脂肪族二元羧酸盐成核剂在聚丙烯中的应用
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摘要
聚丙烯由于其原料来源广、价格低、加工简单等优点拥有良好的市场前景。但其球晶尺寸大、脆化温度高、冲击性能差等缺点导致其应用受到了很大范围的限制。添加成核剂是目前最有效的改性方法之一。作为研究最早的一类β成核剂之一,脂肪族二元羧酸盐对聚丙烯材料的刚性及表面硬度具有一定的积极作用而且成本相对较低,具有良好的热稳定性,并且不会对材料的其他性能产生影响。脂肪族二元羧酸盐类主要有2种制备方法,分别为中和法和复分解法,不同的制备方法也会对聚丙烯的成核性能产生一定的影响,主要综述了一系列脂肪族二元羧酸盐对聚丙烯成核性能的影响,并对脂肪族二元羧酸盐成核剂的发展提出展望。
Polypropylene(PP) has good market prospects due to its wide source of raw materials,low price,easy processing and good mechanical properties. However,large spherulite size,high embrittlement temperature,poor impact and other shortcomings limit its wide range of applications. At present,addition of nucleating agents into PP during processing is one of the most effective modification methods. As one of the earliest types of beta nucleating agents,aliphatic dicarboxylates have positive effect on the rigidity and surface hardness of PP materials,and have such advantages as low cost,good thermal stability,and no impact on other properties of the material. The preparation methods of aliphatic dicarboxylates mainly contain the neutralization method and the metathesis method,different preparation methods will also have some impact on the nucleation performance of polypropylene,influences of a series of aliphatic dicarboxylates on the nucleation properties of PP are summarized and the development prospects of nucleating agents are also discussed.
Polypropylene(PP) has good market prospects due to its wide source of raw materials,low price,easy processing and good mechanical properties. However,large spherulite size,high embrittlement temperature,poor impact and other shortcomings limit its wide range of applications. At present,addition of nucleating agents into PP during processing is one of the most effective modification methods. As one of the earliest types of beta nucleating agents,aliphatic dicarboxylates have positive effect on the rigidity and surface hardness of PP materials,and have such advantages as low cost,good thermal stability,and no impact on other properties of the material. The preparation methods of aliphatic dicarboxylates mainly contain the neutralization method and the metathesis method,different preparation methods will also have some impact on the nucleation performance of polypropylene,influences of a series of aliphatic dicarboxylates on the nucleation properties of PP are summarized and the development prospects of nucleating agents are also discussed.
引文
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[13] LUO F,WANG K,NING N,et al. Dependence of mechanical properties onβ-form content and crystalline morphology forβ-nucleated isotactic polypropylene[J]. Polymers for Advanced Technologies,2011,22(12):2044-2054.
[14] MOHMEYER N,SCHMIDT H,KRISTIANSEN P M,et al. Influence of chemical structure and solubility of bisamide additives on the nucleation of isotactic polypropylene and the improvement of its charge storage properties[J]. Macromolecules,2006,39(17):5760-5767.
[15] LI Z,LIU Y,NIE M,et al. Self-Assembly behavior of aryl amide nucleating agent under supercritical carbon dioxide and its influence on polypropylene[J]. Polymer-Plastics Technology and Engineering,2017,56(18):1937-1941.
[16] BECK H N. Heterogeneous nucleating agents for polypropylene crystallization[J]. Journal of Applied Polymer Science,1967,11(5):673-685.
[17] ZHANG Y,GUO L,CHEN H,et al. Properties and crystallization behaviors of isotactic polypropylene under action of an effective nucleating agent[J]. Journal of Macromolecular Science,Part B:Physics,2015,54(9):1019-1028.
[18] JIANG C,ZHAO S,XIN Z. Influence of a novelβ-nucleating agent on the structure,mechanical properties,and crystallization behavior of isotactic polypropylene[J]. Journal of Thermoplastic Composite Materials,2015,28(5):610-629.
[19] CAI Z,ZHAO S,SHEN B,et al. The effect of bicyclo[2. 2. 1]hept-5-ene-2, 3-dicarboxylate on the mechanical properties and crystallization behaviors of isotactic polypropylene[J]. Journal of Applied Polymer Science,2010,116(2):792-800.
[20] ZHAO S,YU X,GONG H,et al. The crystallization behavior of isotactic polypropylene induced by a novel antinucleating agent and its inhibition mechanism of nucleation[J]. Industrial&Engineering Chemistry Research,2015,54(31):7650-7657.
[21]史观一,张景云.β晶型聚丙烯的研究[J].科学通报,1981,26(12):731-733.
[22]张晓东,史观一.成核剂含量对β晶相聚丙烯结晶与熔融行为的影响[J].高分子学报,1992(3):293-297.
[23]赵艳辉,史建公,张敏宏,等.脂肪二元羧酸及其盐的制备和结构研究进展[J].石化技术,2010,17(4):54-58.
[24]张跃飞,戴益民.聚丙烯成核剂[M].北京:化学工业出版社,2013:32.
[25]马晓雨.二元酸镁的合成及性能研究[D].沈阳:沈阳工业大学,2014.
[26]罗贤祖,张跃飞,杨小俊,等.有机羧酸盐类聚丙烯成核剂的研究进展[J].塑料工业,2012,40(2):9-12.
[27] DOU Q,LU Q,LI H. Effect of metallic salts of malonic acid on the formation ofβcrystalline form in isotactic polypropylene[J]. Journal of Macromolecular Science,Part B:Physics,2008,47(5):900-912.
[28] DOU Q,LU Q. Effect of calcium malonate on the formation ofβcrystalline form in isotactic poly(propylene)[J]. Polymers for Advanced Technologies,2008,19(11):1522-1527.
[29] DOU Q,LU Q,LI H. Effect of metallic salts of glutaric acid on the formation ofβ-crystalline form in isotactic polypropylene[J]. Journal of Elastomers&Plastics,2009,41(6):509-522.
[30]赵世成,宫含章,俞欣,等.β晶成核剂己二酸锌对等规聚丙烯成核效应的影响[J].工程塑料应用,2016,44(8):111-114.
[31] ZHAO S,GONG H,YU X,et al. A highly active and selectiveβ-nucleating agent for isotactic polypropylene and crystallization behavior ofβ-nucleated isotactic polypropylene under rapid cooling[J]. Journal of Applied Polymer Science,2016,133(32):43767.
[32]宫含章.聚丙烯β晶成核剂己二酸锌的制备及成核性能研究[D].上海:华东理工大学,2016.
[33]窦强.庚二酸类成核剂对等规聚丙烯β晶结晶行为的影响[J].中国塑料,2006,20(10):68-73.
[34] DAI X,ZHANG Z,WANG C,et al. A novel montmorillonite withβ-nucleating surface for enhancingβ-crystallization of isotactic polypropylene[J]. Composites Part A:Applied Science and Manufacturing,2013,49:1-8.
[35] LI X,HU K,JI M,et al. Calcium dicarboxylates nucleation ofβ-polypropylene[J]. Journal of Applied Polymer Science,2002,86(3):633-638.
[36]薛建峰,窦强.辛二酸盐成核改性等规聚丙烯的研究[J].塑料科技,2011,39(1):104-108.
[37] VARGA J,MUDRA I,EHRENSTEIN G W. Highly active thermally stableβ-nucleating agents for isotactic polypropylene[J]. Journal of Applied Polymer Science,1999,74(10):2357-2368.
[38] DOU Q. A comparison of the effects of calciumglutarate and pimelate on the formation ofβcrystalline form in isotactic poly(propylene)[J]. Journal of Macromolecular Science,Part B:Physics,2007,47(1):127-138.
[2] ZHANG Y F,LUO X Z,CHANG Y,et al. Non-isothermal crystallization behaviors of isotactic polypropylene with and without 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol as a nucleating agent[J].International Journal of Polymer Analysis and Characterization,2010,15(7):450-459.
[3]谢飞,张祥福,方舫,等.成核剂对增韧聚丙烯力学性能的影响[J].中国塑料,2000,14(11):76-80.
[4] KOTEK J,KELNAR I,BALDRIAN J,et al. Tensile behaviour of isotactic polypropylene modified by specific nucleation and active fillers[J]. European Polymer Journal,2004,40(4):679-684.
[5] VARGA J.β-Modification of isotactic polypropylene:preparation,structure,processing,properties,and application[J]. Journal of Macromolecular Science,Part B:Physics,2002,41(4/5/6):1121-1171.
[6] JONES A T,AIZLEWOOD J M,BECKETT D R. Crystalline forms of isotactic polypropylene[J]. Macromolecular Chemistry and Physics,1964,75(1):134-158.
[7]史建公,蒋绍洋,张敏宏,等.稀土β聚丙烯成核剂研究及应用进展[J].化工进展,2010,29(5):854-860.
[8] PAPAGEORGIOU D G,CHRISSAFIS K,BIKIARIS D N.β-Nucleated polypropylene:processing, properties and nanocomposites[J].Polymer Reviews,2015,55(4):596-629.
[9] CHEN Y,ZHONG G,WANG Y,et al. Unusual tuning of mechanical properties of isotactic polypropylene using counteraction of shear flow andβ-nucleating agent onβ-form nucleation[J]. Macromolecules,2009,42(12):4343-4348.
[10] ZHU J,NI H,LIAO X,et al. Preparation and crystallization property of ternary composites of WBG/AA-RCC/PP[J/OL]. Journal of Chemistry,2015[2015-11-12]. http://dx. doi. org/10. 1155/2015/545016.
[11] XIAO W C,WU P Y,FENG J C,et al. Influence of a novelβ-nucleating agent on the structure,morphology,and nonisothermal crystallization behavior of isotactic polypropylene[J]. Journal of Applied Polymer Science,2009,111(2):1076-1085.
[12] XIAO W,WU P,FENG J. Effect ofβ-nucleating agents on crystallization and melting behavior of isotactic polypropylene[J].Journal of Applied Polymer Science,2008,108(5):3370-3379.
[13] LUO F,WANG K,NING N,et al. Dependence of mechanical properties onβ-form content and crystalline morphology forβ-nucleated isotactic polypropylene[J]. Polymers for Advanced Technologies,2011,22(12):2044-2054.
[14] MOHMEYER N,SCHMIDT H,KRISTIANSEN P M,et al. Influence of chemical structure and solubility of bisamide additives on the nucleation of isotactic polypropylene and the improvement of its charge storage properties[J]. Macromolecules,2006,39(17):5760-5767.
[15] LI Z,LIU Y,NIE M,et al. Self-Assembly behavior of aryl amide nucleating agent under supercritical carbon dioxide and its influence on polypropylene[J]. Polymer-Plastics Technology and Engineering,2017,56(18):1937-1941.
[16] BECK H N. Heterogeneous nucleating agents for polypropylene crystallization[J]. Journal of Applied Polymer Science,1967,11(5):673-685.
[17] ZHANG Y,GUO L,CHEN H,et al. Properties and crystallization behaviors of isotactic polypropylene under action of an effective nucleating agent[J]. Journal of Macromolecular Science,Part B:Physics,2015,54(9):1019-1028.
[18] JIANG C,ZHAO S,XIN Z. Influence of a novelβ-nucleating agent on the structure,mechanical properties,and crystallization behavior of isotactic polypropylene[J]. Journal of Thermoplastic Composite Materials,2015,28(5):610-629.
[19] CAI Z,ZHAO S,SHEN B,et al. The effect of bicyclo[2. 2. 1]hept-5-ene-2, 3-dicarboxylate on the mechanical properties and crystallization behaviors of isotactic polypropylene[J]. Journal of Applied Polymer Science,2010,116(2):792-800.
[20] ZHAO S,YU X,GONG H,et al. The crystallization behavior of isotactic polypropylene induced by a novel antinucleating agent and its inhibition mechanism of nucleation[J]. Industrial&Engineering Chemistry Research,2015,54(31):7650-7657.
[21]史观一,张景云.β晶型聚丙烯的研究[J].科学通报,1981,26(12):731-733.
[22]张晓东,史观一.成核剂含量对β晶相聚丙烯结晶与熔融行为的影响[J].高分子学报,1992(3):293-297.
[23]赵艳辉,史建公,张敏宏,等.脂肪二元羧酸及其盐的制备和结构研究进展[J].石化技术,2010,17(4):54-58.
[24]张跃飞,戴益民.聚丙烯成核剂[M].北京:化学工业出版社,2013:32.
[25]马晓雨.二元酸镁的合成及性能研究[D].沈阳:沈阳工业大学,2014.
[26]罗贤祖,张跃飞,杨小俊,等.有机羧酸盐类聚丙烯成核剂的研究进展[J].塑料工业,2012,40(2):9-12.
[27] DOU Q,LU Q,LI H. Effect of metallic salts of malonic acid on the formation ofβcrystalline form in isotactic polypropylene[J]. Journal of Macromolecular Science,Part B:Physics,2008,47(5):900-912.
[28] DOU Q,LU Q. Effect of calcium malonate on the formation ofβcrystalline form in isotactic poly(propylene)[J]. Polymers for Advanced Technologies,2008,19(11):1522-1527.
[29] DOU Q,LU Q,LI H. Effect of metallic salts of glutaric acid on the formation ofβ-crystalline form in isotactic polypropylene[J]. Journal of Elastomers&Plastics,2009,41(6):509-522.
[30]赵世成,宫含章,俞欣,等.β晶成核剂己二酸锌对等规聚丙烯成核效应的影响[J].工程塑料应用,2016,44(8):111-114.
[31] ZHAO S,GONG H,YU X,et al. A highly active and selectiveβ-nucleating agent for isotactic polypropylene and crystallization behavior ofβ-nucleated isotactic polypropylene under rapid cooling[J]. Journal of Applied Polymer Science,2016,133(32):43767.
[32]宫含章.聚丙烯β晶成核剂己二酸锌的制备及成核性能研究[D].上海:华东理工大学,2016.
[33]窦强.庚二酸类成核剂对等规聚丙烯β晶结晶行为的影响[J].中国塑料,2006,20(10):68-73.
[34] DAI X,ZHANG Z,WANG C,et al. A novel montmorillonite withβ-nucleating surface for enhancingβ-crystallization of isotactic polypropylene[J]. Composites Part A:Applied Science and Manufacturing,2013,49:1-8.
[35] LI X,HU K,JI M,et al. Calcium dicarboxylates nucleation ofβ-polypropylene[J]. Journal of Applied Polymer Science,2002,86(3):633-638.
[36]薛建峰,窦强.辛二酸盐成核改性等规聚丙烯的研究[J].塑料科技,2011,39(1):104-108.
[37] VARGA J,MUDRA I,EHRENSTEIN G W. Highly active thermally stableβ-nucleating agents for isotactic polypropylene[J]. Journal of Applied Polymer Science,1999,74(10):2357-2368.
[38] DOU Q. A comparison of the effects of calciumglutarate and pimelate on the formation ofβcrystalline form in isotactic poly(propylene)[J]. Journal of Macromolecular Science,Part B:Physics,2007,47(1):127-138.