Page 217 - 《精细化工》2020年第8期

第 8 期 彭盼盼，等: 硅基和氨酯基协同改性水性丙烯酸树脂的制备与性能 ·1715·

烯酸树脂分散体的交联密度增加，聚合物体系形成 参考文献：
了封闭的网状结构 [20-21] ，从而提高了膜的力学性能。 [1] CHOI S, YIM T, CHO W, et al. Rosin-embedded poly (acrylic acid)
binder for silicon/graphite negative electrode[J]. ACS Sustainable
从图 6 中还可以看出，当 IPDI-Si 含量提高到 4%时， Chemistry & Engineering, 2016, 4(12): 6362-6370.
PISA4 膜的断面（图 6d）出现部分较光滑地带。这 [2] HUANG S, XIAO J, ZHU Y A, et al. Synthesis and properties of
spray-applied high solid content two component polyurethane
可能是由于 IPDI-Si 的含量过多导致聚合体系反应 coatings based on polycaprolactone polyols[J]. Progress in Organic
Coatings, 2017, 106: 60-68.
不及时，部分预聚体产生团聚凝胶，在一定程度上 [3] LI J F, GE S S, WANG J X, et al. Water-based rust converter and its
对改性 后的丙烯酸树脂膜的力学性能产生了不利 polymer composites for surface anticorrosion[J]. Colloids and Surfaces
A: Physicochemical and Engineering Aspects, 2018, 537: 334-342.
影响，导致膜拉伸强度增长率下降，而断裂伸长率 [4] LI S W, YANG P P, LIU X H, et al. Graphene oxide based dopamine
mussel-like cross-linked polyethylene imine nanocomposite coating
出现明显下降。 with enhanced hexavalent uranium adsorption[J]. Journal of
Materials Chemistry A, 2019, 7(28): 16902-16911.
[5] ELREBII M, MABROUK A, BOUFI S. Synthesis and properties of
hybrid alkyd-acrylic dispersions and their use in VOC-free waterborne
coatings[J]. Progress in Organic Coatings, 2014, 77(4): 757-764.
[6] JIAO C Y, SHAO Q, WU M Y, et al. 2-(3,4-Epoxy)
ethyltriethoxysilane-modified waterborne acrylic resin: Preparation
and property analysis[J]. Polymer, 2020, 190: 122196-122203.
[7] DUAN Y F, HUO Y D, DUAN L. Preparation of acrylic resins
modified with epoxy resins and their behaviors as binders of
waterborne printing ink on plastic film[J]. Colloids and Surfaces A:
Physicochemical And Engineering Aspects, 2017, 535: 225-231.
[8] XU F, QIAN B R, HU Z, et al. A novel route to emulsifier-free,
waterborne hydroxyl functional polyacrylate with low VOC level and
its application in 2K-WPU coatings[J]. Journal of Macromolecular
Science, Part A, 2013, 50(5): 555-561.
[9] NAGHASH H, ABILI B. RETRACTED: Synthesis of a silicone
containing allylic monomer and its uses in the waterborne
polyurethane/vinyl acetate-acrylic hybrid emulsion copolymers[J].
Progress in Organic Coatings, 2010, 69(4): 486-494.
[10] MEHRAVAR S, BALLARD N, TOMOVSKA R, et al. Polyurethane/

acrylic hybrid waterborne dispersions: Synthesis, properties and
a—PISA0; b—PISA2; c—PISA3; d—PISA4 applications[J]. Industrial & Engineering Chemistry Research, 2019,
图 6 PISA0、PISA2、PISA3 和 PISA4 膜断裂面 SEM 图 58(46): 20902-20922.
Fig. 6 SEM images of the fracture surface of PISA0, [11] TAN J Q, LIU W Q, WANG H L, et al. A novel mono-
PISA2, PISA3 and PISA4 films methacryloyloxy terminated fluorinated macromonomer used for the
modification of UV curable acrylic copolymers[J]. Journal of
Applied Polymer Science, 2016, 133(10): 43116-43126.
3 结论 [12] LIU X S (刘信胜), LIU W Q (刘伟区), SHI H Y (石红义), et al.
Synthesis and properties of silicone acrylate modified waterborne
polyurethane[J]. Fine Chemical (精细化工), 2019, 36(6): 1241-1248.
以 TMPS 为含硅改性剂，制备出一系列含硅聚 [13] GUO X K, GE S S, WANG J X, et al. Waterborne acrylic resin
modified with glycidyl methacrylate (GMA): Formula optimization
氨酯改性丙烯酸树脂水分散体。采用 FTIR、XPS、 and property analysis[J]. Polymer, 2018, 143: 155-163.
TGA、TEM、SEM 等对分散体及树脂膜进行了表征， [14] XIE K M (谢凯明), WANG B (王斌), ZHU C H (朱春华).
Preparation and application of sulfhydryl and modified organic
并测试了分散体的硬度、贮存稳定性、附着力等性 silicone finishing agent[J]. Zhejiang Construction (浙江建筑), 2013,
30(2): 55-58, 61.
能。结果如下： [15] XIONG J (熊军), SUN F (孙芳), DU H G (杜洪光). Determination
（1）随着 IPDI-Si 含量的增大，分散体粒径逐 of isocyanate group in polyurethane by di-n-butylamine-acetone
method[J]. Chinese Journal of Analysis Laboratory (分析实验室),
渐变大；当 IPDI-Si 含量为 3%时，改性丙烯酸树脂 2007, 26(8): 73-76.
[16] YONG Q W, NIAN F W, LIAO B, et al. Synthesis and
水分散体粒径大小均一，分布较均匀，具有较好的 characterization of solvent-free waterborne polyurethane dispersion
存储稳定性。 with both sulfonic and carboxylic hydrophilic chain-extending agents
for matt coating applications[J]. RSC Advances, 2015, 5(130):
（2）当 IPDI-Si 含量为 3%时，改性丙烯酸树脂 107413-107420.
[17] SOW C, RIEDL B, BLANCHET P UV-waterborne polyurethane-
膜拉伸强度达到 9.4 MPa，断裂伸长率为 385%，热 acrylate nanocomposite coatings containing alumina and silica
分解温度 T 10% 为 306.1 ℃，具有较好的热稳定性能 nanoparticles for wood: Mechanical, optical, and thermal properties
assessment[J]. Journal of Coatings Technology and Research, 2011,
和力学性能。 8(2): 211-221.
[18] LEI H B, HE D L, GUO Y N, et al. Synthesis and characterization of
（3）IPDI-Si 的加入使改性丙烯酸分散体膜硬度 UV-absorbing fluorine-silicone acrylic resin polymer[J]. Applied
达到 2H，附着力达到 1 级，疏水性能也增强。随着 Surface Science, 2018, 442: 71-77.
[19] JIANG D W, HUAN Y H, SUN C Y, et al. Thermal, mechanical and
IPDI-Si 含量的增加，接触角呈现增大趋势，当含量 magnetic properties of functionalized magnetite/vinyl ester
nanocomposites[J]. RSC Advances, 2016, 6(94): 91584-91593.
为 3%时，水接触角为 96.1°，相对于未改性丙烯酸 [20] PARK S, LEE K, BOZOKLU G, et al. Graphene oxide papers
酯树脂水分散体提高了 28.3°。 modified by divalent ions-enhancing mechanical properties via
chemical cross-linking[J]. ACS Nano, 2008, 2(3): 572-578.
（4）这些性能的提高为其在涂料应用方面提供 [21] ZHANG X, BITARAF V, WEI S Y, et al. Vinyl ester resin:
Rheological behaviors, curing kinetics, thermomechanical, and
了多元化的方向，具有很好的应用价值。 tensile properties[J]. AIChE Journal, 2014, 60(1): 266-274.