Preparation of poly(p-oxybenzoyl) crystals using direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides

Masahiro Kihara, Shin Ichiro Kohama, Shota Umezono, Kanji Wakabayashi, Shinichi Yamazaki, Kunio Kimura

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Poly(p-oxybenzoyl) (POB) crystals were prepared by reaction-induced crystallization during direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides. Polymerizations were carried out at 300 °C in dibenzyltoluene at a concentration of 1% with three kinds of anhydrides of boronic acid such as 3,4,5-trifluorophenylboronic acid (TFB), 4-methoxyphenylboronic acid (MPB) and 4-biphenylboronic acid (BPB). The POB crystals were formed as precipitates in the solution and the morphology was considerably influenced by both the structure of the boronic anhydride and its concentration (cB). Needle-like crystals were firmed in the presence of TFB anhydride (TFBA) at cBs of 5 and 10 mol % by the spiral growth of lamellae. Spherical aggregates of slab-like crystals were formed at c Bs from 50 to 100 mol %. The polymerization with MPB anhydride and BPB anhydride (BPBA) also yielded the needle-like crystals at cBs of 50 and 5 mol %, respectively. The polymerization with TFBA at lower c B was favorable to prepare the needle-like crystal. Molecular weight was also influenced by the structure of the boronic anhydride and cB. Mn increased generally with cB and BPBA gave the highest Mn of 14.7 × 103 at cB of 100 mol %. The loose packing of the molecules in the crystal caused by the bulkiness of the end-groups made the polymerization in the crystals more efficiently. Morphology and molecular weight of the POB crystals could be controlled by the chemical structure and the content of boronic anhydride.

Original languageEnglish
Pages (from-to)1088-1096
Number of pages9
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume49
Issue number5
DOIs
Publication statusPublished - Mar 1 2011

Fingerprint

Hydroxybenzoates
Anhydrides
Polymerization
Crystals
Acids
Needles
Molecular weight
Boronic Acids
Crystallization
Precipitates
Molecules

Keywords

  • crystallization
  • high performance polymers
  • morphology
  • polycondensation
  • polyesters

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Preparation of poly(p-oxybenzoyl) crystals using direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides. / Kihara, Masahiro; Kohama, Shin Ichiro; Umezono, Shota; Wakabayashi, Kanji; Yamazaki, Shinichi; Kimura, Kunio.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 49, No. 5, 01.03.2011, p. 1088-1096.

Research output: Contribution to journalArticle

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abstract = "Poly(p-oxybenzoyl) (POB) crystals were prepared by reaction-induced crystallization during direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides. Polymerizations were carried out at 300 °C in dibenzyltoluene at a concentration of 1{\%} with three kinds of anhydrides of boronic acid such as 3,4,5-trifluorophenylboronic acid (TFB), 4-methoxyphenylboronic acid (MPB) and 4-biphenylboronic acid (BPB). The POB crystals were formed as precipitates in the solution and the morphology was considerably influenced by both the structure of the boronic anhydride and its concentration (cB). Needle-like crystals were firmed in the presence of TFB anhydride (TFBA) at cBs of 5 and 10 mol {\%} by the spiral growth of lamellae. Spherical aggregates of slab-like crystals were formed at c Bs from 50 to 100 mol {\%}. The polymerization with MPB anhydride and BPB anhydride (BPBA) also yielded the needle-like crystals at cBs of 50 and 5 mol {\%}, respectively. The polymerization with TFBA at lower c B was favorable to prepare the needle-like crystal. Molecular weight was also influenced by the structure of the boronic anhydride and cB. Mn increased generally with cB and BPBA gave the highest Mn of 14.7 × 103 at cB of 100 mol {\%}. The loose packing of the molecules in the crystal caused by the bulkiness of the end-groups made the polymerization in the crystals more efficiently. Morphology and molecular weight of the POB crystals could be controlled by the chemical structure and the content of boronic anhydride.",
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