超声辐照作用下PP/POE/SiO_2复合材料结构与性能研究
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摘要
本论文采用聚烯烃弹性体(POE)增韧聚丙烯(PP)，用偶联剂(单一处理与复合处理)对纳米SiO_2进行表面处理以及在经过预处理的纳米SiO_2表面通过乳液聚合接枝上丙烯酸乙酯制成纳米SiO_2／PEA复合粒子，并加入增容剂PP-g-MA，在超声辐照作用下制备了PP／POE、PP／POE／SiO_2、PP／POE／PP-g-MA／SiO_2共混复合体系，研究了在上述不同条件下制备的聚丙烯复合体系的力学性能、结晶性能、弹性体粒子和纳米SiO_2粒子在复合体系中的分散状况以及超声辐照作用下PP／POE共混体系的挤出流变行为，用FTIR和XPS讨论了纳米SiO_2／PEA复合粒子中丙烯酸乙酯在纳米SiO_2表面的接枝反应。
对超声辐照作用下PP／POE共混体系的研究结果表明，PP／POE共混物熔体的表观粘度和口模压力随超声功率的增大而降低。超声辐照能减小分散相POE粒子的尺寸，使分散更均匀，提高与PP的相容性。适宜功率的超声辐照对POE增韧PP能起到协同增韧的效果，而这种效果在脆韧转变前表现更加明显。POE的加入和超声辐照均阻碍了PP的结晶，POE的加入对PPβ晶的生成有一定的诱导作用。
对不同表面处理的纳米SiO_2填充体系的研究结果表明，适当的超声功率辐照可以提高复合体系的冲击强度，断裂伸长率。添加增容剂PP-g-MA后，复合体系的冲击强度、屈服强度均得到提高，但断裂伸长率降低。纳米SiO_2能提高PP／POE／SiO_2复合材料的结晶温度，添加增容剂后，结晶温度得到进一步提高。由偶联剂复合处理的纳米SiO_2填充的PP／POE／SiO_2三元体系，其DSC曲线出现β晶峰，随增容剂的加入，β晶峰消失。纳米SiO_2的加入使PP球晶尺寸变小、晶粒细化，超声辐照、增容剂的加入使得球晶尺寸进一步变小、晶粒进一步细化。
通过乳液聚合可以成功地将EA接枝到预处理的纳米SiO_2表面上，制成纳米SiO_2／PEA复合粒子，由其填充的PP／POE／SiO_2复合体系，在纳米SiO_2含量4wt％时，冲击强度达到最大值，而此时其DSC曲线上的β晶峰的强度最强。这种处理的纳米SiO_2在PP／POE／SiO_2复合体系中的分散尺寸，分布均匀程度都好于偶联剂处理的。
In this paper, a polyolefin elastomer (POE) was selected to toughenpolypropylene (PP). The surface of nano-SiO_2 was modified with the couplingagent. The nano-SiO_2/PEA hybrids were prepared via emulsion polymerization.With the addition of the compatilizer (PP-g-MA), the PP/POE blends and thePP/POE/SiO_2 as well as PP/POE/PP-g-MA/SiO_2 composites were prepared duringextrusion under ultrasonic irradiation. The mechanical properties, crystallizationproperties and morphology of PP composites were studied and the rheologicalbehavior of PP/POE blends also was investigated. Through FTIR and XPS, thegrafting reaction of EA onto the surface of nano-SiO_2 for the nano-SiO_2/PEAhybrids was discussed.
According to the results of the PP/POE blends under ultrasonic irradiation,the apparent viscosity of the PP/POE blends melt and the die pressure decreasewith increasing the ultrasonic intensity. The ultrasonic irradiation can enhance thecompatibility between PP and POE, reduce the size of POE particles and improvethe dispersion of POE in PP matrix. Appropriate ultrasonic irradiation and POEhave the synthetic effects on toughening PP. And the effects show moreremarkably before the brittle-ductile transition. Both POE and the ultrasonicirradiation control the crystallization behaviors of PP, and the addition of POE caninduce the formation ofβ-crystal.
For the PP composites with nano-SiO_2 modified by the different treatments,appropriate ultrasonic irradiation can increase the izod-notched impact strengthand the elongation at break of the composites. The izod-notched impact strengthand the yield strength of the composites are further improved with the addition ofthe compatilizer whereas the elongation at break decreases. Compared with thePP/POE blends, the crystallization temperature of PP/POE/SiO_2 composites isincreased. The addition of the compatilizer further improves the crystallizationtemperature of PP/POE/SiO_2 composites. The melting peak ofβ-crystal occurs inDSC curves for PP/POE/SiO_2 composites with nano-SiO_2 modified with KH-550and NDZ-201. With adding the compatilizer, the melting peak ofβ-crystaldisappears. The spherulite size of PP is reduced and the spherulite is fined withthe addition of nano-SiO_2. The introduction of ultrasonic irradiation or thecompatilizer can strengthen this effect.
Ethyl acrylate can be grafted successfully onto the surface of the pretreatednano-SiO_2 via emulsion polymerization and the nano-SiO_2/PEA hybrids preparedare used to modify the PP/POE blends. The izod-notched impact strength and thepeak intensity ofβ-crystal in DSC curves for PP/POE/SiO_2 compsoties reach themaximum value with 4wt% SiO_2. The dispersion of the nano-SiO_2/PEA hybrids inPP/POE/SiO_2 composites is better than that of SiO_2 treated with the couplingagent.
对超声辐照作用下PP／POE共混体系的研究结果表明，PP／POE共混物熔体的表观粘度和口模压力随超声功率的增大而降低。超声辐照能减小分散相POE粒子的尺寸，使分散更均匀，提高与PP的相容性。适宜功率的超声辐照对POE增韧PP能起到协同增韧的效果，而这种效果在脆韧转变前表现更加明显。POE的加入和超声辐照均阻碍了PP的结晶，POE的加入对PPβ晶的生成有一定的诱导作用。
对不同表面处理的纳米SiO_2填充体系的研究结果表明，适当的超声功率辐照可以提高复合体系的冲击强度，断裂伸长率。添加增容剂PP-g-MA后，复合体系的冲击强度、屈服强度均得到提高，但断裂伸长率降低。纳米SiO_2能提高PP／POE／SiO_2复合材料的结晶温度，添加增容剂后，结晶温度得到进一步提高。由偶联剂复合处理的纳米SiO_2填充的PP／POE／SiO_2三元体系，其DSC曲线出现β晶峰，随增容剂的加入，β晶峰消失。纳米SiO_2的加入使PP球晶尺寸变小、晶粒细化，超声辐照、增容剂的加入使得球晶尺寸进一步变小、晶粒进一步细化。
通过乳液聚合可以成功地将EA接枝到预处理的纳米SiO_2表面上，制成纳米SiO_2／PEA复合粒子，由其填充的PP／POE／SiO_2复合体系，在纳米SiO_2含量4wt％时，冲击强度达到最大值，而此时其DSC曲线上的β晶峰的强度最强。这种处理的纳米SiO_2在PP／POE／SiO_2复合体系中的分散尺寸，分布均匀程度都好于偶联剂处理的。
In this paper, a polyolefin elastomer (POE) was selected to toughenpolypropylene (PP). The surface of nano-SiO_2 was modified with the couplingagent. The nano-SiO_2/PEA hybrids were prepared via emulsion polymerization.With the addition of the compatilizer (PP-g-MA), the PP/POE blends and thePP/POE/SiO_2 as well as PP/POE/PP-g-MA/SiO_2 composites were prepared duringextrusion under ultrasonic irradiation. The mechanical properties, crystallizationproperties and morphology of PP composites were studied and the rheologicalbehavior of PP/POE blends also was investigated. Through FTIR and XPS, thegrafting reaction of EA onto the surface of nano-SiO_2 for the nano-SiO_2/PEAhybrids was discussed.
According to the results of the PP/POE blends under ultrasonic irradiation,the apparent viscosity of the PP/POE blends melt and the die pressure decreasewith increasing the ultrasonic intensity. The ultrasonic irradiation can enhance thecompatibility between PP and POE, reduce the size of POE particles and improvethe dispersion of POE in PP matrix. Appropriate ultrasonic irradiation and POEhave the synthetic effects on toughening PP. And the effects show moreremarkably before the brittle-ductile transition. Both POE and the ultrasonicirradiation control the crystallization behaviors of PP, and the addition of POE caninduce the formation ofβ-crystal.
For the PP composites with nano-SiO_2 modified by the different treatments,appropriate ultrasonic irradiation can increase the izod-notched impact strengthand the elongation at break of the composites. The izod-notched impact strengthand the yield strength of the composites are further improved with the addition ofthe compatilizer whereas the elongation at break decreases. Compared with thePP/POE blends, the crystallization temperature of PP/POE/SiO_2 composites isincreased. The addition of the compatilizer further improves the crystallizationtemperature of PP/POE/SiO_2 composites. The melting peak ofβ-crystal occurs inDSC curves for PP/POE/SiO_2 composites with nano-SiO_2 modified with KH-550and NDZ-201. With adding the compatilizer, the melting peak ofβ-crystaldisappears. The spherulite size of PP is reduced and the spherulite is fined withthe addition of nano-SiO_2. The introduction of ultrasonic irradiation or thecompatilizer can strengthen this effect.
Ethyl acrylate can be grafted successfully onto the surface of the pretreatednano-SiO_2 via emulsion polymerization and the nano-SiO_2/PEA hybrids preparedare used to modify the PP/POE blends. The izod-notched impact strength and thepeak intensity ofβ-crystal in DSC curves for PP/POE/SiO_2 compsoties reach themaximum value with 4wt% SiO_2. The dispersion of the nano-SiO_2/PEA hybrids inPP/POE/SiO_2 composites is better than that of SiO_2 treated with the couplingagent.
引文
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3. 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
4. Mertz E H, Traylor P A. J. Appl. Polym. Sci., 1956, 22:325～334
5．何曼君，陈维孝，董西侠。高分子物理，上海：复旦大学出版社，1990，306～308
6. Newman S, Strella S. J. Appl. Polym. Sci., 1965 (9): 2297～2304
7. Strella S. J. Polym. Sci., A2, 1996 (3): 527～534
8. Bucknall C B. Toughened Plastics, London: Applied Science Publishers: 1977
9. Jang B Z. J. Appl. Polym. Sci., 1984, 29:3409～3415
10. R.A.Pearson, A.R Yee, Toughening mechanisms in elastomer-modified epoxies, d. Mater. Sci., 1986, 21(7): 2475～2488
11. Alla M, Wu S. Polymer, 1988, 29:2170～2175
12. William Y H, Wu S. Polym. Eng. & Sci., 1993, 33:292～234
13. Wu S H, Phase structure and adhesion in polymer blends: A criterion for rubber toughening, Polymer, 1985, 26:1855～1864
14. S. H. Wu, A. Margolina, Percolation model for brittle-tough transition in nylon/rubber blends. Polymer, 1988 (29): 2170～2175
15. A. Margolina, S. H. Wu, Comments Percolation model for brittle-tough transition in nylon/rubber blends. Polymer, 1990 (31): 972
16. S. H. Wu, Y. H. William. The origin of Chain Entanglement: Correlations Between Entanglement and Chain Structure. Polym. Eng. & Sci., 1993 (33): 229
17．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，塑料，2002，31(2)： 47～50
18. Kurauchi, T. Ohta, T. Energy Absorption in Blends of Polycarbonate with ABS and SAN. J. Mat. Sci., 1984,19(5): 1699-1709
19．李风岭，王建民，侯斌等，刚性粒子增韧聚氯乙稀的研究现状，现代塑料加上与应用，1999．11(2)：46～50
20. Long YU, Shanks RA, PP-elastomer-filler hybrids: 1. Processing, microstructure and mechanical properties, J. Appl. Polym. Sci., 1986(61): 1877～1885
21. Rong MZ, Ji QL, Zhang MQ, Klaus F, Graft polymerization of vinyl monomers onto nanosized alumina particles, European Polymer Journal, 2002(38): 1573～1582
22．王坷，徐布衣，曾汉民。PP／POE／BaSO4三相复合体系的形态控制和力学性能的研究[J]．高分子材料科学与工程，2002，18(2)：165～173
23．欧玉春，方晓萍，冯宇鹏。高性能无机粒子填充聚丙烯／三元乙丙橡胶复合材料[J]．高分子学报，1996(5)：601～606
24. Hammer C O, MaurerF H J, MolnarSetal et.al, Journal of Material Science, 1999, 34: 5911～5918
25. Long Y, Shanks R A. Journal of Applied Polymer Science, 1999, 61: 1877～1885
26. Homsby P R, Premphet K. Journal of Applied Polymer Science, 1998, 70:587～597
27. Jancar J, Dibenedetto A T. The mechanical properties of temary composites of polypropylene with inorganic fillers and elastomer inclusions[J]. Journal of Material Science, 1994, 29(17): 4651～4658
28．刘英俊，聚丙烯塑料改性及应用进展。工程塑料应用，1995，23(5)：49
29. T. J. Mason ed., Chemistry with Ultrasound, Elsevier Applied Science, London and New York, 1991
30. J. Blitz, "Fundamentals of Ultrasonics," 2nd ed., Chap. 8, Butterworth, London, 1967.
31. S. I. Khamad, E. N. Popova and Z. I. Salina, et al., Deposited Doc. (RUSS), VINITI 1829 (1984); From CA, 103 (2), 7358(1985)
32. S. L. Peshkovskii, M. L. Fridman and A. I. Tukachinskii, et al., Polymer Composites, 4 (2), 126 (1983)
33．陈光顺，李云涛，郭少云，李惠林，1999年全国功率超声会议论文集，中国无锡，1999
34．李云涛，博士学位论文，四川大学，成都，2000
35. A. I. Isayev, J. Chen and A. Tukachinsky, Rubber Chemistry and Technology, 68 (2), 267 (1995).
36. A. I. Isayev, S. P. Yushanov and J. Chen, J. Appl. Polym. Sci., 59 (5), 803 (1996).
37．张云灿，李惠林，高分子材料科学与工程，18(2)，159(2002)
38. Sung K. Byon and Jae R. Youn, Polymer Engineering and Science, 30 (3), 147 (1990)
39. A. I. Isayev and S. Mandelbaum, Polymer Engineering and Science, 31 (14), 1051 (1991)
40. A. K. Panov, I. N. Dorokhov, T. V. Shulaeva, and V. V. Kafarov, Doklady Akademii Nauk USSR, 301 (1), 155 (1988)
41．李云涛，郭少云，陈光顺，李惠林，高分子材料科学与工程，15(6)，142(1999)
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