不同改性剂对PP/CaCO_3复合材料结晶和动态力学性能的影响
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摘要
以马来酸酐(MAH)、聚丙烯蜡(PPW)为主要原料,采用原位固相接枝改性法制得PP/Ca-CO3-MAH-PPW复合材料,对改性CaCO_3进行表面性能分析,并与PP/PP-g-MAH/CaCO_3复合材料进行结晶、动态力学和耐热性能的比较.结果表明,CaCO_3经原位固相接枝改性后,表面极性减弱,与PP的界面张力降低、相容性提高; CaCO_3表面的PPW层虽会阻碍CaCO_3的异相成核作用,但其可使复合材料形成适宜的界面粘接,有利于材料韧性的提高; CaCO_3-MAH-PPW可降低基体分子链的缠绕程度,增加其柔顺性,使复合材料玻璃化转变温度下降. PP-g-MAH的存在有助于提高PP/PP-g-MAH/CaCO_3复合材料的结晶温度,与基体形成较强的界面粘接,提高复合材料的模量、强度以及耐热性能.
PP/CaCO_3-MAH-PPW composite was prepared by means of in-situ solid phase graft copolymerization using maleic anhydride( MAH) and polypropylene wax( PPW) as the main raw materials. The surface properties of the modified CaCO_3 were analyzed. Its crystallization behavior,dynamic mechanical properties and heat-resistance performance were compared with PP/PP-g-MAH/CaCO_3 composite. Results show that surface polarity of the modified CaCO_3 and the interfacial tension between CaCO_3 and PP fall down,but the compatibility improve after CaCO_3 having been modified through in-situ solid phase graft copolymerization. At the same time,PPW on CaCO_3 surface can weaken the heterogeneous nucleation effect to CaCO_3,but it prompts to form the appropriate interfacial bonding which is benefit the improvement of toughness. Results also reveal that good dispersion of CaCO_3-MAH-PPW can reduce the winding of PP molecular chain,and improve the molecular flexibility resulting the decline of glass temperature. PP-g-MAH can help improve the crystallization temperature of PP/PP-g-MAH/CaCO_3 composite,and form strong interfacial bonding between CaCO_3 and PP,as well as to increase the modulus,strength and heat resistant performance of the composite.
PP/CaCO_3-MAH-PPW composite was prepared by means of in-situ solid phase graft copolymerization using maleic anhydride( MAH) and polypropylene wax( PPW) as the main raw materials. The surface properties of the modified CaCO_3 were analyzed. Its crystallization behavior,dynamic mechanical properties and heat-resistance performance were compared with PP/PP-g-MAH/CaCO_3 composite. Results show that surface polarity of the modified CaCO_3 and the interfacial tension between CaCO_3 and PP fall down,but the compatibility improve after CaCO_3 having been modified through in-situ solid phase graft copolymerization. At the same time,PPW on CaCO_3 surface can weaken the heterogeneous nucleation effect to CaCO_3,but it prompts to form the appropriate interfacial bonding which is benefit the improvement of toughness. Results also reveal that good dispersion of CaCO_3-MAH-PPW can reduce the winding of PP molecular chain,and improve the molecular flexibility resulting the decline of glass temperature. PP-g-MAH can help improve the crystallization temperature of PP/PP-g-MAH/CaCO_3 composite,and form strong interfacial bonding between CaCO_3 and PP,as well as to increase the modulus,strength and heat resistant performance of the composite.
引文
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[3] PUSTAK A,DENAC M,EKAPIN A S,et al. Mechanical and rheological properties of silica-reinforced polypropylene/m-EPR blends[J]. Journal of Polymer Research,2016,23(7):1-13.
[4] ZHU P,CHEN J,WU C. Crystallization behavior and mechanical properties of polypropylene/modified carbon black com-posites[J]. Polymer Composites,2009,30(4):391-398.
[5] LIN Y,CHEN H,CHAN C M,et al. Nucleating effect of calcium stearate coated Ca CO3nanoparticles on polypropylene[J]. Journal of Colloid&Interface Science,2011,354(2):570-576.
[6] PEREZ E,BERNAL C,PIACQUADIO M. Multifractal analysis of tensile toughness and filler dispersion for polypropylene-Ca CO3composites[J]. Applied Surface Science,2012,258(22):8940-8945.
[7]生瑜,朱德钦,王剑峰.一种经表面改性制备具有“核-壳”结构的无机粉体的方法:中国,200710144038. 6[P],2007-12-18.
[8]生瑜,朱德钦,王剑峰,等. Ca CO3表面包覆改性及其对填充PP力学性能的影响[J].高分子学报,2008(8):813-817.
[9]朱德钦,生瑜,邹寅将,等.不同改性剂对聚丙烯/碳酸钙复合材料性能的影响[J].应用化学,2013,30(6):655-660.
[10]朱德钦,生瑜,邹寅将,等.原位固相接枝Ca CO3/聚丙烯复合材料中界面相互作用与力学性能的关系[J].高分子材料科学与工程,2013,29(11):31-35.
[11] VAN Krevelen D W,HOFTYZER P J. Properties of polymers,their estimation and correlation with chemical structure[M]. New York:Elsevier Scientific Pub Co,1976:121-127.
[12] WU S. Polymer interface and adhesion[M]. New York:Marcel Dekkar,1982:102-106.
[13]张良均,童身毅,樊庆春.马来酸酐接枝聚丙烯增容聚丙烯/碳酸钙复合物力学性能与增容机理[J].塑料工业,2004,32(7):36-38.
[14]王玉海,章自涛,沈浩.纳米Ca CO3/相容剂/PP中的界面相互作用研究[J].高分子学报,2010(12):1444-1450.
[15] LUIS I,DAVID P. Dynamic properties of thermoplastics butadiene-styrene(SBS)and oxidized short carbon fiber compos-ites materials[J]. Journal of Applied Polymer Science,1998,67(10):1819-1826.
[16] ASHIDA M,NOGUCHI T,MASHIMO S. Effrct of matrix's type on the dynamic properties for short fiber elastomer com-posite[J]. Journal of Applied Polymer Science,1985,30(3):1011-1021.
[17]邹寅将.原位固相接枝改性碳酸钙在聚丙烯复合材料中的应用[D].福州:福建师范大学,2013.