新型PVC辅助热稳定剂乙酰丙酮镁的制备及热稳定性能
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摘要
以氢氧化镁[Mg(OH)_2]和乙酰丙酮为原料,乙醇为溶剂,通过一步异相沉淀转化法制备配合物乙酰丙酮镁[Mg(acac)_2],用作聚氯乙烯(PVC)辅助热稳定剂。首先,采用XRD、FTIR、TG对产物进行了结构表征,然后通过静态热老化试验和刚果红试验,对乙酰丙酮镁的热稳定性能进行研究。结果表明,成功制备出产物乙酰丙酮镁,且含有2个结晶水;在PVC中,当主效热稳定剂与辅助热稳定剂的质量比为3∶5时,PVC的热稳定时间长达57min。该生产技术克服了乙酰丙酮镁传统合成方法产率低、操作过程复杂、污染等缺点,制备的产物乙酰丙酮镁与主效热稳定剂具有良好的协同作用,可以有效提高PVC的热稳定性能。
Magnesium acetylacetonate used as a polyvinyl chloride(PVC) auxiliary heat stabilizer was synthesized from magnesium hydroxide [Mg(OH)_2] and acetylacetone as raw materials and ethanol as solvent by one-step heterogeneous precipitation conversion technology. The as-prepared magnesium acetylacetonate was characterized by XRD, FTIR and TG-TGA, and its thermal stability was studied by static thermal aging and Congo red test paper.The results show that the prepared product is magnesium acetylacetonate and contains two crystalline water. In PVC, when the mass ratio of the main thermal stabilizer and the auxiliary heat stabilizer is 3∶5, the thermal stability time of PVC is up to 57 min. The production technology overcomes the disadvantages of low yield, complex operation and pollution of the traditional method of synthesis of magnesium acetylacetonate. The prepared product has a good synergistic effect with the main heat stabilizer, and can effectively improve the thermal stability of PVC.
Magnesium acetylacetonate used as a polyvinyl chloride(PVC) auxiliary heat stabilizer was synthesized from magnesium hydroxide [Mg(OH)_2] and acetylacetone as raw materials and ethanol as solvent by one-step heterogeneous precipitation conversion technology. The as-prepared magnesium acetylacetonate was characterized by XRD, FTIR and TG-TGA, and its thermal stability was studied by static thermal aging and Congo red test paper.The results show that the prepared product is magnesium acetylacetonate and contains two crystalline water. In PVC, when the mass ratio of the main thermal stabilizer and the auxiliary heat stabilizer is 3∶5, the thermal stability time of PVC is up to 57 min. The production technology overcomes the disadvantages of low yield, complex operation and pollution of the traditional method of synthesis of magnesium acetylacetonate. The prepared product has a good synergistic effect with the main heat stabilizer, and can effectively improve the thermal stability of PVC.
引文
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[24]闫晓红. PVC辅助热稳定剂β-二酮的合成与应用[J].现代塑料加与应用, 2000, 12(3):37-38.YAN X H. Synthesis and application of PVC-assisted thermal stabilizerβ-diketones[J]. Modern Plastics&Applications, 2000, 12(3):37-38.
[25]吴茂英,梁玲,林莅蒙.β-二酮盐对聚氯乙烯的热稳定作用——性能递变规律与机理[J].高分子材料科学与工程, 2014, 30(5):87-91.WU M Y, LIANG L, LIN L M. Thermal stabilization of polyvinyl chloride withβ-diketonates[J]. Polym. Mater. Sci. Eng., 2014, 30(5):87-91.
[26] MICHEL A, VAN H T, PERRIN B, et al. Synergistic mechanisms ofβ-diketone derivatives and zinc-calcium soaps in PVC stabilisation[J].Polym. Degrad.&Stab., 1981, 3(2):107-119.
[27] PAPPA A, MIKEDI K, AGAPIOU A, et al. TG-MS analysis of nitrile butadiene rubber blends(NBR/PVC)[J]. Journal of Analytical&Applied Pyrolysis, 2011, 92(1):106-110.
[28] BENSEMRA N, VAN HOANG T, GUYOT A, et al. Thermal dehydrochlorination and stabilization of poly(vinyl chloride)in solution:PartⅣ. Synergistic effects ofβ-diketone compounds and metal soap stabilizers[J]. Polym. Degrad.&Stab., 1989, 24(2):89-111.
[29]晏苏学,黄建国.β-二酮在钙/锌皂复合稳定剂中的应用[J].塑料助剂, 2006, 59(5):16-28.YAN S X, HUANG J G. Application ofβ-diketone in calcium/zinc soap compound stabilizer[J]. Plastics Additives, 2006, 59(5):16-28.
[30]吴茂英,林悟森,林莅蒙.β-二酮作用模式和锌基热稳定剂协同作用机理研究(下)[J].塑料助剂, 2010, 80(2):42-47.WU M Y, LIN W S, LIN L M. Study on the synergistic action mechanism ofβ-diketone action mode and zinc-based heat stabilizer(Part 2)[J]. Plastics Additives, 2010, 80(2):42-47.
[2]杨涛.聚氯乙烯配方设计与制品加工[M].北京:化学工业出版社,2011:978.YANG T. PVC formulation design and product processing[M]. Beijing:Chemical Industry Press, 2011:978.
[3]王丹,李花,李宏,等.甘油锌热稳定剂的合成及在PVC中的应用[J].塑料工业, 2015, 43(2):106-109.WANG D, LI H, LI H, et al. Synthesis of glycerin zinc heat stabilizer and its application in PVC[J]. Plastics Industry, 2015, 43(2):106-109.
[4] URETA E, CANTU M E. Zinc maleate and zinc anthranilate as thermal stabilizers for PVC[J]. J. Appl. Polym. Sci., 2000, 77(12):2603-2605.
[5]张启兴.热稳定剂在PVC塑料制品加工中的应用[J].聚氯乙烯,2007(7):1-4.ZHANG Q X. Application of heat stabilizer in the processing of PVC plastic products[J]. Polyvinyl Chloride, 2007(7):1-4.
[6]瞿英俊,唐伟,高尔金,等.辅助助剂对钙锌复合热稳定剂性能的影响[J].聚氯乙烯, 2013, 41(2):29-32.QU Y J, TANG W, GAO E J, et al. The influences of additives on properties of Ca/Zn composite heat stabilizers[J]. Polyvinyl Chloride,2013, 41(2):29-32.
[7]吴茂英,张祺满,林莅蒙.含β-二酮填充PVC塑料发红现象的原因与解决办法[J].塑料工业, 2011, 39(6):74-76.WU M Y, ZHANG Q M, LIN L M. Reasons and solutions method for the reddening phenomenon of filled PVC Containingβ-diketones[J].Plastics Industry, 2011, 39(6):74-76.
[8] HENRY F. Acetylacetone zinc hydrate used as halogenated polymer and its preparation method:US09623989[P], 2002-09-10.
[9]唐伟,陈语.我国PVC热稳定剂的现状与发展趋势[J].聚氯乙烯,2017, 45(8):11-15.TANG W, CHEN Y. Present situation and development trend of PVC heat stabilizers in China[J]. Polyvinyl Chloride, 2017, 45(8):11-15.
[10] BENANIBA M T, BELHANECHE-BENSEMRA N, GELBARD G.Stabilization of PVC by epoxidized sunflower oil in the presence of zinc and calcium stearates[J]. Polym. Degrada.&Stab., 2003, 83(2):245-249.
[11]刘青宝.乙酰丙酮金属化合物的合成及其对PVC的热稳定作用研究[D].北京:北京化工大学, 2009.LIU Q B. Synthesis of acetyl acetone metal compound and its thermal stabilization effect on PVC[D]. Beijing:Beijing University of Chemical Technology, 2009.
[12]王兴为.塑料助剂与配方设计技术[M].北京:化学工业出版社,2016:978.WANG X W. Plastics additives and formulation design technology[M].Beijing:Chemical Industry Press, 2016:978.
[13]唐新根,张晓春,乐长高.β-二酮新型辅助稳定剂的合成与应用[J].合成材料老化与应用, 1996,3(3):12-16.TANG X G, ZHANG X C, LE C G. Synthesis and application of a new type of auxiliary stabilizer ofβ-diketones[J]. Aging and Application of Synthetic Materials, 1996, 3(3):12-16.
[14]蒋金博.新型PVC热稳定剂合成、应用及机理研究[D].长沙:湖南大学, 2006.JIANG J B. New PVC heat stabilizer synthesis, application and mechanism research[D]. Changsha:Hunan University, 2006.
[15]杨静,晏苏学,童敏伟,等.高白度乙酰丙酮钙的制备及应用研究[J].塑料助剂, 2016, 6(2):24-25,28.YANG J, YAN S X, TONG M W, et al. Study on preparation and application of high whiteness calcium acetylacetonate[J]. Plastic Additives, 2016, 6(2):24-25,28.
[16]李兑,张宏量,王艳,等.乙酰丙酮钙的合成研究[J].塑料助剂,2013, 5(1):18-21.LI D, ZHANG H L, WANG Y, et al. Synthesis of calcium acetylacetonate[J]. Plastic Additives, 2013, 5(1):18-21.
[17]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.塑料热老化试验方法:GB/T7141—2008[S].北京:中国标准出版社, 2008.General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People’s Republic of China. The thermal aging test method of plastics:GB/T7141—2008[S]. Beijing:Standard Press of China, 2008.
[18]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.以氯乙烯均聚和共聚物为主的共混物及制品在高温时放出氯化氢和任何其他酸性产物的测定:GB/T 2917.1—2002[S].北京:中国标准出版社, 2002.General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People’s Republic of China. Determination of hydrogen chloride and any other acidic products emitted from blends and products of vinyl chloride homopolymers and copolymers at high temperatures:GB/T 2917.1—2002[S]. Beijing:Standard Press of China, 2002.
[19] LI S M, YAO Y W. Effect of thermal stabilizers composed of zinc barbiturate and calcium stearate for rigid poly(vinyl chloride)[J].Polym. Degrad.&Stab., 2011, 96(4):637-641.
[20] STEENWIJK J, LANGEROCK R, ES D S V. Long-term heat stabilisation by(natural)polyols in heavy metal-and zinc-free poly(vinyl chloride)[J]. Polymer Degradation&Stability, 2006, 91(1):52-59.
[21] FU M, LI D G, LIU H, et al. Insights into the use of zinc-mannitol alkoxide as a novel thermal stabilizer for rigid poly(vinyl chloride)[J].Journal of Applied Polymer Science, 2015, 132(23):42038.
[22] HUANG Y, YANG Z D. The effect of sodium stearate-modified hydrocalumite on the thermal stability of poly(vinyl chloride)[J].Journal of Applied Polymer Science, 2018, 135(4):45758.
[23]蔡宏国.β-二酮新型辅助稳定剂[J].精细化工, 1992, 9(2):34-37.CAI H G. New auxiliary stabilizers ofβ-diketone[J]. Fine Chemicals,1992, 9(2):34-37.
[24]闫晓红. PVC辅助热稳定剂β-二酮的合成与应用[J].现代塑料加与应用, 2000, 12(3):37-38.YAN X H. Synthesis and application of PVC-assisted thermal stabilizerβ-diketones[J]. Modern Plastics&Applications, 2000, 12(3):37-38.
[25]吴茂英,梁玲,林莅蒙.β-二酮盐对聚氯乙烯的热稳定作用——性能递变规律与机理[J].高分子材料科学与工程, 2014, 30(5):87-91.WU M Y, LIANG L, LIN L M. Thermal stabilization of polyvinyl chloride withβ-diketonates[J]. Polym. Mater. Sci. Eng., 2014, 30(5):87-91.
[26] MICHEL A, VAN H T, PERRIN B, et al. Synergistic mechanisms ofβ-diketone derivatives and zinc-calcium soaps in PVC stabilisation[J].Polym. Degrad.&Stab., 1981, 3(2):107-119.
[27] PAPPA A, MIKEDI K, AGAPIOU A, et al. TG-MS analysis of nitrile butadiene rubber blends(NBR/PVC)[J]. Journal of Analytical&Applied Pyrolysis, 2011, 92(1):106-110.
[28] BENSEMRA N, VAN HOANG T, GUYOT A, et al. Thermal dehydrochlorination and stabilization of poly(vinyl chloride)in solution:PartⅣ. Synergistic effects ofβ-diketone compounds and metal soap stabilizers[J]. Polym. Degrad.&Stab., 1989, 24(2):89-111.
[29]晏苏学,黄建国.β-二酮在钙/锌皂复合稳定剂中的应用[J].塑料助剂, 2006, 59(5):16-28.YAN S X, HUANG J G. Application ofβ-diketone in calcium/zinc soap compound stabilizer[J]. Plastics Additives, 2006, 59(5):16-28.
[30]吴茂英,林悟森,林莅蒙.β-二酮作用模式和锌基热稳定剂协同作用机理研究(下)[J].塑料助剂, 2010, 80(2):42-47.WU M Y, LIN W S, LIN L M. Study on the synergistic action mechanism ofβ-diketone action mode and zinc-based heat stabilizer(Part 2)[J]. Plastics Additives, 2010, 80(2):42-47.