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 : DHN^b	()^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)-TMEDA^d	50 : 50	29	47 : 53	9.0 (1.3)
7	2,6-DHN	CuCl(OH)-TMEDA^e	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.