and
an electroluminescent layer between said pair of electrodes, the electroluminescent layer containing a spirofluorene-based polymer having a number average molecular weight ranging from 10,000 to 200,000, said spirofluorene-based polymer represented by Formula 3:
wherein each of R 1 to R 4 is a mono-substituted or multi-substituted substituent, and is independently selected from the group consisting of a hydrogen, a hydroxy group, an amino group, a substituted or unsubstituted C 1-30 alkylamino group, a substituted or unsubstituted C 6-30 arylamino group, a substituted or unsubstituted C 2-30 heteroarylamino group, a cyano group, a halogen atom, a substituted or unsubstituted C 1-30 alkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 1-30 alkoxy group, a substituted or unsubstituted C 6-30 aryl group, a substituted or unsubstituted C 6-30 aryloxy group, a substituted or unsubstituted C 6-30 aryl alkyl group, a substituted or unsubstituted C 2-30 heteroaryl group and a substituted or unsubstituted C 2-30 heterocyclic group;
at least one of R 1 and R 2 , and R 3 and R 4 may be linked to each other to form a saturated or unsaturated ring;
Ec 1 and Ec 2 are independently selected from the group consisting of the moieties having the formulae 2a through 2w:
wherein R 5 to R 10 are mono-substituted or multi-substituted functional groups and are independently selected from the group consisting of at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 6-30 aryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 2-30 heteroaryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 2-30 heterocyclic group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, a substituted or unsubstituted C 3-30 cycloalkyl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12, and a substituted or unsubstituted C 6-30 fused aryl group having at least one F or —(CF 2 ) n CF 3 where n=an integer of 1 to 12;
Ar is selected from the group consisting of a substituted or unsubstituted C 6-30 arylene group, a substituted or unsubstituted C 2-30 heteroarylene group, and a substituted or unsubstituted C 2-30 heterocyclic group;
x is a real number of 1 or 0.01 to 0.99:
y is a real number of 0 or 0.01 to 0.99: and
z represents the degree of polymerization and is a real number of 10 to 150.
17. The organic electroluminescent device of claim 16 , wherein
x is a real number of 0.01 to 0.99; and
y is a real number of 0.01 to 0.99.
18. The organic electroluminescent device of claim 17 , wherein the polymer is represented by Formula 4:
wherein each of R′ and R″ is independently a C 1-12 alkyl group,
m and n are independent real numbers of 0 to 2;
x is 0.01 to 0.99;
y is 0.01 to 0.99; and
z is a real number of 10 to 150.
19. The organic electroluminescent device of claim 18 , wherein the polymer is represented by Formula 5:
20. The organic electroluminescent device of claim 16 , wherein the molecular weight distribution of the spirofluorene-based polymer ranges from 1.5 to 5.