二元羧酸单酯金属盐对PVC的热稳定作用——性能递变规律与机理
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摘要
用烘箱变色法测试了丙二酸、丁二酸和马来酸单丁酯的钙、锶、钡、锌和镉盐对聚氯乙烯(PVC)热稳定性的影响。结果表明,二元羧酸单酯金属盐所稳定PVC的变色随其分子中羧酸根羰基C原子的正电性和金属离子的极化力的增强而减慢,而分子中含有亲双烯结构的二元羧酸单酯金属盐所稳定的PVC的着色减轻;据此可以推知,二元羧酸单酯金属盐之所以能抑制PVC的变色,并不是因为能取代不稳定氯(Frye和Horst机理),而是因为能以羧酸根羰基C原子和金属离子与PVC发生亲电反应,而之所以分子中含有亲双烯结构的二元羧酸单酯金属盐所稳定的PVC着色减轻,则是因为它们还能与PVC发生Diels-Alder环加成反应。
The effects of calcium,strontium,barium,zinc and cadmium salts of monobutyl malonate,succinate and maleate on the heat stability of poly(vinyl chloride)(PVC)were determined by an oven discoloration method.The results indicated that the discoloration rate of PVC stabilized with dicarboxylic acid monoester metal salts decreased with an increase of the positive electricity of carbon atom in carbonyl groups and the polarization force of metal ions in the molecules.However,PVC stabilized with dicarboxylic acid monoester metal salt containing a dienophilic structure presented a weaker coloring effect.It was deduced that the reduction mechanism of discoloration rate for PVC by dicarboxylic acid monoester metal salts was attributed to the electrophilic reactions of carbon atom in carbonyl groups and metal ions with PVC.Moreover,the Diels-Alder cycloaddition reaction led to the weak coloring effect on PVC when stabilized with dicarboxylic acid monoester metal salt containing a dienophilic structure.
The effects of calcium,strontium,barium,zinc and cadmium salts of monobutyl malonate,succinate and maleate on the heat stability of poly(vinyl chloride)(PVC)were determined by an oven discoloration method.The results indicated that the discoloration rate of PVC stabilized with dicarboxylic acid monoester metal salts decreased with an increase of the positive electricity of carbon atom in carbonyl groups and the polarization force of metal ions in the molecules.However,PVC stabilized with dicarboxylic acid monoester metal salt containing a dienophilic structure presented a weaker coloring effect.It was deduced that the reduction mechanism of discoloration rate for PVC by dicarboxylic acid monoester metal salts was attributed to the electrophilic reactions of carbon atom in carbonyl groups and metal ions with PVC.Moreover,the Diels-Alder cycloaddition reaction led to the weak coloring effect on PVC when stabilized with dicarboxylic acid monoester metal salt containing a dienophilic structure.
引文
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[16]吴茂英,粟颖.二元羧酸有机锡对PVC的热稳定作用---性能递变规律与机理[J].中国塑料,2016,30(11):88-92.WU M Y,SU Y.Heat Stabilization of Organotin Two Carboxylates on PVC---Progressive Change Law of Performance and Mechanism[J].China Plastics,2016,30(11):88-92.
[17]姜淑芳.Diels-Alder反应活性及其理论分析[J].哈尔滨师范大学自然科学学报,1990,6(3):51-60.JIANG S F.The Activities of Diels-Alder Reactions and Their Theoretical Analysis[J].Natural Science Journal of Harbin Normal University,1990,6(3):51-60.
[18]KISELEV V D,SHAKIROVAL I,KONOVALOV A I.Internal and External Factors Promoting the Diels-Alder Reaction[J].Russian Chemical Bulletin,2013,62(2):285-303.
[2]吴茂英.PVC热稳定剂及其应用技术[M].北京:化学工业出版社,2011:17-33.
[3]吴茂英.PVC热稳定剂的发展趋势与技术进展[J].塑料,2010,39(3):1-7.WU M Y.Development Trend and Technological Progress of Heat Stabilizers for PVC[J].Plastics,2010,39(3):1-7.
[4]曹先贵,吴茂英,何家俊.氨基脲嘧啶对PVC的热稳定作用---性能递变规律与机理[J].中国塑料,2017,31(9):97-101.CAO X G,WU M Y,HE J J.Heat Stabilization of Aminouracils on PVC---Progressive Change Law of Performance and Mechanism[J].China Plastics,2017,31(9):97-101.
[5]Frye A H,Horst R W.The Mechanism of Poly(vinyl Chloride)Stabilization by Barium,Cadmium,and Zinc Carboxylates.I.Infrared Studies[J].J Polym Sci,1959,40(137):419-431.
[6]Frye A H,Horst R W.The Mechanism of Poly(vinyl Chloride)Stabilization by Barium,Cadmium,and Zinc Carboxylates.II.Radioactive Tracer Studies[J].J Polym Sci,1960,45(145):1-12.
[7]Frye A H,Horst R W,Marko A.The Chemistry of Poly(vinyl Chloride)Stabilization.V.Organotin Stabilizers Having Radioactively Tagged Y Groups[J].J Polym Sci,Part A,1964,2:1 801-1 814.
[8]Quattlebaum Jr W M,Noffsinger C A.Stabilized Vinyl Resin:US2307157[P].1943-7-5.
[9]Mufti A S,Poller R C.The Stabilization of Poly(vinyl chloride)by Organotin Maleates.Polymer,1966,7(12):641-642.
[10]吴茂英,粟颖.二元羧酸有机锡对PVC的热稳定作用---性能递变规律与机理[J].中国塑料,2016,30(11):88-92.WU M Y,SU Y.Heat Stabilization of Organotin Two Carboxylates on PVC---Progressive Change Law of Performance and Mechanism[J].China Plastics,2016,30(11):88-92.
[11]胡振锟,狄超.马来酸单辛酯与苯酐单辛酯的制备[J].江苏化工,2003,31(1):38-39,47.HU Z K,DI C.Preparation of Mono-2-ethylhexyl Maleate and Mono-2-ethyl o-Phthalate[J].Jiangsu Chem Ind,2003,31(1):38-39,47.
[12]顾庆超.新编化学用表[M].南京:江苏教学出版社,1998.
[13]天津大学无机化学教研室.无机化学[M].北京:高等教育出版社,2010.
[14]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):87-91,97.WU M Y,LIANG L,LIN L M.Heat Stabilization ofβ-Diketone Salts on PVC:Progressive Change Law of Performance and Mechanism[J].Polym Mater Sci Eng,2014,30(5):87-91,97.
[15]粟颖,吴茂英.对取代苯甲酸盐对PVC的热稳定性能递变规律[J].塑料,2015,44(2):63-65,82.SU Y,WU M Y.Progressive Change Law of Heat Stabilization Performance of Substituted Benzoates on PVC[J].Plastics,2015,44(2):63-65,82.
[16]吴茂英,粟颖.二元羧酸有机锡对PVC的热稳定作用---性能递变规律与机理[J].中国塑料,2016,30(11):88-92.WU M Y,SU Y.Heat Stabilization of Organotin Two Carboxylates on PVC---Progressive Change Law of Performance and Mechanism[J].China Plastics,2016,30(11):88-92.
[17]姜淑芳.Diels-Alder反应活性及其理论分析[J].哈尔滨师范大学自然科学学报,1990,6(3):51-60.JIANG S F.The Activities of Diels-Alder Reactions and Their Theoretical Analysis[J].Natural Science Journal of Harbin Normal University,1990,6(3):51-60.
[18]KISELEV V D,SHAKIROVAL I,KONOVALOV A I.Internal and External Factors Promoting the Diels-Alder Reaction[J].Russian Chemical Bulletin,2013,62(2):285-303.