Synthesis of Amorphous Polyaryletherketone Containing Phthalein and Fluorene as Side Groups†

doi:10.7503/cjcu20140564

Abstract

Abstract:

A series of linear high molecular weight amorphous polyaryletherketone(PAEK) copolymers with phthalein and fluorene side groups was synthesized on the basis of the polyetherketone with phthalein cardo group(PEK-C). The structures were characterized by FTIR, ¹H NMR, ¹³C NMR. Gel permeation chromatography(GPC) data indicated that the $M ¯ n$ and the $M ¯ w$ of the copolymer were higher than 6.0×10⁴ and 1.0×10⁵, respectively, with a polydisperity index(PDI) ranging from 1.6 to 1.7. The X-ray diffraction(XRD) data revealed that the copolymers were amorphous structure. Thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC) tests showed that the copolymers exhibited good heat resistant property. The onset temperature of mass loss was higher than 467 ℃. The char yield at 700 ℃ was more than 58.9%. There was a single glass transition temperature(T_g), with T_g>243 ℃. The elastic modulus and elongation at break of the copolymer showed a significant increase, up to 3.1 GPa and 58%, respectively, which were 1.4 folds and 8.3 folds compared to that of PEK-C when the feed ratio of phenolphthalein and 9,9-bis(4-hydroxyphenyl) fluorene was between 3:7 and 5:5. Amorphous polyaryletherketone containing phthalein and fluorene as side groups kept good solubility in chloroform, dichloromethane, tetrahydrofuran(THF), N-methyl-2-pyrrolidone(NMP) and other aprotic solvents. The mechanical and thermal properties were improved significantly.

Key words: Amorphous polyaryletherketone, Copolymer, Phenolphthalein, 9, 9-Bis(4-hydroxyphenyl)fluorene, High-performance resin

CLC Number:

O633.1

TrendMD:

WANG Zhipeng, WANG Feifei, WANG Honghua, ZHOU Guangyuan. Synthesis of Amorphous Polyaryletherketone Containing Phthalein and Fluorene as Side Groups^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2487.

Figures/Tables 12

Scheme 1 Synthesis of PHT-DFK-BPF copolymers with phthalein and fluorene side groups

Table 1 Characterization of the PHT-DFK-BPF copolymers

Copolymer	n(PHT):n(BPF)	η_sp·c^-1/(dL·g^-1)	10^-4M_n	10^-4M_w	PDI
T10F0	100:0	2.15	17.8	28.6	1.6
T9F1	90:10	1.47	11.4	18.9	1.7
T8F2	80:20	0.88	10.3	17.3	1.7
T7F3	70:30	0.82	6.0	10.1	1.7
T6F4	60:40	0.97	7.3	12.5	1.7
T5F5	50:50	1.30	6.7	11.2	1.7
T4F6	40:60	1.12	9.9	16.0	1.6
T3F7	30:70	1.81	15.9	25.8	1.6
T2F8	20:80	0.80	6.0	10.1	1.7
T1F9	10:90	0.82	6.2	10.8	1.7
T0F10	0:100	1.77	15.9	27.7	1.7

Fig.1 1H NMR(A) and quantitative 13C NMR spectra of PHT-DFK-BPF copolymers(B)

Fig.2 FTIR spectra of PHT-DFK-BPF copolymers

Fig.3 DSC curves(A) of PHT-DFK-BPF copolymers and the linear fit curves of Tg(B)

Table 2 Heat-resistant properties of PHT-DFK-BPF copolymer

Copolymer	$T g a$ /℃	T_g'^b/℃	$T onset c$ /℃	$T 5 % d$ /℃	$T 10 % e$ /℃	$T max f$ /℃	CY^g(%)
T10F0	240	240.0	462	479	496	499	60.9
T9F1	243	241.4	467	480	497	502	58.9
T8F2	243	242.7	469	486	503	503	60.7
T7F3	243	244.0	476	492	508	510	60.5
T6F4	246	245.3	478	495	512	511	61.6
T5F5	247	246.7	480	496	514	514	62.1
T4F6	248	247.9	484	501	520	519	63.2
T3F7	251	249.2	495	508	528	554	63.2
T2F8	249	250.5	512	519	539	561	66.5
T1F9	251	251.8	522	524	544	557	67.6
T0F10	253	253.0	537	540	557	572	65.6

Table 2 Heat-resistant properties of PHT-DFK-BPF copolymer

Copolymer	$T g a$ /℃	T_g'^b/℃	$T onset c$ /℃	$T 5 % d$ /℃	$T 10 % e$ /℃	$T max f$ /℃	CY^g(%)
T10F0	240	240.0	462	479	496	499	60.9
T9F1	243	241.4	467	480	497	502	58.9
T8F2	243	242.7	469	486	503	503	60.7
T7F3	243	244.0	476	492	508	510	60.5
T6F4	246	245.3	478	495	512	511	61.6
T5F5	247	246.7	480	496	514	514	62.1
T4F6	248	247.9	484	501	520	519	63.2
T3F7	251	249.2	495	508	528	554	63.2
T2F8	249	250.5	512	519	539	561	66.5
T1F9	251	251.8	522	524	544	557	67.6
T0F10	253	253.0	537	540	557	572	65.6

Fig.4 XRD pattern of PHT-DFK-BPF copolymer(T5F5)

Fig.5 TGA curves(A) and DTG of PHT-DFK-BPF copolymers(B)

Table 3 Solubility of PHT-DFK-BPF copolymers in different solvents*

Copolymer	NMP	THF	CHCl₃	DMSO	DMF	DMAc	Toluene	Acetone
T10F0	+	+	+	+	+	+	-	-
T9F1	+	+	+	+	+	+	-	-
T8F2	+	+	+	+	+	+	-	-
T7F3	+	+	+	+	+	+	-	-
T6F4	+	+	+	+	+	+	-	-
T5F5	+	+	+	+	+	+	-	-
T4F6	+	+	+	+	+	+	-	-
T3F7	+	+	+	+	+	+	-	-
T2F8	+	+	+	+	+	+	-	-
T1F9	+	+	+	+	+	+	-	-
T0F10	+	+	+	+	+	+	-	-

Table 4 Tensile property of PHT-DFK-BPF copolymers*

Copolymer	σ_m/MPa	E_t/GPa	ε_b(%)	Copolymer	σ_m/MPa	E_t/GPa	ε_b(%)
T10F0	82	2.2	7	T4F6	81	3.1	58
T9F1	83	2.5	12	T3F7	82	2.8	35
T8F2	80	2.9	29	T2F8	83	2.9	27
T7F3	86	2.8	25	T1F9	77	2.0	24
T6F4	77	2.6	48	T0F10	70	1.3	12
T5F5	82	2.7	52

Fig.6 Mechanical properties of T4F6 and homopolymers

Fig.7 Interaction of the two side groups in PHT-DFK-BPF copolymers

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