摘要
聚丙烯(PP)复合化是实现聚丙烯高性能化的重要途径，本文受陕西省自然科学基金研究项目资助，针对PP/弹性体二元复合体系增韧时造成刚性大幅度下降以及PP/无机刚性粒子二元复合体系增韧效果差等问题，采用PP/POE/CaCO_3三元复合体系进行PP的增韧改性研究。重点探讨了CaCO_3粒子表面处理及其表征，以及PP/POE/CaCO_3三元复合体系的微观结构形貌与宏观力学性能。其目的是在三元复合体系中获得良好的弹性体包覆无机刚性粒子的“核-壳”结构，从而使得三元体系较二元体系具有更好的增韧与增强效果。
本论文通过溶液法制备出了POE-g-MAH柔性界面层包覆CaCO_3，采用反气相色谱(IGC)、红外光谱(FTIR)研究了CaCO_3粒子表面处理后所产生的吸附作用、表面化学反应以及表面自由能变化，采用双螺杆挤出造粒制备了不同的PP复合材料，通过注射成型出了标准试件，并进行了宏观力学性能的测试，通过扫描电镜(SEM)进行了PP三元复合体系微观结构形貌的观测。
本论文主要成果为：
采用IGC方法对CaCO_3表面处理前后进行分析表征，并对其表面自由能色散组分进行研究。结果表明表面偶联处理以及界面层设计可以缓和其色散组分随温度的变化，改善CaCO_3的分散性以及与聚合物的相容性，并可推算出钛酸酯类偶联剂(NDZ101)单分子层含量约为1.9wt％。
相比于CaCO_3偶联处理后在其表面产生的简单物理吸附分子层，柔性界面层POE-g-MAH能够和CaCO_3粒子之间产生化学反应，形成弹性体包覆层，促使PP/POE-g-MAH/CaCO_3三元体系中“核-壳”包覆结构的形成。
PP/POE-g-MAH/CaCO_3具有优于PP二元复合体系以及PP/POE/CaCO_3三元复合体系的增韧效果，在配比为(55/15/30)时，其缺口冲击强度提高到17.82KJ/m~2，约为纯PP体系的3倍，且该体系强度和刚性降低程度很小。说明了包覆结构较独立分散结构更有利于体系的增韧。
通过对三元复合体系断裂表面的SEM观测并结合了空洞化增韧机理研究发现，相比于PP/POE/CaCO_3三元复合体系呈现出平滑的断裂表面特征，PP/POE-g-MAH/CaCO_3体系具有明显的韧性断裂特征。
Preparation of Polypropylene composites is one of the main methods to realize high properties of PP. As both PP/elastomer and PP/inorganic rigid particles binary composites couldn't enhance the toughness and strength of PP together, this paper, which is sponsored by Shaanxi Province Science Fund, amis at improving the toughness of PP plastics. The surface modification of inorganic rigid particles and its characterization were studied. The relationship between the structure and properties of PP/elastomer/CaCO_3 ternary composites was also discussed. The main purpose of this paper is to improve the toughness and strength of PP ternary composites via the elastomer/particles core-shell encapsulation morphology.
In this paper, a novel kind soft interface layer POE-g-MAH was prepared through solution method. FTIR and IGC technology were used to study the surface reaction and surface energy change of CaCO_3 after surface modification. PP composites were prepared by the twin screw extrusion and molding process and then the mechanical properties and morphology of PP ternary composites were investigated by the mechanical performance test and SEM technology respectively.
The main conclusions of this paper are as follows:
The characterization of CaCO_3 before and after surface modification and its dispersive component of the surface energy were studied by IGC. The results indicated that the change of the dispersive component of the surface energy as increasing temperature became stable when with coupling agents or POE-g-MAH, which improved the dispersion of rigid fillers and the compatibility between CaCC>3 and polymer. It could also be deduced from the IGC results that the monolayer coverage is around 1.9% for the CaCO_3 treated with titanate coupling agents NDZ101.
Compared to the physical absorption layer on CaCO_3 surface by the coupling agents, there was obvious chemical reaction between POE-g-MAH and CaCO_3 via FTIR, which resulted the elastomer encapsulation layer and the core-shell structure in the PP/POE-g-MAH/CaCO_3 ternary composites.
The mechanical performance tests indicated that PP/POE-g-MAH/PP system had a much better toughness than PP binary composites or other PP/POE/CaCO_3 systems. The Izod notched impact strength of PP/POE-g-MAH/CaCO_3 system (55/15/30)
引文
[1] 赵敏，高俊刚，邓奎林等．改性聚丙烯新材料，北京，化学工业出版社，2002．8
[2] 杨维红．聚丙烯发展状况[J]．国内外石油化工快报，2004，34(2)：1-5
[3] 张克惠主编．塑料材料学．西北工业大学出版社，2000．5
[4] 惠雪梅，张炜，王晓洁．聚丙烯增韧改性研究进展[J]．化工新型材料，2003，31(8)：6-10
[5] 方治齐，唐龙祥，严满清等．聚丙烯改性新进展[J]．现代塑料加工应用，2002，14(6)：36-39
[6] 敖玉辉，孙伟权，杨海东等．不同弹性体增韧聚丙烯的研究[J]．中国塑料，2005，19(10)：53-56
[7] 谈华平．PP的共混改性研究进展[J]．广东塑料，2004(1)：52-59
[8] 常平，洪重奎．乙丙橡胶增韧聚丙烯共混物中橡胶相形态[J]．塑料科技，2002，(1)：4-6
[9] 李艳霞，刘建军。加相容剂的聚丙烯汽车仪表盘专用料的研制[J]．工程塑料应用，2001，29(6)：8-10
[10] 彭学成．杜邦陶氏Engage弹性体POE及其应用[J]．橡胶工业，2003(8)：501-504
[11] 张金柱．新型热塑性弹性体POE的性能及其在PP增韧改性中的应用[J]．塑料科技，1999(2)：5-7
[12] 邱桂学，吴人洁，王展旭．茂金属聚乙烯弹性体和二元乙丙橡胶增韧聚丙烯的比较[J]．合成橡胶工业，2001，24(6)：354-357
[13] 李馥梅．新型抗冲击改性剂茂金属乙烯-1-辛烯共聚物的特性及应用[J]．中国塑料，2003，17(2)：15
[14] Kurauchi T, Ohta T. Energy absorption in blends of polycarbonate with ABS and SAN[J]. J Mat Sci,1984,19:1699-1709
[15] 欧玉春，方晓萍，郭庭泰等．高性能聚合物/刚性粒子复合材料制备的新技术[J]．工程塑料应用，2001，21(12)：8-11
[16] 吴永刚，马懿，李敬泽等．无机刚性粒子增韧PP的研究[J]．中国塑料，1999(4)：29
[17] 王珂，徐布衣，曾汉民．PP/POE/BaSO_4三相复合体系的形态控制和力学性能的研究．高分子材料科学与工程，2002，18(2)：165-167
[18] 郭涛，王炼石，何一帆．聚丙烯/弹性体/无机刚性粒子三元复合材料的研究进展[J]．塑料，2004，33(1)：36-40
[19] Stamhuis J E. Mechanical properties and morphology of polypropylene composites: Ⅱ Short glass fiber reinforced elastomer modified polypropylene[J]. Polym Comps, 1998,9(4): 280
[20] Kolarik J, Jancar J. Ternary composites of polypropylene/elastomer/calcium carbonate: Effect of functionalized components on phase structure and mechanical [J].Polymer, 1992, 33(23):4961-4967
[21] Long Y.U., Shanks R.A. PP- elastomer-filler hybrids. Ⅰ. Processing, microstructure and mechanical properties [J].J Appl Polym Sci, 1996, 61: 1877-1885.
[22] Long Y.U., Shanks R.A. PP-elastomer-filler hybrids. Ⅱ. Morphologies and fracture, J.Appl.Polym.Sci., 1996,62:639-646
[23] Pukanzky B, Turczanyi B, Tudos F.Composites Dependence of Tensile Yileld Stress in Filled Polymers[J]. J. Master.Sci.Lett., 1988,7:160-162
[24] Jancar J, Kucera J. Yield Behavior of Polypropylene Filled with CaCO_3 and Mg(OH)_2-Ⅰ. "Zero" Interfacial adhension [J].Polym.Eng.Sci., 1990,30:707-713
[25] Jancar J, Kucera J. Yield Behavior of PP/CaCO_3 and PP/Mg(OH)_2 Composites-Ⅱ. Enhanced Interfacial Adhesion. [J].Polym.Eng. Sci., 1990,30:714-720.
[26] 吴培熙，张留城编．聚合物共混改性．北京：轻工业出版社，1996
[27] 石智强，刘晓蕾，刘孝波．有机/无机纳米粒子复合材料研究进展[J]．合成化学，2004(3)：251-255
[28] 孟季茹，梁国正，秦华宇等．刚性粒子增韧增强聚合物的研究概况[J]．塑料，2002，31(2)：46-50
[29] 史学涛，张广成，陈挺等．无机刚性粒子增韧增强聚丙烯研究进展[J]．中国塑料，2005，19(11)：6-11
[30] Bramuzzo M, Savadori A, Bacci D. Polypropylene composites: Fracture mechanics analysis of impact strength [J]. Polymer Composites, 1985 (6):1-8
[31] 欧玉春，方晓萍，郭庭泰等．刚性粒子增强增韧聚合物复合材料的制备新技术[J]．材料研究学报，2001，15(1)，110-116
[32] 黄锐，王旭，张玲等．熔融共混法制备聚合物/纳米无机粒子复合材料[J]．中国塑料，2003，17(4)：20-23
[33] 黄锐，陈晓媛．高速混合机的应用及研究进展[J]．中国塑料，2001，15(7)：11-14
[34] 傅强，王贵恒，刘春晓．HDPE/CaCO_3共混物中的”芯-壳”模型[J]．高分子材料科学与工程，1993(3)：120～125
[35] Jancar J, Dianselmo A, Dibenedetto A T The yield strength of particulate reinforced thermoplastic composites[J]. Polym. Eng. Sci., 1992,32:1394～1399.
[36] 乔放，朱晓光，关淑敏等．硅灰石增韧聚合物的界面粘接判据[J]．高分子材料科学与工程，1996，12(16)：63-67
[37] 吕素平，朱晓光，漆宗能．聚合物共混体脆韧转变的损伤竞争理论：基体性能对脆韧转变的影响[J]．高分子材料科学与工程，1996，12(15)：61-66
[38] 吕素平，朱晓光，刘浙辉．聚合物共混体脆韧转变的损伤竞争理论：分散相形态和界面粘接对脆韧转变的影响[J]．高分子材料科学与工程，1996，12(16)：9-15
[39] Turcsanyi B, Pukanszky B, Tados F. Composition dependence of tensile yield stress in filled polymers[J]. J Mater Sci Lett, 1988,7:160～162
[40] Pukanszky B. Particulate-filled polypropylene: structure and properties. In: Karger-Krocsis J, ed.Polypropylen Structure, Blends and Composites, Vol.3.New York: Chapman & Hall Press, 1995
[41] Wu.S. Phase structure and adhension in polymer blends: A criterion for rubber Toughening [J]. Polymer, 1985, 26:1855-1863
[42] Wu.S.A generalized criterion for rubber toughening: The critical matrix ligament thickness [J]. J.Appl.Polym.Sci, 1988, 35, 549-561.
[43] 朱晓光，漆宗能．聚合物增韧研究进展[J]．材料研究学报，1997，6：623-638
[44] 於莉莉，于经元，康仕芳．碳酸钙粉末的表面改性[J]．天津化工，2000(3)：11-13
[45] 马进，邓先和，潘朝群．纳米碳酸钙表面改性研究进展[J]．橡胶工业，2006(6)：377-341
[46] 施辉忠．以有机酸与有机酸盐作填料处理剂的研究[J]．聚氯乙烯，1989(4)：17～24
[47] Okayama. Rubber Chemistry and Technology, 1992(28): 107～114
[48] Nakatsuka T.; Kawasaki H.; Itadani K.; Yamashita S.Phosphate Coupling Agents for Calcium-Carbonate Filler.[J]. Appl Polym Sci 1982, 27, (1), 259-269
[49] Shinzi, Yamsshita.[J]. J Collid and interf Sciu, 1981(82):348～359
[50] Jeanette González, Carmen Albano, Miren Ichazo, Berenice Diaz. Effect of coupling agents on mechanical and morphological behavior of the PP/HDPE blend with two different CaCO_3[J]. European polymer journal, 2002(38): 2465-2475.
[51] Bajaj P, Jha NK, Jia RK. Effect of titanate coupling agent on mechanical properities of mica-filled polypropylene [J]. Polym Eng Sci 1989, 29(8): 557-563.
[52] Wang Y, Huang JS. Single screw extrusion compounding of particulate filled thermoplastics: State of dispersion and its influence on impact properties [J]. J Appl Polym Sci 1996(60): 1779-1791.
[53] Qing-Xin Zhang, Zhong-Zhen Yu, Xiao-Lin Xie, Yiu-Wing Mai. Crystallization and impact energy of polypropylene/CaCO3 nanocomposites with noninic modifier[J]. Polymer 2004(45): 5985-5994
[54] G.-X. Wei, H.-J. Sue, J. Chu, C.Huang, K.Gong. Toughening and strengthening of polypropylene using the rigid-rigid polymer toughening concept: Part Ⅰ.. Morphology and mechanical property investigations [J]. Polymer 2000(41): 2947-2960.
[55] Matonis V A, Small N C. A macroscopic analysis of composites containing layered spherical inclusions [J]. Polym Eng Sci, 1969 (9): 99-100.
[56] 欧玉春．刚性粒子填充聚合物的增韧增强与界面相结构[J]．高分子材料科学与工程，1998，14(2)：12-15
[57] Kolarik J, Jancar J. Ternary composites of polypropylene/elastomer/calcium carbonate: Effect of functionalized componets on phase structure and mechanical properties[J]. Polymer, 1992, 33(23):4961-4967
[58] Mertz E H, Claver G C, Baer M. J. Studies on heterogeneous polymeric systems. Polym.Sci., 1956(22):325-334.
[59] Bucknall C B, Smith R P. Stress-whitening in high-impact polystyrene. Polymer, 1965(6):437-442
[60] Newman S, Strella S. J. Stress-strain behavior of rubber-rein forced glassy polymers. J. Appl. Polym. Sci., 1965(9):2297～2304.
[61] Jang B Z, Uhlmann D R, Vander S J B. Crystalline morphology of polypropylene and rubber modified polypropylene[J]. J Appl Polym Sci, 1984(29):4377-4393
[63] William Y H, Souheng Wu. Percolation behavior in morphology and modulus of polymer blends. Polym Eng & Sci, 1993(33): 292-302
[64] Alla Margolina, Souheng Wu. Percolation model for brittle-tough transition in nylon/rubber blends [J]. Polymer, 1988, 29(12):2170-2181
[65] Kurauch T, Ohta T. Application of mineral particles in electric industry[J]. J Mater Sci, 1984(19): 1699-1702
[66] Pukanszky B, Todos F. Polym Eng Sci,1995,35(24):1962
[67] 李东明，漆宗能．碳酸钙增强聚丙烯复合材料的断裂韧性[J]．高分子材料科学与工程，1991(2)：18-25
[68] Fu Q, Wang G, Liu C. Morphology and Tensile Properties of Glass Bead Filed Lowdensity PP Composite [J,]. Polymer, 1995,36(12) :2397-2401
[69] Jancar J, DiBenedetto A, Dianselmo A. Polym Eng Sci,1993,33:559-563
[70] 吕素平，朱晓光，漆宗能．聚合物共混体脆韧转变的损伤竞争理论(Ⅱ)．基体性能对脆韧转变的影响[J]．高分子材料科学与工程，1996，12(5)：61-65
[71] 廖凯荣，陈学信，卢泽俭等．复合材料的拉伸断裂韧性[J]．高分子材料科学与工程，1997，13(2)：48-53
[72] McGenity P, Paynter C, Adams J. Filplas'89, BPF/PRIConf, 1989, Manchester
[73] Darlington M, Hutley T. Polym Commun, 1985(26): 264
[74] Takashi Inoue, Takayuki Kojima. Toughening mechanism in a ternary alloy: PBT/PC/rubbersystem [J]. Polymer1993, 34(23):4868-4876.
[75] Qi-Zhi Wang, Dong-Joo Lee. Predictive modelling for rubber-toughened polymers [J]. Mechanics of Materials, 1999 (31):705-716.
[76] Matja Denac, Ivan mit, Vojko Musil. Polypropylene/talc/SEBS (SEBS-g-MA) composites. Part Ⅰ: Structure [J]. Composites: PartA, 2005,36 (8):1094-1101.
[77] Matja Denac, Ivan mit, Vojko Musil. Polypropylene/talc/SEBS (SEBS-g-MA) composites. Part Ⅱ: Mechanical properties [J]. Composites: PartA, 2005, 36(9): 1282-1290.
[78] Ichazo M, González J, Albano C, Rosalea C, Prerea R, Nava R.Mechanical behavior of PP/HDPE/EPR blends with calcium carbonate[A]. In: the Annual Technical Conference of the Society of Plastics Engineers (SPE)1998: Plastics on My Mind, Volume 3:3503-3506.
[80] K.Premphet, P.Hornont. Phase sturcture of ternary polypropylene/elastomer/filler composites: effect of elastomer polarity[J]. Polymer, 2000, 41 (26):9283-9290.
[81] Sz.Molnár, B.Pukánszky, C.O.Hammer, F.H.J.Maurer. Impact fracture study of multicomponent polypropylene composites[J]. Polymer, 2000, 41(4):1529-1539.
[82] C.W.Liauw, G.C.Lees, S.J.Hurst, R.N.Rothon and S.All. Effect of silane-baced filler surface treatment formulation on the interfacial properties of impact modified polypropylene/magnesium hydroxide composites[J]. Composite: Part A, 1998 (29A):1313-1318.
[83] Dirk Kaempfer, Ralf Thomann, Rolf Mülhaupt. Melt compounding of syndiotactic polypropylene nanocomposites containing oragnophilic layered silicates and in situ formed core/shell[J]. Polymer, 2002(43):2909-2916.
[84] 卢锡年，张芮．颗粒填充复合材料强韧化效应的力学分析[J]．力学学报，1995，27(5)：619-623
[85] 吕素平，漆宗能．聚合物共混体脆韧转变的损伤竞争理论(Ⅰ)——损伤竞争准数与脆韧转变判据[J]．中国科学B辑，1994，24(10)：1028-1034
[86] 吕素平，朱晓光，漆宗能．聚合物共混体脆韧转变的损伤竞争理论(Ⅱ)——基体性能对脆韧转变的影响[J]．高分子材料科学与工程，1996：12(5)：61～65
[87] 吕素平，朱晓光，刘浙辉，漆宗能．聚合物共混体脆韧转变的损伤竞争理论(Ⅲ)——分散相形态和界面粘接对脆韧转变的影响[J]．高分子材料科学与工程，1996，12(16)：9-14．
[88] Z.H.Liu, X.G.Zhu, Q.Li, Z.N. Qi and F.S. Wang. Effect of morphology on the brittle ductile transition of composites [J]. Polymer, 1998 (39): 1863-1868.
[89] Andrzej Galeski. Strength and toughness of crystalline polymer systems [J]. Progress in polymer science, 2003 (28): 1643-1699.
[90] Y.S.Thio, A.S.Argon, R.E.Cohen, M.Weinberg. Toughening of isotactic polypropylene with CaCO3 particles. Polymer [J], 2002 (43):3661-3674.
[91] D.Metin, F.Tihminlioglu, D.Balkǒse, S.ülkü. The effect of interracial interactions on the mechanical properties of polypropylene/natural zeolite composites [J]. Composites: Part A, 2004 (35):23-32.
[92] Q.Fu, G.H. Wang, J.S.Shen. Polyethylene Toughened by CaCO3 Particle: Bittle-Duetile Transition of CaCO3-toughened HDPE [J]. J.Appl.Polym.Sci, 1993, 49(4): 673～677.
[93] Jancar J., Kucera J.Yield behavior of polyprolene filled with CaCO3 and Mg(OH)_2:zero interfacial adhesion..Polym.Eng.Sci., 1990, 30(12):707～713
[94] H.-J. Sue, J. Huang, A.F. Yee, Interfacial adhesion and toughening mechanisms in an alloy of polycarbonate/polyethylene [J]. Polymer, 1992, 33(22).: 4868-4871.
[95] Ke Wang, Jingshen W U, Liu Ye, Hanmin Zeng. Mechanical properties and toughening mechanisms of polypropylene/barium sulfate composites [J]. Composites: Part A, 2003 (34):1199-1205.
[96] J.Lee, A.F.Yee. Inorganic particle toughening Ⅱ: toughening mechanisms of glass bead filled epoxies[J]. Polymer, 2001(42): 589-597.
[97] S.M.Zebarjad, M.Tahani, S.A.Sajjadi. Influence of filler particles on deformation and fracture mechanism of isotactic polypropylene [J]. Journal of Materials Processing Technology, 2004 (155-156): 1459-1464.
[98] Papirer E, Schultz J and Tirchi C. Surface Properties of a Calcium Carbonate Filler treated with Stearic Acid.European Polymer Journal 1984, 20:155-1158.
[99] Miao Shui. Polymer surface modification and characterization of particulate calcium carbonate filles. Applied Surface Scinece, 2003,220: 359-366.
[100] Doris G M, Gray D G. Adsorption, spreading pressure, and London force interactions of hydrocarbons on cellulose and wood fiber surfaces[J]. J.Colloid Interface Sci. 1979, 71: 93-106.
[101] Prempher K, Horanont P. Phase Structure of Ternary Polypropylene/Elastomer/ Filler Composites: Effect of Elastomer Polarity.Polymer, 2000, 41: 9283-9290.
[102] Zhang Ling, Wang Zhenghua, Li Liangbin, Zhang Xinyuan. PP/Elastomer/Calcium Carbonate Composites Effect of Elastomer and Calcium Carbonate Contents on the Deformation and Impact Behavior. Jounaral of Materials Science, 2002, 37:2615-2621.
[103] 殷敬华，莫志深，现代高分子物理学(上册)，2001，科学出版社
[104] 何曼君 等 编著．高分子物理．上海：复旦大学出版社，1990
[105] W.C.J.Zuiderduin, C.Westzaan, J.Huétink, R.J.Gaymans. Toughening of polypropylene with calcium carbonate particles [J]. Polymer, 2003 (44): 261-275.