Oxidative Coupling Copolymerization of 2,6-Dimethylphenol and Dihydroxynaphthalene Affording Poly(phenylene oxide) Derivatives
Table 2
Copolymerization between DMP and DHNs.
Run
Comonomer
Catalyst
Feed ratio
Yield
Unit ratio
DMP : DHN
(%)a
DMP : DHNb
()c
1
2,3-DHN
CuCl-BPy
50 : 50
11
9 : 91
3.6 (1.2)
2
2,3-DHN
CuCl(OH)-TMEDA
50 : 50
38
5 : 95
4.5 (1.3)
3
2,3-DHN
CuCl(OH)-TMEDA
70 : 30
48
12 : 88
9.5 (1.3)
4
2,3-DHN
CuCl(OH)-TMEDA
30 : 70
54
2 : 98
9.9 (1.3)
5
2,6-DHN
CuCl-BPy
50 : 50
66
17 : 83
4.7 (1.3)
6
2,6-DHN
CuCl(OH)-TMEDAd
50 : 50
29
47 : 53
9.0 (1.3)
7
2,6-DHN
CuCl(OH)-TMEDAe
50 : 50
50
50 : 50
10.3 (1.3)
8
2,6-DHN
CuCl(OH)-TMEDA
50 : 50
91
46 : 54
15.2 (2.4)
9
2,6-DHN
CuCl(OH)-TMEDA
70 : 30
50
68 : 32
10.4 (1.2)
10
2,6-DHN
CuCl(OH)-TMEDA
30 : 70
68
31 : 69
8.8 (1.2)
Conditions: [monomers]/[Cu] = 10/1, solvent = THF, time = 24 h, temp. = r.t., and O2 atmosphere. aMeOH-insoluble part of the products after phenylacetylation. bDetermined by 1H NMR analysis (CDCl3). cDetermined by SEC (THF, polystyrene standard). dPolymerization time = 3 h. ePolymerization time = 18 h.