新型聚三唑酯和聚三唑醚树脂的合成及性能

doi:10.11949/0438-1157.20190126

摘要/Abstract

摘要：

合成了三种含酯基和三种含醚键的炔单体，通过核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)、质谱(MS)、液相色谱(LC)对其结构进行了表征。用这六种炔单体与叠氮单体反应制备了一系列新型聚三唑酯树脂(PTAE)和聚三唑醚树脂(PTAO)。利用差示扫描量热分析(DSC)、FT-IR、动态力学热分析(DMA)、力学试验机和热失重分析(TGA)表征了树脂的固化行为、固化树脂的力学性能、耐热性和热稳定性。结果表明PTAE和PTAO树脂易溶于有机溶剂，可低温(60℃)固化，固化树脂的弯曲强度超过了100 MPa，可达158 MPa，玻璃化转变温度(T _g)超过180℃，高者达251℃，热分解温度可达360℃。

关键词: 合成, 制备, 聚合, 聚三唑酯, 聚三唑醚, 低温固化高性能树脂

Abstract:

Three kinds of alkyne monomers with ester groups and three kinds of alkyne monomers with ether groups were synthesized, and characterized by nuclear magnetic resonance spectroscopy(¹H NMR), fourier transform infrared spectroscopy(FT-IR), mass spectrometry (MS) and liquid chromatography (LC). Three poly(triazole ester) resins (PTAEs) and three poly(triazole ether) resins (PTAOs) were prepared from these alkyne monomers and polyfunctional azide monomers. The curing behavior, mechanical properties, heat resistance and thermal stability of the resins were characterized by differential scanning calorimetry (DSC), FT-IR, dynamic mechanical thermal analysis (DMA), mechanical tests, and thermogravimetric analysis(TGA). The results show that PTAE and PTAO resins can be dissolved in common organic solvents and can be cured at low temperature (60℃). The flexural strength of cured resins exceeds 100 MPa, and the highest 158 MPa. The glass transition temperature (T _g) of cured resins exceeds 180℃, and the highest 251℃. The thermal decomposition temperature(T _d5) exceeds 300℃, and the highest 360℃. The mechanical properties, heat resistance and thermal stability of the cured PTAO resins are higher than those of the cured PTAE resins.

Key words: synthesis, preparation, polymerization, poly(triazole ester), poly(triazole ether), high performance resins with low curing temperature

中图分类号:

TQ 322.4⁺1

王海军, 王露雨, 马明明, 万里强, 黄发荣. 新型聚三唑酯和聚三唑醚树脂的合成及性能[J]. 化工学报, 2019, 70(9): 3527-3536.

Haijun WANG, Luyu WANG, Mingming MA, Liqiang WAN, Farong HUANG. Synthesis and properties of novel poly(triazole ester) and poly(triazole ether) resins[J]. CIESC Journal, 2019, 70(9): 3527-3536.

图/表 21

图1 DPB的合成路线

Fig.1 Synthesis route of DPB

图2 TRPB的合成路线

Fig.2 Synthesis route of TRPB

图3 TEPB的合成路线

Fig.3 Synthesis route of TEPB

图4 BPOB的合成路线

Fig.4 Synthesis route of BPOB

图5 TPOB的合成路线

Fig.5 Synthesis route of TPOB

图6 TPE—OH的合成路线

Fig.6 Synthesis route of TPE—OH

图7 TPOBE的合成路线

Fig.7 Synthesis route of TPOBE

表1 不同树脂的原料单体

Table 1 Monomers for various resins

Resins	Alkyne monomers	Azide monomers
PTAE-32	DPB	TAMTMB
PTAE-23	TRPB	BAMBP
PTAE-24	TEPB	BAMBP
PTAO-32	BPOB	TAMTMB
PTAO-23	TPOB	BAMBP
PTAO-24	TPOBE	BAMBP

图8 PTAE和PTAO树脂的合成与固化过程

Fig.8 Schematic diagram of synthesis and curing process of PTAE and PTAO resins

表2 PTAE和PTAO树脂的溶解性

Table 2 Solubility of PTAE and PTAO resins

Solvent	Solubility
Solvent	PTAE-32	PTAE-23	PTAE-24	PTAO-32	PTAO-23	PTAO-24
acetone	+	+	+	+	+	+
toluene	-	+	-	-	-	-
tetrahydrofuran	+	+	+	+	+	+
methanol	-	-	-	-	-	-
acetonitrile	+	+	+	+	+	-
dichloromethane	+	+	+	+	+	+
1,2-dichloroethane	+	+	+	+	+	+
diethyl ether	-	-	-	-	-	-
ethyl acetate	+	+	+	+	+	-
DMF	+	+	+	+	+	+
DMSO	+	+	+	+	+	+
petroleum ether	-	-	-	-	-	-

图9 PTAE和PTAO树脂的DSC曲线

Fig.9 DSC curves of PTAE and PTAO resins

表3 PTAE和PTAO树脂的DSC数据

Table 3 DSC results of PTAE and PTAO resins

Resins	T _i/℃	T _p/℃	T _f/℃
PTAE-32	97.7	148.2	185.3
PTAE-23	91.1	132.1	174.4
PTAE-24	91.6	132.4	165.2
PTAO-32	92.7	135.0	174.0
PTAO-23	91.9	133.3	177.6
PTAO-24	90.5	133.2	184.1

图10 PTAE-32树脂固化各阶段的DSC曲线

Fig.10 DSC curves of PTAE-32 resin at different curing stages

表4 PTAE和PTAO树脂的固化跟踪

Table 4 Curing trace of PTAE and PTAO resins

Resins in different curing stages	Degree of cure, α/%
Resins in different curing stages	PTAE-32	PTAE-23	PTAE-24	PTAO-32	PTAO-23	PTAO-24
raw resins	0	0	0	0	0	0
60℃/6 h	83.6	76.5	81.2	79.7	84.6	77.4
60℃/6 h+120℃/2 h	97.8	94.8	93.5	95.7	97.1	96.4
60℃/6 h+120℃/2 h+150℃/2 h	98.5	97.6	97.8	98.7	98.2	97.9
60℃/6 h+120℃/2 h+150℃/2 h+180℃/2 h	$≈$ 100	$≈$ 100	$≈$ 100	$≈$ 100	$≈$ 100	$≈$ 100

表4 PTAE和PTAO树脂的固化跟踪

Table 4 Curing trace of PTAE and PTAO resins

Resins in different curing stages	Degree of cure, α/%
Resins in different curing stages	PTAE-32	PTAE-23	PTAE-24	PTAO-32	PTAO-23	PTAO-24
raw resins	0	0	0	0	0	0
60℃/6 h	83.6	76.5	81.2	79.7	84.6	77.4
60℃/6 h+120℃/2 h	97.8	94.8	93.5	95.7	97.1	96.4
60℃/6 h+120℃/2 h+150℃/2 h	98.5	97.6	97.8	98.7	98.2	97.9
60℃/6 h+120℃/2 h+150℃/2 h+180℃/2 h	$≈$ 100	$≈$ 100	$≈$ 100	$≈$ 100	$≈$ 100	$≈$ 100

图11 PTAE-32固化各阶段的FT-IR谱

Fig.11 FT-IR spectrum of PTAE-32 resin at different curing stages

表5 固化PTAE-C 和PTAO-C树脂的弯曲性能

Table 5 Flexural properties of PTAE-C and PTAO-C resins

Resins	Flexural strength/MPa	Flexural modulus/GPa
PTAE-32-C	102.1±5.1	3.1±0.4
PTAE-23-C	132.5±5.7	2.9±0.3
PTAE-24-C	107.9±3.2	2.6±0.3
PTAO-32-C	136.1±4.4	3.2±0.2
PTAO-23-C	158.2±3.5	3.0±0.3
PTAO-24-C	122.3±4.1	2.7±0.3

图12 PTAE-C和PTAO-C树脂的DMA曲线

Fig.12 DMA curves of PTAE-C and PTAO-C resins

表6 PTAE-C和PTAO-C树脂的T g

Table 6 T g of PTAE-C and PTAO-C resins

Resins	T _g/℃
PTAE-32-C	183(214)
PTAE-23-C	185(207)
PTAE-24-C	189(213)
PTAO-32-C	204
PTAO-23-C	208
PTAO-24-C	251

表7 PTAE-C和PTAO-C树脂的交联密度d c

Table 7 Crosslink density of PTAE-C and PTAO-C resins

Resins	d _c×10³/(mol/cm³)
PTAE-32-C	1.27
PTAE-23-C	0.68
PTAE-24-C	1.36
PTAO-32-C	2.87
PTAO-23-C	4.61
PTAO-24-C	6.92

图13 PTAE-C树脂的TGA曲线

Fig.13 TGA curves of PTAE-C resins

表8 PTAE-C和PTAO-C树脂的T d5

Table 8 T d5 of PTAE and PTAO resins

Resins	T _d5/℃
PTAE-32-C	317
PTAE-23-C	320
PTAE-24-C	300
PTAO-32-C	341
PTAO-23-C	343
PTAO-24-C	360

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