Synthesis and properties of novel poly(triazole ester) and poly(triazole ether) resins

doi:10.11949/0438-1157.20190126

Abstract

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

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

CLC Number:

TQ 322.4⁺1

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.

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.

Figures/Tables 21

Fig.1 Synthesis route of DPB

Fig.2 Synthesis route of TRPB

Fig.3 Synthesis route of TEPB

Fig.4 Synthesis route of BPOB

Fig.5 Synthesis route of TPOB

Fig.6 Synthesis route of TPE—OH

Fig.7 Synthesis route of TPOBE

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

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

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	-	-	-	-	-	-

Fig.9 DSC curves of PTAE and PTAO resins

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

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

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

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

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

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

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

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

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

Fig.13 TGA curves of PTAE-C resins

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

References 33

1	Michael A . Ueber die einwirkung von diazobenzolimid auf acetylendicarbonsäuremethylester[J]. Adv. Synth. Catal., 1893, 48(1): 94-95.
2	Kolb H C , Finn M G , Sharpless K B . Click chemistry: diverse chemical function from a few good reactions[J]. Cheminform, 2001, 32(35): 2004-2021.
3	Rostovtsev V V , Green L G , Fokin V V , et al . A stepwise huisgen cycloaddition process: copper(Ⅰ)-catalyzed regioselective “ligation” of azides and terminal alkynes[J]. Angew. Chem. Int. Ed., 2002, 114(14): 2708-2711.
4	Ackermann L , Potukuchi H K , Landsberg D , et al . Copper-catalyzed “click” reaction/direct arylation sequence: modular syntheses of 1,2,3-triazoles[J]. Org. Lett., 2008, 10(14): 3081-3084.
5	Um J E , Song S G , Yoo P J , et al . Large-scale separation of single-walled carbon nanotubes by electronic type using click chemistry[J]. Appl. Surf. Sci., 2017, 429(6): 278-283.
6	Liu H H , Li S X , Zhang M J , et al . Facile synthesis of ABCDE-type H-shaped quintopolymers by combination of ATRP, ROP, and click chemistry and their potential applications as drug carriers[J]. J. Polym. Sci. Part A: Polym. Chem., 2015, 50(22): 4705-4716.
7	Lee K S , Park S Y , Moon H C , et al . Thermal stability of ester linkage in the presence of 1,2,3-triazole moiety generated by click reaction[J]. J. Polym. Sci., Part A: Polym. Chem., 2017, 55(3): 427-436.
8	Thibault R J , Takizawa K , Lowenheilm P , et al . A versatile new monomer family: functionalized 4-vinyl-1,2,3-triazoles via click chemistry[J]. J. Am. Chem. Soc., 2006, 128(37): 12084-12085.
9	Li H , Li L , Wu H , et al . Ferrocene-based poly(aroxycarbonyltriazole)s: synthesis by metal-free click polymerization and use as precursors to magnetic ceramics [J]. Polym. Chem., 2013, 4(22): 5537-5541.
10	Tang J , Wan L , Zhou Y , et al . Strong and efficient self-healing adhesives based on dynamic quaternization cross-links[J].J. Mater. Chem.A, 2017, 5(40): 21169-21177.
11	Nagao Y , Takasu A . Click polyester: synthesis of polyesters containing triazole units in the main chain by click chemistry and improved thermal property[J]. Macromol. Rapid. Commun., 2009, 30(3): 199-203.
12	Katritzky A R , Meher N K , Hanci S , et al . Preparation and characterization of 1,2,3-triazole-cured polymers from endcapped azides and alkynes[J]. J. Polym. Sci., Part A: Polym. Chem., 2010, 46(1): 238-256.
13	Gorman I E , Willer R L , Kemp L K , et al . Development of a triazole-cure resin system for composites: evaluation of alkyne curatives[J]. Polymer, 2012, 53(13): 2548-2558.
14	Gilday L C , White N G , Beer P D . Triazole- and triazolium-containing porphyrin-cages for optical anion sensing[J]. Dalton Transactions, 2012, 41(23): 7092-7097.
15	Baranek A , Song H B , Mcbride M , et al . Thermomechanical formation-structure-property relationships in photopolymerized copper-catalyzed azide-alkyne (CuAAC) networks[J]. Macromolecules, 2016, 49(4): 1191-1200.
16	Li Y , Zhou H , Yanpeng E , et al . Synthesis and characterization of a new series of rigid polytriazole resins[J]. Designed Monomers and Polymers, 2013, 16(6): 556-563.
17	Tian J , Wan L , Huang J , et al . Preparation and properties of a new polytriazole resin made from dialkyne and triazide compounds and its composite[J]. Polymer Bulletin, 2008, 60(4): 457-465.
18	Wang X , Zhao Z , Tian J , et al . Synthesis and characterization of a new polytriazole resin derived from N,N-dipropargyl-p-propargyloxyaniline[J]. Polymer Journal, 2009, 41(6): 498-502.
19	Li Y , Zhou H , Yanpeng E , et al . Synthesis and characterization of a new series of rigid polytriazole resins[J]. Designed Monomers and Polymers, 2013, 16(6): 556-563.
20	Wang Y , Wan L , Han D , et al . Investigation of novel polytriazole resins[J]. Designed Monomers & Polymers, 2016, 19(7): 1-8.
21	Xue L , Wan L , Hu Y , et al . Thermal stability of a novel polytriazole resin[J]. Thermochimica Acta, 2006, 448(2): 147-153.
22	Huang F , Wan L , Du L , et al . The effects of structures on properties of new polytriazole resins[M]//Mittal V. High Performance Polymers and Engineering Plastics. New Jersey: John Wiley & Sons, Inc., 2011: 243-267.
23	Huang J , Wan L , Jian Z , et al . Synthesis and characterization of a novel silicon-containing polytriazole resin[J]. Journal of Applied Polymer Science, 2010, 114(3): 1725-1730.
24	Tian J , Wan L , Huang J , et al . Synthesis and characterization of a novel polytriazole resin with low-temperature curing character[J]. Polymers for Advanced Technologies, 2010, 18(7): 556-561.
25	E Y, Wan L , Huang F , et al . New heat-resistant polytriazole adhesives: investigation of adhesion of polytriazole resins to metals[J]. J. Adhes. Sci. Technol., 2013, 27(16): 1767-1777.
26	Jiang S , Wan L , Zhou X , et al . Synthesis and property of polytriazole resins derived from dipropargyl ethynylaniline[J]. Polymer Materials Science & Engineering, 2018, 34(3): 17-21.
27	潘博, 王露雨, 王海军, 等 . 聚三唑酯树脂的合成及其性能[J]. 过程工程学报, 2019, 19(1): 181-188.
	Pan B , Wang L Y , Wang H J , et al . Synthesis and properties of poly(triazole ester) resins[J]. The Chinese Journal of Process Engineering 2019, 19(1): 181-188.
28	黄建智, 万里强, 田建军, 等 . 1,3-二(炔丙基氧)苯与4,4'-二叠氮甲基联苯聚合反应及聚合物性能的研究[J]. 化学学报, 2007, 65(22): 2629-2634.
	Huang J Z , Wan L Q , Tian J J , et al . Study on polymerization of 1,3-di(propargyloxy)benzene with 4,4'-diazide methyl biphenyl and properties of polymer[J]. Acta Chimica Sinica, 2007, 65(22): 2629-2634.
29	扈艳红, 罗永红, 万里强, 等 . 双酚A二炔丙基醚与4,4’-联苯二苄叠氮的合成及聚合反应研究[J]. 高分子学报, 2005, (4): 560-565.
	Hu Y H , Luo Y H , Wan L Q , et al . 1,3-Dipolar cycloaddition polymerization of bispropargyl ether of bisphenol-A with 4,4'-biphenyl dibenzyl azide and their thermal analyses[J]. Acta Polymerica Sinica, 2005, (4): 560-565.
30	Ohashi S , Kilbane J , Heyl T , et al . Synthesis and characterization of cyanate ester functional benzoxazine and its polymer[J]. Macromolecules, 2015, 48(23): 8412-8417.
31	罗渝然 . 化学键能数据手册[M]. 北京: 科学出版社, 2005: 100-224.
	Luo Y R . Chemical Bond Energy Data Handbook [M]. Beijing: Science Press, 2005: 100-224.
32	谭德新, 王艳丽, 吴小乐, 等 . 二炔丙基双酚A醚聚合物的非等温热分解过程[J]. 固体火箭技术, 2015, 38(6): 877-881.
	Tan D X , Wang Y L , Wu X L , et al . Non-isothermal thermal decomposition process of dipropargyl bisphenol A ether polymer[J]. Journal of Solid Rocket Technology, 2015, 38(6): 877-881.
33	Raghunanan L , Narine S S . Influence of structure on chemical and thermal stability of aliphatic diesters[J]. Journal of Physical Chemistry B, 2013, 117(47): 14754-14762.

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