Page 180 - 《精细化工》2020年第4期

·814· 精细化工 FINE CHEMICALS 第 37 卷

由图 7 可知，当 PVC+ATAL 和 PVC+ATAL/PER [2] YANG Zhanfeng (杨占峰), ZHANG Yuxi (张玉玺), YU Xiaoli (于
晓丽), et al. Application of a new rare earth co-heat stabilizers in
两个 样品降解时 间均为 0 min 时， ATAL 和
PVC profile[J]. Chinese Rare Earth (稀土), 2016, 37(6): 49-54.
ATAL/PER 复合热稳定剂（图中细小的颗粒）均较 [3] WANG M, SONG X H, JIANG J C, et al. Influence of zeolitic
好地分散在 PVC 颗粒表面。当 PVC+ ATAL 和 imidazolate framework-8 on the thermal stabilization of poly(vinyl
chloride)[J]. Polymer Degradation and Stability, 2018, 149: 112-118.
PVC+ATAL/PER 两个样品降解时间为 30 min 时， [4] YU Xiaoli (于晓丽), YANG Zhanfeng (杨占峰), ZHANG Yuxi (张
ATAL 和 ATAL/PER 复合热稳定剂仍然分散在 PVC 玉玺), et al. Preparation of cerium stearate compound heat stabilizer
and application in PVC formwork[J]. Chinese Rare Earth (稀土),
颗粒表面，但此时添加 ATAL 的 PVC 样品已经发生 2018, 39(2): 18-24.
降解，颜色开始加深，表面棱角也逐渐减少，而添 [5] ZHANG Ning (张宁), LI Deling (李德玲), YANG Jing (杨静).
Effect of rare earth complex thermal stabilizer with myristic acid on
加 ATAL/PER 复合热稳定剂的 PVC 样品降解较缓
PVC properities[J]. China Plastics (中国塑料), 2013, 27(7): 81-85.
慢，颜色未发生明显变化，表面形貌也变化不大。 [6] LI Mei (李梅), WANG Xiaochuan (王晓川), WU Jinxiu (吴锦绣), et
但当 PVC+ATAL 和 PVC+ATAL/PER 两个样品降解 al. Study on alkali type lanthanum citrate as a heat stabilizer of
PVC[J]. Chinese Rare Earths, 2017, 38(3): 60-67.
时间为 60 min 时，添加 ATAL 的 PVC 样品已发生 [7] LIU Zhaogang (柳召刚), DONG Xin (董昕), HU Yanhong (胡艳宏),
明显的熔融，样品颜色进一步加深，说明 PVC 明显 et al. synthesis of lanthanum iso-nicotinate and its heat-stabilizing
降解，共轭双键增多 [18-19] ；而添加 ATAL/PER 复合 effect on PVC[J]. China Plastics (中国塑料), 2018, 32(11): 117-123.
[8] LI M, LIANG Y D, WANG X B, et al. Synthesis of the complex of
热稳定剂的 PVC 样品颗粒间虽也有熔融粘连，但样 lanthanum (III) with N-(2-amino ethyl) maleamic acid radical and its
品颜色变化不明显，仅较 30 min 时略有加深，而样 application to PVC as thermal stabilizer[J]. Polymer Degradation and
Stability, 2016, 124: 87-94.
品表面的热稳定剂则与 PVC 相容良好。综合以上分 [9] YE Q F, MA X T, LI B B, et al. Development and investigation of
析，说明 ATAL 对 PVC 的热降解具有一定的抑制作 lanthanum sulfadiazine with calcium stearate and epoxidisedsoyabeanoil
as complex thermal stabilizers for stabilizing poly(vinyl chloride)[J].
用，而与 PER 复配后，二者间可发挥较好的协同作 Polymers, 2019, 11(3): 531. DOI: 10.3390/polym11030531.
用，能有效抑制 PVC 的热降解，抑制其着色。 [10] HU Chengcheng (胡程程), CHEN Ying (陈颖), LI Xiaobin (李晓
斌), et al. Preparation of calcium/zinc cyanurate and its application in
3 结论 PVC products[J]. Fine Chemicals (精细化工), 2019, 36(2): 328-335.
[11] American Society of Testing Materials. ASTM D4202-92:
Thermalstability of poly (vinyl chloride) (PVC) resin[S]. New York:
（1）采用廉价的生物代谢中间体 ATA 和硝酸 American Society of Testing Materials, 1992: 1-2.
镧、NaOH 为原料，水为溶剂制得了 ATAL，并通过 [12] LIU Hongliang (刘洪亮), JIANG Pingping (蒋平平), ZHANG Kai
(张凯), et al. Synthesis, characterization of bismuth oleate and its
元素分析、ICP-OES、红外光谱确定了目标产物的 application in PVC[J]. Fine Chemicals (精细化工), 2017, 34(6):
生成。 690-695, 702.
[13] YU Jing (于静), LI Minxian (李敏贤), LI Dengling (李德玲). Effect
（2）刚果红实验和热失重分析表明，ATAL 对
of carboxylic acid on property of composite carboxylate lanthanum
PVC 具有一定的热稳定作用并能抑制着色，可将 thermal stabilizer[J]. Journal of the Chinese Society of Rare Earths
PVC 热降解的平均活化能提高 15.78 kJ/mol，较好 (中国稀土学报), 2015, 33(1): 60-65.
[14] CHEN J, NIE X A, JIANG J C, et al. Thermal degradation and
地抑制了 PVC 的降解反应活性。 plasticizing mechanism of poly (vinyl chloride) plasticized with a
（3）协同性实验及扫描电镜观察表明，ATAL novel cardanol derived plasticizer[J]. IOP Conf Series: Materials
Science and Engineering, 2018, 292: 1-8.
与β-二酮、PDOP、PER、ESO 之间都有协同性， [15] LI M, ZHANG J W, XIN J N, et al. Design of green zinc-based
且与 PER 间的协同性能最佳，可将 PVC 的静态热 thermal stabilizers derived from tung oilfatty acid and study of
稳定时间延长至 37 min，动态热稳定时间达到 thermal stabilization for PVC[J]. Journal of Applied Polymer
Science, 2017, 134(14): 44679. DOI: 10.1002/app.44679.
3480 s，平衡扭矩为 25 N·m；ATAL 及 ATAL/PER [16] WANG M, XIA J L, JIANG J C, et al. Mixed calcium and zinc salts
复合热稳定剂在 PVC 热降解过程中较好地分散在 of N-(3-amino-benzoic acid)terpene-maleamic acid: PREPARATION
and its application as novel thermal stabilizer for poly (vinyl
PVC 颗粒表面，起到抑制 PVC 降解的作用，但 chloride)[J]. RSC Advances, 2016, 6: 97036-97047.
ATAL/PER 复合热稳定剂抑制 PVC 降解的性能优于 [17] YANG Tao (杨涛). Application of phosphite in polyvinyl chloride[J].
Plastics Additives (塑料助剂), 2003, (4): 25-28.
单独使用 ATAL 的。
[18] WANG M, SONG X H, JIANG J C, et al. Excellent hydroxyl and
nitrogen rich groups-containing tung-oil-based Ca/Zn and polyol
参考文献： stabilizers for enhanced thermal stability of PVC[J]. Thermochimica
[1] KANG Jie (康洁), LI Kanshe (李侃社), CHEN Chuangqian (陈创 Acta, 2017, 658(10): 84-92.
前). Preparation of a rare earth heat stabilizers and the effect on [19] ARRIETA M P, SAMPER M D, JIMÉNEZ-LÓPEZ M, et al.
thermal degradation of PVC[J]. Journal of Materials Science & Combined effect of linseed oil and gum rosin as natural additives for
Engineering (材料科学与工程学报), 2018, 36(2): 272-277. PVC[J]. Industrial Crops and Products, 2017, 99: 196-204.