主链含酞和芴结构的无定形聚芳醚酮的合成

doi:10.7503/cjcu20140564

摘要/Abstract

摘要：

通过共聚改性在酚酞聚芳醚酮(PEK-C)的主链上引入含芴侧基, 制备了一系列主链含酞和芴结构的线性高分子量无定形聚芳醚酮无规共聚物. 通过傅里叶红外光谱(FTIR)、核磁共振谱(¹H, ¹³C NMR)等手段确定了共聚物结构. 凝胶渗透色谱(GPC)数据表明, 共聚物的 $M ˉ n$ >6.0×10⁴, $M ˉ w$ >1.0×10⁵, PDI( $M ˉ w$ / $M ˉ n$ )范围在1.6~1.7之间. X射线衍射(XRD)数据表明共聚物系无定形结构, 差示扫描量热法(DSC)和热重分析(TGA)测试表明聚合物具有良好的耐热性; 初始热分解温度高于467 ℃; 700 ℃时残炭率大于58.9%; 共聚物呈现单一的玻璃化转变温度(T_g>243 ℃). 当酚酞与双酚芴摩尔比在3:7~5:5范围时, 共聚物的弹性模量和断裂伸长率显著提高, 可分别达到3.1 GPa和58%, 是酚酞聚芳醚酮的1.4倍和8.3倍. 这类含酞和芴侧基的无定形聚芳醚酮保持了在氯仿、二氯甲烷、四氢呋喃(THF)和甲基吡咯烷酮(NMP)等极性非质子溶剂中良好的溶解性能, 并显著提高了聚合物的力学性能和热性能.

关键词: 无定形聚芳醚酮, 共聚物, 酚酞, 双酚芴, 高性能树脂

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

中图分类号:

O633.1

TrendMD:

王志鹏, 王菲菲, 王红华, 周光远. 主链含酞和芴结构的无定形聚芳醚酮的合成. 高等学校化学学报, 2014, 35(11): 2487.

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

图/表 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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