Synthesis and Properties of a Novel Boron-containing Poly(arylether ketone) and Its Application in the Preparation of Azo Poly(aryl ether ketone)†

doi:10.7503/cjcu20131109

Abstract

Abstract:

Novel poly(aryl ether ketone)s with pendant pinacolboronate groups(PAEK-Bpin) and boric acid groups(PAEK-BOH) were synthesized. PAEK-Bpin was prepared by the borylation of poly(aryl ether ketone) in the presence of [IrCl(COD)]₂ and dtbpy. The quantitative introduction of borate can be controlled by the amount of Bis(pinacolato)diboron(B₂pin₂). PAEK-BOH was obtained under the action of NaIO₄. Azo-PAEK was obtained via Suzuki-Miyaura reaction. The structure and property characterizations of all related products were carried out using ¹H-nuclear magnetic resonance(¹H NMR), ultraviolet and visible spectrophotometer(UV-Vis), gel permeation chromatography(GPC), differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA). The results of structure characterization suggest that products are synthesized. The results of GPC show that Ir catalyst and Suzuki-Miyaura reaction do not affect the molecular weight of the polymers. DSC results indicate that the glass transition temperature of PAEK-Bpin increases with the increase of the amount of boronate. However, PAEK-Bpin has good solubility in most of polar aprotic solvents. The preparation of boron-containing poly(aryl ether ketone) provides more broad prospects for further functionalization of the poly(aryl ether ketone).

Key words: Poly(aryl ether ketone), Borylation, Borate, Boric acid, Suzuki-Miyaura Reaction, Azo

CLC Number:

O632

TrendMD:

WANG Yongpeng, LIU Mengzhu, ZHANG Yuxuan, LIN Yingjian, SHANG Yingshuang, ZHU Xuanbo, ZHANG Haibo, JIANG Zhenhua. Synthesis and Properties of a Novel Boron-containing Poly(arylether ketone) and Its Application in the Preparation of Azo Poly(aryl ether ketone)^†[J]. Chem. J. Chinese Universities, 2014, 35(5): 1086.

Figures/Tables 11

Scheme 1 Synthetic route of PAEK

Table 1 Iridium-catalyzed arene C—H borylation of poly(arylene ether ketone)(PAEK) with bis(pinacolato)diboron(B2pin2)

Sample	10^-4 M_n	PDI, M_w/M_n	x(Bpin)(%)
PAEK-Bpin-15	7.7	1.62	15
PAEK-Bpin-30	8.4	1.35	30
PAEK-Bpin-150	9.3	1.36	150

Scheme 2 Iridium-catalyzed C—H borylation of poly(arylene ether ketone) and preparation of PAEK-BOH

Scheme 3 Synthesis of 4-[(4-iodophenyl)diazenyl]-N,N-dimethylaniline

Scheme 4 Synthesis of azo-PAEK

Fig.1 1H NMR spectra of PAEK(a), PAEK-Bpin-30(b) and PAEK-BOH-30(c)

Fig.2 1H NMR spectra of azo-PAEK

Table 2 Solubility of PAEK, PAEK-Bpin-15, PAEK-Bpin-30, PAEK-Bpin-150, PAEK-BOH-15 and PAEK-BOH-30 in different solvents

Polymer	Solvent
Polymer	DMF	DMAc	DMSO	NMP	Dioxane	THF	CHCl₃	Actone	Ethanol
PAEK	-	-	-	-	++	++	++	-	-
PAEK-Bpin-15%	-	-	-	-	++	++	++	-	-
PAEK-Bpin-30%	-	-	-	-	++	++	++	-	-
PAEK-Bpin-150%	-	-	-	-	+	+	+	-	-
PAEK-BOH-15%	-	-	-	-	++	++	++	-	-
PAEK-BOH-30%	-	-	-	-	+	+	+	-	-

Fig.3 DSC curves of PAEK(a), PAEK-Bpin-15(b), PAEK-Bpin-30(c), PAEK-Bpin-150(d), PAEK-BOH-15(e), PAEK-BOH-30(f) and azo-PAEK(g)

Fig.4 TGA curves of PAEK(a), PAEK-Bpin-30(b), PAEK-BOH-30(c) and azo-PAEK(d)

Fig.5 UV-Vis spectra of PAEK(a), and azo-PAEK(b) in CHCl3

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