Page 213 - 精细化工2019年第8期

第 8 期 向 尧，等: 烯基聚乙二醇嵌段共聚物的合成及室温固化 ·1701·

触角为 59°，两者均表现为亲水性。固体表面的化学 [5] Zhou W Y, Cai J T. Mechanical and dielectric properties of epoxy
组成是决定固体表面亲水性和疏水性的重要因素 resin modifieusing reactive liquid rubber (HTPB)[J]. Journal of
Applied Polymer Science, 2012, 124(5): 4346-4351.
[20-21]
。制备的嵌段共聚物与腈氧化物反应制备的交 [6] Liu Lei (刘磊), Chen Jing (陈京), Zheng Yuansuo (郑元锁), et al.
联弹性体主链中含有大量的羟基，从而表现出亲水 Study on properties of epoxidized hydroxyl terminated polybutadiene
性。PEG-PGA-PAGE-1 弹性体比 PEG-PGA-PAGE-2 cured at room temperature[J]. Journal of Solid Rocket Technology
(固体火箭技术), 2012, 35(6): 807-811.
弹性体的接触角大是因为 PEG-PGA-PAGE-1 弹性体 [7] Wang Ligang (王利刚), Li Xiaojiang (李笑江), Yan Qilong (严启
形成的异唑啉环更多，弹性体网络紧密性更强， 龙), et al. Research progress of polyethylene glycol blend systems[J].
且异  唑 啉 环 是弱极 性基 团，疏 水性 较强 ， Chemical Propellants & Polymeric Materials (化学推进剂与高分子
材料), 2012, 10(2): 43-47.
PEG-PGA- PAGE-1 弹性体总体表现出与水更难结 [8] Chi M S. Compatibility of cross-linked polymers with plasticizers by
合，故接触角更大。 glass transition temperature measurement and swelling tests[J].
Journal of Polymer Science, Polymer Chemistry Edition, 1981,
3 结论 19(7): 1767-1779.
[9] Zhang Wanbin (张万斌), Fan Xiaodong (范晓东), Zhu Xiuzhong (朱
秀忠). Synthesis and mechanical properties of poly(tetrahydrofuran)-
利用聚乙二醇 400 为引发剂，三氟化硼乙醚为
poly(butadiene)-poly(tetrahydrofuran) triblock copolymer[J]. Journal
催化剂，GA 和 AGE 为共聚单体，采用阳离子开环 of Solid Rocket Technology (固体火箭技术), 2015, 38(2): 251-260.
聚合的方法合成了烯基聚乙二醇嵌段共聚物粘合剂 [10] Fan W W, Fan X D, Tian W, et al. Poly(ethylene glycol)-poly
(tetrahydrofuran)-poly(ethylene glycol) triblock copolymer: Synthesis,
（PEG-PGA-PAGE）。将 GA、AGE 按两种不同的加
crystallization behavior and novel morphology[J]. Express Polymer
料 顺序， 合成 了两种 不同 分子结 构的 粘合 剂 Letters, 2013, 7(5): 416-430.
PEG-PGA-PAGE-1 和 PEG-PGA-PAGE-2。以对苯二 [11] Wang Cundong (汪存东), Luo Yunjun (罗运军), Xia Min (夏敏), et
al. Synthesis and characterization of hydroxyl-terminated block
腈氧化物为固化剂，与以上两种粘合剂固化制得两
copolyether of PTHF-PEO-PTHF[J]. Journal of Solid Rocket
种弹性体。结果表明：GA、AGE 分段加制备的 Technology (固体火箭技术), 2011, 34(2): 202-206.
PEG-PGA-PAGE-1 嵌段共聚物粘合剂和 GA、AGE [12] Weygand C, Bauer E. Über die reaktion des hydroxylamins mit
enoläthern und acetylenketonen und über eine neue konstitutiv
同时加制备的 PEG-PGA-PAGE-2 嵌段共聚物粘合剂
eindeutige isoxazolsynthese[J]. Justus Liebigs Annalen der Chemie ,
均能与对苯二腈氧化物在室温条件下固化，固化后 1927, 459: 123-143.
的两种弹性体热分解温度基本一致，均具有较好的 [13] Hu Hongmei (胡红梅), Yan Changwang (闫长旺), Hou Yibin (侯一
斌). Influences of curing factors on the glass transition temperature
力学性能：拉伸强度分别为 0.948、0.923 MPa，断 of polymer[J]. Chinese Adhesive (中国胶粘剂), 2013, 22(9): 11-13.
裂伸长率分别为 89.32%、103.33%。较本课题组前 [14] Wang Yulong (王玉龙), Li Zhenzhong (李振中), Bai Jingjing (白静
期制备弹性体的力学性能有所提升，且 PEG-PGA- 静). Preparation and properties of PCDL/MDI type thermoplastic
polyurethane elastomer[J]. Engineering Plastics Application (工程塑
PAGE-1 弹性体比 PEG- PGA-PAGE-2 弹性体的拉伸
料应用), 2014, 11(42): 1-2.
强度、储能模量、邵氏硬度、接触角和 T g 更大，断 [15] Holzworth K, Jia Z, Amirkhizi A V, et al. Effect of isocyanate content
裂伸长率和晶粒更小，脆断面更粗糙。这些均表明 on thermal and mechanical properties of polyurea[J]. Polymer, 2013,
54(12): 3079-3085.
GA、AGE 分段加制备的 PEG-PGA-PAGE-1 弹性体
[16] Liao Mingyi (廖明义), Fan Cheng (范诚), Zhang Xiaojuan (张晓娟),
的力学性能更好。本研究结果有望应用于复合固体 et al. Morphology and properties of polybutadiene/allyl isobutyl
推进剂中。 polyhedral oligomeric siisesquioxane nanohybrids[J]. China
Synthetic Rubber Industry (合成橡胶工业), 2011, 34(5): 346-351.
参考文献： [17] Kissane M, Lawrence S E, Maguire A R, et al. ChemInform abstract:
1, 3-dipolar cycloadditions of 2-thio-3-chloroacrylamides with nitrile
[1] Ahmad N, Khan M B, Ma X, et al. The influence of oxides and nitrones[J]. ChemInform, 2010, 41(44), DOI: 10.
cross-linking/chain extension structures on mechanical properties of 1002/chin. 201044144.
HTPB-based polyurethane elastomers[J]. Arabian Journal for Science [18] Sugium S, Ueno H, Kono M. Process for producing butadiene
& Engineering, 2014, 39(1): 43-51. polymers: US3778424[P]. 1970-12-11.
[2] Hailu K, Guthausen G, Becker W, et al. In-situ characterization of the [19] Jiang L Y, Xiong C D, Jiang L X, et al. Effect of HA with different
cure reaction of HTPB and IPDI by simultaneous NMR and IR grain size range on the crystallization behaviors and mechanical
measurements[J]. Polymer Testing, 2010, 29(4): 513-519.
[3] Fan Yaqin (樊亚勤), Xiang Yao (向尧), Lei Yonglin (雷永林), et al. property of HA/PLGA composite[J]. Thermochimica Acta, 2013,
Synthesis of terephthalonnitrile oxides and its curing properties at 565: 52-57.
room temperature[J]. Fine Chemicals (精细化工), 2017, 34(9): 1063- [20] Yang Taisheng ( 杨泰 生 ). Research and preparation of
1069. superhydrophobic silica thin films by emulsion method[D]. Jinan:
[4] Wang Xiaochuan (王晓川), Shu Yuanjie (舒远杰), Mo Hongchang Shandong Tnstitute of Light Industry (山东轻工业学院), 2009.
(莫洪昌), et al. Synthesis and curing of energetic binder triblock [21] Jiang L, Wang R, Yang B, et al. Binary cooperative complementary
alkenyl poly NIMMO[J]. Chinese Journal of Explosives & nanoscale interfacial materials[J]. Pure and Applied Chemistry, 2000,
Propellants (火炸药学报), 2018, 41(6): 562-566. 72(1/2): 73-81.