Synthesis of poly (2,6-dimethyl-1,4-phenylene oxide) by double-step polymerization in supercritical carbon dioxide

Hidenori Murata, Takuro Sato, Kenichi Oyaizu, Takeshi Furuya, Yoshihiro Takebayashi, Satoshi Yoda, Katsuto Otake, Makoto Yuasa

Research output: Contribution to journal › Article

Abstract

Oxidative polymerization of 2,6-dimethylphenol (2,6-DMP) is a convenient method to prepare poly (2,6-dimethyl-1,4-phenyleneoxide) (PPO), an important plastic in engineering. The polymerization of 2,6-DMP is carried out in organic solvents under oxygen; thus, a solvent-recovery system and an anti-explosive reactor are required for the industrial application. The use of scCO2 instead of organic solvents is expected to make the polymerization of 2,6-DMP safer and environmentally more benign. We have studied the oxidative polymerization of 2,6-DMP in scCO2. In this report, we have applied the 'double-step polymerization' method in scCO2 to synthesize PPO with better polymer properties, i.e., higher average molecular weight (Mw) and narrower molecular weight distribution (Mw/Mn). In the first step, a prepolymer with a narrow molecular weight distribution (Mw/Mn = 1.4) was synthesized under a homogeneous-phase condition. The prepolymer was purified and dried to remove water. In the second step, the prepolymer was further polymerized to increase the molecular weight. The second-step polymerization was performed at 40°C and 20 MPa. The Mw was increased from 4.9 × 103 to 9.0 × 103, keeping the narrow molecular weight distribution (Mw/Mn = 1.4). We further optimized the polymerization condition in the second step to obtain higher molecular weight. The Mw was increased to 3.4 × 104 (Mw/Mn = 2.3) at 80°C and 15 MPa in the presence of CuBr (0.0004 mol) and pyridine (0.019 mol).

Original languageEnglish
Pages (from-to)688-694
Number of pages7
JournalKobunshi Ronbunshu
Volume65
Issue number11
DOIs
Publication statusPublished - 2008 Nov
Externally publishedYes

Fingerprint

polymerization
Carbon Dioxide
Carbon dioxide
carbon dioxide
Molecular weight
Polymerization
oxide
Oxides
Molecular weight distribution
Polyphenylene oxides
Organic solvents
poly(2,6-dimethyl-1,4-phenylene oxide)
Pyridine
Industrial applications
Polymers
Oxygen
Plastics
explosive
Recovery
2,6-xylenol

Keywords

  • Molecular weight distribution
  • Oxidative polymerization
  • Poly (phenylene oxide)
  • Supercritical carbon dioxide

ASJC Scopus subject areas

  • Polymers and Plastics
  • Environmental Science(all)
  • Materials Science (miscellaneous)
  • Chemical Engineering (miscellaneous)

Cite this

Synthesis of poly (2,6-dimethyl-1,4-phenylene oxide) by double-step polymerization in supercritical carbon dioxide. / Murata, Hidenori; Sato, Takuro; Oyaizu, Kenichi; Furuya, Takeshi; Takebayashi, Yoshihiro; Yoda, Satoshi; Otake, Katsuto; Yuasa, Makoto.

In: Kobunshi Ronbunshu, Vol. 65, No. 11, 11.2008, p. 688-694.

Research output: Contribution to journal › Article

Murata, H, Sato, T, Oyaizu, K, Furuya, T, Takebayashi, Y, Yoda, S, Otake, K & Yuasa, M 2008, 'Synthesis of poly (2,6-dimethyl-1,4-phenylene oxide) by double-step polymerization in supercritical carbon dioxide', Kobunshi Ronbunshu, vol. 65, no. 11, pp. 688-694. https://doi.org/10.1295/koron.65.688
Murata H, Sato T, Oyaizu K, Furuya T, Takebayashi Y, Yoda S et al. Synthesis of poly (2,6-dimethyl-1,4-phenylene oxide) by double-step polymerization in supercritical carbon dioxide. Kobunshi Ronbunshu. 2008 Nov;65(11):688-694. https://doi.org/10.1295/koron.65.688
Murata, Hidenori ; Sato, Takuro ; Oyaizu, Kenichi ; Furuya, Takeshi ; Takebayashi, Yoshihiro ; Yoda, Satoshi ; Otake, Katsuto ; Yuasa, Makoto. / Synthesis of poly (2,6-dimethyl-1,4-phenylene oxide) by double-step polymerization in supercritical carbon dioxide. In: Kobunshi Ronbunshu. 2008 ; Vol. 65, No. 11. pp. 688-694.
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abstract = "Oxidative polymerization of 2,6-dimethylphenol (2,6-DMP) is a convenient method to prepare poly (2,6-dimethyl-1,4-phenyleneoxide) (PPO), an important plastic in engineering. The polymerization of 2,6-DMP is carried out in organic solvents under oxygen; thus, a solvent-recovery system and an anti-explosive reactor are required for the industrial application. The use of scCO2 instead of organic solvents is expected to make the polymerization of 2,6-DMP safer and environmentally more benign. We have studied the oxidative polymerization of 2,6-DMP in scCO2. In this report, we have applied the 'double-step polymerization' method in scCO2 to synthesize PPO with better polymer properties, i.e., higher average molecular weight (Mw) and narrower molecular weight distribution (Mw/Mn). In the first step, a prepolymer with a narrow molecular weight distribution (Mw/Mn = 1.4) was synthesized under a homogeneous-phase condition. The prepolymer was purified and dried to remove water. In the second step, the prepolymer was further polymerized to increase the molecular weight. The second-step polymerization was performed at 40°C and 20 MPa. The Mw was increased from 4.9 × 103 to 9.0 × 103, keeping the narrow molecular weight distribution (Mw/Mn = 1.4). We further optimized the polymerization condition in the second step to obtain higher molecular weight. The Mw was increased to 3.4 × 104 (Mw/Mn = 2.3) at 80°C and 15 MPa in the presence of CuBr (0.0004 mol) and pyridine (0.019 mol).",
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T1 - Synthesis of poly (2,6-dimethyl-1,4-phenylene oxide) by double-step polymerization in supercritical carbon dioxide

AU - Murata, Hidenori

AU - Sato, Takuro

AU - Oyaizu, Kenichi

AU - Furuya, Takeshi

AU - Takebayashi, Yoshihiro

AU - Yoda, Satoshi

AU - Otake, Katsuto

AU - Yuasa, Makoto

PY - 2008/11

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N2 - Oxidative polymerization of 2,6-dimethylphenol (2,6-DMP) is a convenient method to prepare poly (2,6-dimethyl-1,4-phenyleneoxide) (PPO), an important plastic in engineering. The polymerization of 2,6-DMP is carried out in organic solvents under oxygen; thus, a solvent-recovery system and an anti-explosive reactor are required for the industrial application. The use of scCO2 instead of organic solvents is expected to make the polymerization of 2,6-DMP safer and environmentally more benign. We have studied the oxidative polymerization of 2,6-DMP in scCO2. In this report, we have applied the 'double-step polymerization' method in scCO2 to synthesize PPO with better polymer properties, i.e., higher average molecular weight (Mw) and narrower molecular weight distribution (Mw/Mn). In the first step, a prepolymer with a narrow molecular weight distribution (Mw/Mn = 1.4) was synthesized under a homogeneous-phase condition. The prepolymer was purified and dried to remove water. In the second step, the prepolymer was further polymerized to increase the molecular weight. The second-step polymerization was performed at 40°C and 20 MPa. The Mw was increased from 4.9 × 103 to 9.0 × 103, keeping the narrow molecular weight distribution (Mw/Mn = 1.4). We further optimized the polymerization condition in the second step to obtain higher molecular weight. The Mw was increased to 3.4 × 104 (Mw/Mn = 2.3) at 80°C and 15 MPa in the presence of CuBr (0.0004 mol) and pyridine (0.019 mol).

AB - Oxidative polymerization of 2,6-dimethylphenol (2,6-DMP) is a convenient method to prepare poly (2,6-dimethyl-1,4-phenyleneoxide) (PPO), an important plastic in engineering. The polymerization of 2,6-DMP is carried out in organic solvents under oxygen; thus, a solvent-recovery system and an anti-explosive reactor are required for the industrial application. The use of scCO2 instead of organic solvents is expected to make the polymerization of 2,6-DMP safer and environmentally more benign. We have studied the oxidative polymerization of 2,6-DMP in scCO2. In this report, we have applied the 'double-step polymerization' method in scCO2 to synthesize PPO with better polymer properties, i.e., higher average molecular weight (Mw) and narrower molecular weight distribution (Mw/Mn). In the first step, a prepolymer with a narrow molecular weight distribution (Mw/Mn = 1.4) was synthesized under a homogeneous-phase condition. The prepolymer was purified and dried to remove water. In the second step, the prepolymer was further polymerized to increase the molecular weight. The second-step polymerization was performed at 40°C and 20 MPa. The Mw was increased from 4.9 × 103 to 9.0 × 103, keeping the narrow molecular weight distribution (Mw/Mn = 1.4). We further optimized the polymerization condition in the second step to obtain higher molecular weight. The Mw was increased to 3.4 × 104 (Mw/Mn = 2.3) at 80°C and 15 MPa in the presence of CuBr (0.0004 mol) and pyridine (0.019 mol).

KW - Molecular weight distribution

KW - Oxidative polymerization

KW - Poly (phenylene oxide)

KW - Supercritical carbon dioxide

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