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第 5 期 丁政茂,等: 阻燃 OMMT/WPU 纳米复合材料的制备及性能 ·933·
由图 5 可见,纯 WPU 胶膜在空气中燃烧产生 参考文献:
了大量的熔滴,胶膜及炭层破坏严重;在锥形量热 [1] AHMADI Y, AHMAD S. Recent progress in the synthesis and
property enhancement of waterborne polyurethane nanocomposites:
仪中燃烧后,残炭量非常少,可以清晰地看到底部 Promising and versatile macromolecules for advanced applications[J].
的铝膜。而 OMMT/WPU-5 纳米胶膜在空气中燃烧 [2] Polymer Reviews, 2020, 60(2): 226-266.
KIM B K. Aqueous polyurethane dispersions[J]. Colloid & Polymer
几乎不发生熔滴现象,燃烧后的炭层具有自支撑性; Science, 1996, 274(7): 599-611.
[3] THOMSON T. Design and applications of hydrophilic polyurethanes[M].
在锥形量热仪中燃烧后,剩余的残炭量明显增多, 1st ed. Boca Raton, CRC Press, 2000: 55-56.
[4] FILIP D, MACOCINSCHI D, VLAD S. Micellar behavior of some
整体呈现松垮碎块。 amphiphilic block polyurethanes in aqueous/nonaqueous media[J].
图 6 为 OMMT/WPU-0 和 OMMT/WPU-5 纳米 European Polymer Journal, 2012, 48(3): 464-471.
[5] FENG J J, GE Z, CHAI C P, et al. Flame retardant modification of
胶膜炭层形貌的表面形貌图。由图 6 可见,纯 WPU waterborne polyurethane fabric coating agent with high hydrostatic
pressure resistance[J]. Progress in Organic Coatings, 2016, 97: 91-98.
胶膜的燃烧炭层中仅有一层分布比较松散的灰烬, [6] CHANG C W, LU K T. Natural castor oil based 2-package waterborne
而 OMMT/WPU-5 纳米胶膜的燃烧炭层表面存在大 polyurethane wood coatings[J]. Progress in Organic Coatings, 2012,
75(4): 435-443.
量的瓦片状蒙脱土,它们相互穿插形成具有一定硬 [7] YONG Q W, HUANG H, LIAO B, et al. Preparation and
characterization of low gloss aqueous coating via forming self-
度的团簇体。与纯 WPU 的燃烧炭层相比,这种结 roughed surface based on waterborne polyurethane acrylate hybrid
emulsion[J]. Progress in Organic Coatings, 2018, 115: 18-26.
构的炭层能够更加有效地限制分子的热运动,阻隔 [8] WANG Y, DENG L Y, FAN Y H. Preparation of soy-based adhesive
热、氧、可燃性挥发气体在燃烧区域与未燃材料之 enhanced by waterborne polyurethane: Optimization by response
surface methodology[J]. Advances in Materials Science & Engineering,
间的传递,降低热释放速率、增加不完全燃烧的程 2018, 2018: 9253670.
[9] ZHOU X, LI Y, FANG C Q, et al. Recent advances in synthesis of
度,从而更有利于保护内部材料,起到阻燃、抗熔 waterborne polyurethane and their application in water-based ink: A
滴的作用。 review[J]. Journal of Materials Science & Technology, 2015, 31(7):
708-722.
[10] LI J J, ZHENG W, ZENG W B, et al. Structure, properties and
application of a novel low-glossed waterborne polyurethane[J].
Applied Surface Science, 2014, 307: 255-262.
[11] LI G Q (李桂琴), LI S W (李树伟), GUO X Y (郭逍遥) , et al. Study
on preparation of aqueous polyurethane basecoats for automotive
refinish[J]. Modern Paint and Finishing (现代涂料与涂装), 2016,
19(6): 1-4.
[12] FERREL-ÁLVAREZ A, DOMÍNGGUEZ-CRESPO M A, TORRES-
HUERTA A, et al. Intensification of electrochemical performance of
AA7075 aluminum alloys using rare earth functionalized water-based
图 6 OMMT/WPU-0(a)和 OMMT/WPU-5 纳米胶膜(b) polymer coatings[J]. Polymers, 2017, 9(5): 178.
[13] SHIN E J, CHOI S M. Advances in waterborne polyurethane-based
燃烧炭层的 SEM 图 biomaterials for biomedical applications[J]. Advances in Experimental
Fig. 6 SEM images of carbon residue for OMMT/WPU-0 Medicine & Biology, 2018, 1077: 251-283.
(a) and OMMT/WPU-5 (b) nanofilms [14] FUKUSHIMA Y, OKADA A, KAWASUMI M, et al. Swelling
behaviour of montmorillonite by poly-6-amide[J]. Clay Minerals,
1988, 23(1): 27-34.
3 结论 [15] OKADA A, USUKI A. Twenty years of polymer-clay nanocomposites
[J]. Macromolecular Materials and Engineering, 2006, 291(12): 1449-1476.
[16] MIRANDA G S, DELPECH M C, REIS R A, et al. Synthesis and
利用纳米片可以有效限制分子链运动的特点, characterization of waterborne poly(urethane-urea)s and their
nanocomposites containing hydrophilic and organophilic clays[J].
用 HTPB 将 OMMT 剥离为纳米片,并与 IPDI、DMPA Science of Advanced Materials, 2015, 7(12): 2557-2569.
[17] RATH S K, PATRI M, KHAKHAR D V. Structure-thermomechanical
等单体通过原位聚合法制备了一种具有多功能性的 property correlation of moisture cured poly(urethane-urea)/clay
nanocomposite coatings[J]. Progress in Organic Coatings, 2012,
OMMT/WPU 纳米复合材料。分别探讨了 OMMT 纳 75(3): 264-273.
米片含量对 WPU 粒径、弹性模量、热稳定性和阻 [18] HE D (何栋). Modification of waterborne polyurethane and the
preparation and research of its composite materials[D]. Wuhan:
燃性能的影响。 Wuhan University of Technology (武汉理工大学), 2015.
[19] SUBRAMANI S, CHOI S W, LEE J Y, et al. Aqueous dispersion of
(1)在 80 ℃、3 h、100 r/min 转速下,HTPB novel silylated (polyurethane-acrylic hybrid/clay) nanocomposite[J].
可以完全剥离含量为 11.7%的 OMMT,被剥离的纳 Polymer, 2007, 48(16): 4691-4703.
[20] LEE H T, LIN L H. Waterborne polyurethane/clay nanocomposites:
米片具有均匀的衬度和较好的完整性。 Novel effects of the clay and its interlayer ions on the morphology
and physical and electrical properties[J]. Macromolecules, 2006,
(2)OMMT/WPU 纳米乳液可稳定储存 6 个 39(18): 6133-6141.
[21] MALKAPPA K, RAO B N, JANA T. Functionalized polybutadiene
月,随着 OMMT 纳米片含量的增加,粒径逐渐从 diol based hydrophobic, water dispersible polyurethane nanocomposites:
153.3 nm 增大到 300.9 nm;Zeta 电位绝对值逐渐从 Role of organo-clay structure[J]. Polymer, 2016, 99: 404-416.
[22] NICOLOSI V, CHHOWALLA M, KANATZIDIS M G, et al. Liquid
28.2 mV 降低到 19.3 mV;胶膜的弹性模量提高了约 exfoliation of layered materials[J]. Science, 2013, 340(6139): 1226419.
[23] CHEN T H, ZHU J J, LI B H, et al. Exfoliation of organo-clay in
59.4%;硬段的 DTG 峰值明显地降低和延后;LOI telechelic liquid polybutadiene rubber[J]. Macromolecules, 2005,
38(9): 4030-4033.
可从 16.6%增加到 18.4%,pHRR 下降了约 36.9%。 [24] SUTER J L, GROEN D, COVENEY P V. Mechanism of exfoliation
(3)瓦片状的 OMMT 纳米片相互穿插形成的 and prediction of materials properties of clay-polymer nanocomposites
from multiscale modeling[J]. Nano letters, 2015, 15(12): 8108-8113.
团簇体覆盖在燃烧区域的表面,可有效地改善 WPU [25] DING Z M, LI J, XIN W, et al. Low gloss waterborne polyurethane
coatings with anti-dripping and flame retardancy via montmorillonite
胶膜的抗熔滴性能和阻燃性能。 nanosheets[J]. Progress in Organic Coatings, 2019, 136: 105273.