Page 101 - 《精细化工》2020年第1期

第 1 期 刘 丽，等: 原子灰 BPO-DMA-Co(Ⅱ)固化体系的探讨 ·87·

method of air-drying unsaturated polyester resin: CN103724604A[P].
2014-04-16.
[5] Zhu Xinbao (朱新宝), Wu Xiaodi (吴笑弟), Cheng Zhenshuo (程振
朔), et al. Synthesis of a air-drying unsaturated polyester resin:
CN106800645A[P]. 2017-06-06.
[6] Zhou Meiying (周梅英), Li Xinjuan (李新娟), Wu Shuzhen(吴淑贞).
Study on two-component peroxide curing agent[J]. Thermosetting
resin (热固性树脂), 1996, (1): 5-8.
[7] Li Fengqi (李凤起), Zhu Shuquan (朱书全), Li Shuqin (李淑琴).
Study on increasing productive rate and stability of methyl ethyl
ketone peroxide[J]. Thermosetting Resin(热固性树脂), 2000, 15(2):
18-20.

[8] Storey R F, Smith D L. Improved room temperature cure of unsaturated
图 8 T-β 外推曲线 polyester resins[J]. Mod Plast, 1984, 61(12): 458-465.
Fig. 8 T-β extrapolation curves [9] Li L, Cao X, Lee L J. Effect of dual-initiator on low temperature curing
of unsaturated polyester resins[J]. Polymer, 2004, 45(19): 6601-6612.

[10] Brydson J A. Plastics materials [M]. 8th ed. London: Butterw-
3 结论 orth-Heinemann Publishing, 2017: 743-772.
[11] Johannes K F. Reactive polymers: Fundamentals and applications [M].
（1）经实验证实，自制 UPR 采用 BPO-DMA- 3rd ed. New York: William Andrew Publishing, 2018: 1-69.
[12] Wang Qing (王庆). Study on curing and thickening characteristics of
Co(Ⅱ)制灰固化，不仅使反应活化能降低，固化时 Indefinite polyester resin[D]. Nanjing: Nanjing Technology
间缩短至 25 min，而且原子灰的固化程度、附着力、 University (南京工业大学), 2006.
抗冲击性、韧性等较优，有可能完全替代进口产品， [13] Shao Zhixuan (邵志轩). Preparation and application of atomic ash
resin[D]. Shijiazhuang: Hebei University of Science and Technology
省外汇、降成本。 (河北科技大学), 2013.
（2）采用非等温 DSC 对原子灰 BPO-DMA- [14] Dong Lvping (董吕平). Synthesis and mechanism of LCC combined
accelerator[J]. Fiber Reinforced Plastics/Composites (玻璃钢/复合材
Co( Ⅱ ) 固化体系进行 了动力学 探究，并 采用
料), 1998,(4): 26-29.
Kissinger 极值法、FWO 积分法计算出该体系的活化 [15] Irving H, Williams R J P. Order of stability of metal complexes[J].
7
–1
能 E a =54.57 kJ/mol、指前因子 A=9.153×10 min ， Nature, 1948, 162(4123): 746-747.
[16] Irving H, Williams R J P. The stability of transition-metal complexes
且发现以上两种方法计算得到的活化能与等温测试 [J]. Journal of Chemical Society, 1953, 3192-3210[2019-06-13].
计算的活化能具有很好的一致性。 DOL: 10.1039/JR9530003192
[17] Zhao Mali (赵玛利). Research of surface treatment technology of
（3）采用 Friedman 方程来判定 BPO-DMA-Co
Cu-containing materials based on 3D laser processing system[D].
(Ⅱ)固化体系的固化模型，得出该体系遵从自催化 Tianjin: Tianjin University (天津大学), 2015.
反应模型，并根据线性回归计算得到动力学方程为 [18] Guo Junqi (郭君岐), Sun Youmei (孙友梅), Ma Xiaoyan (马晓燕).
Study on air-drying and corrosion-resistant unsaturated polyster resin
lnda/dt=lnβ(da/dT)= –E a/(R·T)+nln(1–a)+mlna+lnA，采 [J]. Thermosetting Resin (热固性树脂), 2012, 27(3): 42-45.
用该方程对固化过程进行模拟，结果证实自催化反应 [19] Li Qiangjun (李强军), Jiang Qibin (姜其斌), Li Lalian (李拉练), et al.
模型拟合的曲线与实验测试曲线有很好的吻合性。 Study on air-dry property unsaturated polyester resin[J]. Insulation
Materials (绝缘材料), 2008, (3): 8-10,14.
（4）当升温速率 β=0 时，原子灰采用 BPO- [20] Yu Tongfu (于同福), Bi Hongqin (毕鸿琴), Tang Shihang (唐世珩),
DMA-Co(Ⅱ)体系进行固化实验，当环境温度为 et al. The curing of unsaturated polyester resin[J]. Thermosetting
Resin (热固性树脂), 2006, (4): 50-53.
307.88 K 时，固化有较快的起始反应速度；当达到
[21] Li Fei (李飞). Study of the impact of thermal stability to UPR with
最大放热速度时，其体系温度为 323.50 K；温度达 complex inhibitors[D]. Wuhan: Wuhan University of Technology (武
371.15 K 时反应完成。 汉理工大学), 2012.
[22] Li Jianguo (李建国). The curing behaviors and the curing kinetics of
参考文献： the vinylester resin used in pultrusion process[D]. Beijing: Beijing
University of Chemical Technology (北京化工大学), 2003.
[1] Zhang Bingzhu (张炳烛), Wu Mingjun (吴命君). Property modifica- [23] Wang Congcai (王聪彩). Curing kinetics of unsaturated polyester
tion of unsaturated polyester resin for poly putty[J]. Chemical Prope- resin and characterization of structure of cured UPR[D]. Tianjin:
llants & Polymeric Materials (化学推进剂与高分子材料), 2005, 3(6): Tianjin University (天津大学), 2014.
22-25. [24] Zhang Di (张帝). Thermo catalytic curing of bisphenol A benzoxazine/
[2] Li Dedong (李德东). Study on improving the compositive function iodonium salt[D]. Chengdu: Southwest Petroleum University (西南
of poly-putty[J]. Surface Technology (表面技术), 2010, 39(3): 97-99. 石油大学), 2016.
[3] Zhang Yubo (张育波), Feng Zhaohua (冯兆华). Synthesis of air-dried [25] Jubsilp C, Punson K, Takeichi T, et al. Curingkinetics of benzoxazine
unsaturated polyester resin for automobile putty[J]. Coatings Tech- epoxy copolymer investigated by non-isothermal differential scanning
nology & Abstracts (涂料技术与文摘), 2016, 37(3): 29-32, 45. calorimetry[J]. Polymer Degadation and Stability, 2010, 95(6): 918-
[4] Chen Zhixiang (陈志祥), Fang Jun (方俊), Ma Yong (马勇). Preparation 924.