Page 231 - 《精细化工》2023年第1期

第 1 期 张新超，等: 沉淀法合成联苯基液晶环氧及强韧化体系的制备 ·223·

度的改善，液晶域的存在带来的裂纹-钉铆机理也进 体系提升 20.8%和 24.7%。而 P 7-A-H 体系的室温储能
一步提升了交联网络的韧性。这种有序液晶域在断 模量达到了 2570 MPa。同时 T g 也有所提高，实现了
裂过程中起到了抵抗裂纹扩展的作用，并大大提升 环氧树脂综合性能的全面提升，在胶膜领域有巨大
了受力方向的强度、模量，实现了环氧树脂的强韧化。 的应用前景。
2.3.5 P x -A-H 改性体系的应用案例-胶膜
参考文献：
改性环氧树脂室温下为橡皮泥状，且使用了潜
[1] LI S (李帅), ZHANG K (张坤), WANG Y G (王义刚), et al.
伏性固化剂，储存稳定性良好，且其强度、模量、 Synthesis and application of waterborne hyperbranched epoxy
韧性都有明显提升，非常适合作为胶膜材料。为制 resin[J]. Fine Chemicals (精细化工), 2022, 39(3): 611-617.
[2] MUÑOZ B K, DEL BOSQUE A, SÁNCHEZ M, et al. Epoxy resin
备胶膜，在热压机上下放置隔离纸，将面团状树脂 systems modified with ionic liquids and ceramic nanoparticles as
放置其中，在 60 ℃下进行热压，控制压力，制备 structural composites for multifunctional applications[J]. Polymer,
2021, 214: 123233.
相应厚度的胶膜，制备好的胶膜需要低温储存。剪 [3] WANG X Q, MA B, CHEN S S, et al. Properties of epoxy-resin
切强度是评价胶黏剂粘接性能最重要的指标，图 14 binders and feasibility of their application in pavement mixtures[J].
Construction and Building Materials, 2021, 295: 123531.
为各配方胶膜的剪切强度。由图 14 可以看到，随着 [4] RICO M, LÓPEZ J, MONTERO B, et al. Phase separation and
DGEBP 含量的增加，剪切强度也随之上升，当 morphology development in a thermoplastic-modified toughened
epoxy[J]. European Polymer Journal, 2012, 48(10): 1660-1673.
DGEBP 含量为 5%时，剪切强度最大，为 19.43 MPa。 [5] DENG S Q, DJUKIC L, PATON R, et al. Thermoplastic-epoxy
interactions and their potential applications in joining composite
structures—A review[J]. Composites Part A: Applied Science and
Manufacturing, 2015, 68: 121-132.
[6] CHEN S F, XU Z J, ZHANG D H. Synthesis and application of
epoxy-ended hyperbranched polymers[J]. Chemical Engineering
Journal, 2018, 343: 283-302.
[7] WANG J F, ZHANG X H, JIANG L, et al. Advances in toughened
polymer materials by structured rubber particles[J]. Progress in
Polymer Science, 2019, 98: 101160.
[8] ZHOU W Y (周文英), ZHANG F (张帆), WANG X (汪旭), et al.
Study on EHTPB liquid rubber modified epoxy resin[J]. Modern
Plastics Processing Applications (现代塑料加工应用), 2020, 32(5): 4-7.
[9] DITTANET P, PEARSON R A. Effect of silica nanoparticle size on
toughening mechanisms of filled epoxy[J]. Polymer, 2012, 53(9):

1890-1905.
图 14 P x -A-H 胶膜的剪切强度 [10] RAJU T, DING Y M, HE Y L, et al. Miscibility, morphology,
Fig. 14 Shear strength of P x -A-H films thermal, and mechanical properties of a DGEBA based epoxy resin
toughened with a liquid rubber[J]. Polymer, 2008, 49(1): 278-294.
[11] FOIX D, RAMIS X, FERRANDO F, et al. Improvement of epoxy
3 结论 thermosets using a thiol-ene based polyester hyperbranched polymer
as modifier[J]. Polymer International, 2012, 61(5): 727-734.
本文“一步沉淀法”制备了 DGEBP；通过调控 [12] MANJULA D D, JAISANKAR S N, PATHAK M. Effect of new
hyperbranched polyester of varying generations on toughening of
投料比和反应温度探究了最佳制备工艺；使用FTIR、 epoxy resin through interpenetrating polymer networks using urethane
linkages[J]. European Polymer Journal, 2013, 49(11): 3561-3572.
NMR 表征了其结构；并通过相转变行为与光学行为研 [13] ZHANG B L, TANG G L, SHI K Y, et al. A study on the properties
究了其基本性能与液晶行为。将 DGEBP 与几类固化 of epoxy resin toughened by a liquid crystal-type oligomer[J].
Journal of Applied Polymer Science, 1999, 71(1): 177-184.
剂混合，研究了其固化行为及热性能。利用 DGEBP [14] ASIF A A, JOHN B, RAO V L, et al. Surface morphology,
的增韧机理，将 DGEBP 添加到 DGEBA 和 PKHH thermomechanical and barrier properties of poly(ether sulfone)-
toughened epoxy clay ternary nanocomposites[J]. Polymer International,
的二元共混体系中，得到了 P x -A-H 体系。 2010, 59(7): 986-997.
（1）成功合成了高结晶度、高环氧值的 DGEBP， [15] SIDDHAMALLI S K, KYU T. Toughening of thermoset/thermoplastic
composites via reaction-induced phase separation: Epoxy/phenoxy
且工艺安全、后处理简单；收率达到 93%、结晶度为 blends[J]. Journal of Applied Polymer Science, 2000, 77(6): 1257-1268.
91%、环氧值 0.635 mol/100 g。POM、DSC 分析表明， [16] LIU T A, NIE Y X, CHEN R S, et al. Hyperbranched polyether as an
all-purpose epoxy modifier: Controlled synthesis and toughening
DGEBP 单体固化前并不具备液晶性，属于非本体液晶 mechanisms[J]. Journal of Materials Chemistry A, 2015, 3(3): 1188-1198.
环氧树脂。 [17] YANG T (杨涛). Study on the control design and properties of
flexible segments of epoxy/anhydride rigid network structures[D].
（2）热力学分析表明：DGEBP 与各种固化剂的 Beijing: Beijing University of Chemical Technology (北京化工大
固化物热性能良好。其中，与芳香二胺固化剂得到 学), 2016.
[18] BAO Q R, WANG B W, LIU Y A, et al. Epoxy resin flame retarded
的固化物具有最佳的热性能，DGEBP/DDS 体系 T g and toughed via flexible siloxane chain containing phosphaphenanthrene[J].
可达 185.60 ℃，T 5% 达 399.78 ℃。 Polymer Degradation and Stability, 2020, 172: 109055.
[19] WANG W, LIU Y A, WEN H, et al. Synthesis of a hyperbranched
（3）P 5 -A-H 体系力学和热性能等测试表明：强 polyamide charring agent and its flame-retarding and toughening
behavior in epoxy resin[J]. Polymer Degradation and Stability, 2021,
度、模量、韧性都有相当大程度的提升，拉伸强度达
184: 109479.
到 84.19 MPa，冲击强度和拉伸断裂能分别比 P 0 -A-H （下转第 232 页）