Molecular Weight Control of Thermosetting Poly(phenylene ether) Copolymer Produced by Heterogeneous Oxidative Coupling Polymerization

Abstract

An efficient synthetic method to control the molecular weights of poly(phenylene ether) copolymer (Allyl-PPE) with a narrow molecular weight distribution (MWD) by oxidative coupling polymerization of 2,6-dimethylphenol (DMP) and 2-allyl-6-methylphenol (AMP) has been developed. This polymerization was carried out in the presence of the di-μ-hydroxo-bis[( N , N , N ^′ , N ^′ -tetramethylethylenediamine)copper(II)] chloride (Cu/TMEDA) catalyst in a water droplet/toluene heterogeneous system. The polymerization conditions such as the effects of the Cu/TMEDA concentration and the amount of water were investigated, and it was found that the molecular weight of Allyl-PPE could be easily controlled by changing the concentration of Cu/TMEDA aqueous solution.

Keywords

Poly(phenylene ether)thermosets oxidative coupling polymerization heterogeneous polymerization molecular weight control dielectric properties

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References

Maier, G. ( 2001). Low Dielectric Constant Polymers for Microelectronics, Prog. Polym. Sci., 26: 3-65.

Vrtis, R.N. , Heap, K.A. , Burgoyne, W.F. and Robeson, L.M. (1997). Poly(Arylene Ethers) as Low Dielectric Constant Materials for ULSI Interconnect Applications, Mater . Res. Soc. Proc., 443, 171-176.

Watanabe, Y. , Shibasaki, Y. , Ando , S. and Ueda, M. (2006). Synthesis and Characterization of Novel Low-k Polyimides from Aromatic Dianhydrides and Aromatic Diamine Containing Phenylene Ether and Perfluorobiphenyl Units , Polym. J., 38, 79-84.

Tsuchiya, K. and Ueda, M. (2006). Synthesis of Poly(Naphthylene Ether) Containing Tetraphenylmethane Group with a Low Dielectric Constant , Polym. J., 38, 956-960.

Hay, A.S. (1962). Polymerization by Oxidative Coupling. II. Oxidation of 2,6-Disubstituted Phenols, J. Polym. Sci., 58, 581-591.

Fukuhara, T. , Shibasaki, Y. , Ando , S. and Ueda, M. (2004). Synthesis of Thermosetting Poly(Phenylene Ether) Containing Allyl Groups, Polymer 45, 843-847.

Nunoshige, J. , Akahoshi, H. , Shibasaki , Y. and Ueda, M. (2007). Low Dielectric Loss Copolymer Obtained from 2,6-Dimethylphenol and 2-Allyl-6-methylphenol via Cu-catalyzed Oxidative Coupling Polymerization, Chem. Lett., 36: 238-239.

Nunoshige, J. , Akahoshi, H. , Shibasaki , Y. and Ueda, M. (2008). Efficient Oxidative Coupling Polymerization for Synthesis of Thermosetting Poly(Phenylene Ether) Copolymer with a Low Dielectric Loss, J. Polym. Sci. Part A: Polym. Chem., 46, 5278-5282.

Nunoshige, J. , Akahoshi, H. , Liao , Y. , Horiuchi, S. , Shibasaki, Y. and Ueda, M. (2007). Mechanical and Dielectric Properties of a New Polymer Blend Composed of 1,2-Bis(vinylphenyl)ethane and Thermosetting Poly(phenylene ether) Copolymer Obtained from 2,6-Dimethylphenol and 2-Allyl-6-methylphenol, Polym. J. 39: 828-833.

10.

Endres, G.F. and Kwiatek, J. (1962). Polymerization by Oxidative Coupling. III. Mechanistic Type in the Copper-Amine Catalyzed Polymerization of 2,6-Dimethylphenol, J. Polym. Sci., 58, 593-609.