煤矸石/SBS复合材料的制备与性能研究
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摘要
煤矸石是采煤和选煤过程中所产生的工业废料,大量排放的煤矸石对环境和人体健康都有一定的危害。本论文采用廉价废弃物煤矸石作原料,通过粉碎筛分,偶联剂表面改性制成了一种高分子聚合物的补强填料,用它对热塑性弹性体-热塑性丁苯橡胶(SBS)进行补强,能够提高SBS的力学性能、耐热性等性能,既可以利用废物,又能降低橡胶制品的价格,具有明显的经济效益和社会效益。
本课题采用硅烷偶联剂、钛酸酯偶联剂和铝酸酯偶联剂对不同粒径的煤矸石进行了表面改性,通过红外光谱、扫描电子显微镜显示在改性后的煤矸石表面覆盖了偶联剂分子,并对偶联机理进行了讨论。
本论文对不同偶联剂改性不同粒径煤矸石/SBS复合材料的性能进行了对比,结果表明,200克SBS添加4mL钛酸酯偶联剂改性20克250目煤矸石复合材料的性能最佳,其中拉伸强度达到11.35Mpa,较纯SBS(6.6Mpa)提高了近2倍,而抗老化性能、耐摩擦性能都有明显提高。热分析表明,煤矸石/SBS复合材料的软化点和初始分解温度均较纯SBS有所提高,其中以钛酸酯偶联剂改性250目煤矸石复合材料最佳。
Coal gangue is an industrial solid waste produced during the processing of coal mining and mineral processing. The coal gangue not only takes up the land of large quantity, but pollutes the circumstance and endanger the health of human body.Using coal gangue as raw material, a kind of new type polymer reinforcing filler for thermoplastic elastomer–polystyrene-butadiene rubber(SBS) has been made by ultra-fine grinding and surface treatment and the properties of mechanics and resisting heat could be improved. Which not only make use of waste material bu also reduce the price of rubber product, and which have economic and social benefits.
The coal gangue were modified with silance coupling agent、titanate alkoxide coupling agent and aluminate coupling agent in this paper. The result showed the surface of coal gangue is covered with organic coupling agent molecular by IR、SEM and the mechanism of coupling is discussed.
The properties of composites different coupling agent modificative coal gangue/SBS were compared in my paper,which indicated the composites of 4mL titanate alkoxide coupling agent modificative 20g 250 eyes coal gangue accessing 200g SBS is the best, the tensile strength achieved 11.35Mpa and it enhanced double than pure SBS. Moreover properties of resisting aging and resisting fuection were enhanced. The thermic analysis showed the intenerated point and decompound temperature of coal gangue/SBS composites enhanced than pure SBS and the composites of titanate alkoxide coupling agent modificative coal gangue is the best.
本课题采用硅烷偶联剂、钛酸酯偶联剂和铝酸酯偶联剂对不同粒径的煤矸石进行了表面改性,通过红外光谱、扫描电子显微镜显示在改性后的煤矸石表面覆盖了偶联剂分子,并对偶联机理进行了讨论。
本论文对不同偶联剂改性不同粒径煤矸石/SBS复合材料的性能进行了对比,结果表明,200克SBS添加4mL钛酸酯偶联剂改性20克250目煤矸石复合材料的性能最佳,其中拉伸强度达到11.35Mpa,较纯SBS(6.6Mpa)提高了近2倍,而抗老化性能、耐摩擦性能都有明显提高。热分析表明,煤矸石/SBS复合材料的软化点和初始分解温度均较纯SBS有所提高,其中以钛酸酯偶联剂改性250目煤矸石复合材料最佳。
Coal gangue is an industrial solid waste produced during the processing of coal mining and mineral processing. The coal gangue not only takes up the land of large quantity, but pollutes the circumstance and endanger the health of human body.Using coal gangue as raw material, a kind of new type polymer reinforcing filler for thermoplastic elastomer–polystyrene-butadiene rubber(SBS) has been made by ultra-fine grinding and surface treatment and the properties of mechanics and resisting heat could be improved. Which not only make use of waste material bu also reduce the price of rubber product, and which have economic and social benefits.
The coal gangue were modified with silance coupling agent、titanate alkoxide coupling agent and aluminate coupling agent in this paper. The result showed the surface of coal gangue is covered with organic coupling agent molecular by IR、SEM and the mechanism of coupling is discussed.
The properties of composites different coupling agent modificative coal gangue/SBS were compared in my paper,which indicated the composites of 4mL titanate alkoxide coupling agent modificative 20g 250 eyes coal gangue accessing 200g SBS is the best, the tensile strength achieved 11.35Mpa and it enhanced double than pure SBS. Moreover properties of resisting aging and resisting fuection were enhanced. The thermic analysis showed the intenerated point and decompound temperature of coal gangue/SBS composites enhanced than pure SBS and the composites of titanate alkoxide coupling agent modificative coal gangue is the best.
引文
[1]蒋爱良.煤矸石的组成特征及利用途径[J].中国煤炭,2000,26(3):25~27
[2]唐晓徽,刘永新.煤矸石的综合利用[J].河北化工,2007,30(4):27~29
[3]刘新,赵晓龙.煤炭开采副产品煤矸石的危害及其治理[J].科技情报开发与经济,2007,17(25):131~132
[4]陈小玲.淮南矿区煤矸石综合利用与途径[J].淮南师范学院学报,2006,8:133~135
[5]曾小梅.我国煤矸石的综合利用现状[J].山东煤炭科技,2005,(2):8~10
[6]李海珍,姜有.煤矸石的综合利用[J].煤炭技术,1999,(10):25~26
[7]石磊,等.煤矸石的综合利用[J].煤化工,2005,(4):15~18
[8]常万林.煤矸石的综合利用[J].河北煤炭,2002,(3):6~8
[9]邵群,等.矸石粉组成及其与橡胶的相容性研究[J].煤炭加工与综合利用,1997,(2):25~27
[10]沁心波、赵鸣.超细煤矸石矿粉作天然橡胶补强填充剂的性能研究,能源环境保护,2004.18(1):27~30
[11]郭玉文.SBS现状及其在塑料改性方面的应用[J].市场研究,2006,6:29~30
[12] E.S.Metzler.New developments in Kraton G thermoplastic elas-tomers[J].Rubber World.1988,10:38~39
[13]李文波,赵艳芬. SBS的化学改性及其[J].应用广东橡胶,2001,8:2~6
[14]韩丙勇,等.二嵌段SB对SBS性能的影响[J].洽成橡胶工业,2002,25(4):245~24
[15] D.C.Huang,R.C.C.Tsiang. Effects of Tetrahydrofuran as a Structure Modifier in Preparation of SBS Thermoplastic Block Copolymer in Cyclohexane [J]. Journal of Applied Polymer Science. 1996,61:333~341
[16] Gregor Radonjie,et al.. Compatibilization of Polypropylene/Polysryrene Blends with Poly(styrene-b-butadience-B-styrene) Block opolymer[J]. Journal of Applied Polymer Science. 1988,69:2625~2639
[17] U.Plawky , et al. The RaleofStyrene-EthylenelButylene-Styrene Triblock Copolymer as Impact Modifier in Palypropylene-Polyethyle-ne Blends[J]. Journal of Applied Polymer Science. 1996,59:1891~1896
[18] Hanqiao Feng, et al. Compatibiiization effect of graft copolymer on immiscible polymerblends.Polymer[J]. 1998,39:1787~1792
[19]张仕飚,等.热塑性弹性体SBS的改性研究[J].河北工业科技,2004,21(4):3～6
[20]辛浩波,等. .塑料合金及塑橡共混改性(M).北京,中国轻工业出版社,2000,674～700
[21]方少明,等.SBS/EVA改性PP力学性能的研究[J].弹性体,2001,11(6):9～11
[22]韩萍,等. PP/SBS/OMMT复合材料的结构和形态[J].合成树脂及塑料,2006,23(3):63～66
[23]康永锋. PS/PE合金的研究[J].石化技术与应用,2000,18(5):269~271
[24]刘新民. PS/SBS共混体系的性能研究[J].医用塑料,2003,4:18~22
[25]王奇观,等. PVC/EVA/SBS共混体系研究[J].化学研究,2000,l1(1):43~44
[26]甄健. PVC/SBS共混改性波纹套线管的研制[J].塑料加工,2001,34(6):36~37
[27]陈晓浪,等.ABS/PBT/弹性体三元共混合金的研究[J].塑料工业,2005,33(6):16~18
[28]林寅福,等.橡胶改性道路沥青及其微观结构[J].合成橡胶工业,2000,23 (3):196~199
[29]郭玉文. SBS现状及其在塑料改性方面的应用[J].当代石油石化,2006,14(7):29~31
[30]李晓湘,陈志堂,李国斌,煤矸石粉用于橡胶补强的研究[J],云南化工,1998,1:27~30
[31] Koopman M, et al. Compression testing of hollow microspheres (microballoons) to obtain mechanical properties[J]. Scripta Materialia , 2004, 50:593~596.
[32] Nikhil G, et al. Compressionproperties of syntactic foams: effect of cenosphere radius ratio and specimen aspect ratio[J]. Composites: Part A , 2004,35:103~111.
[33]薛颜彬.玻璃微珠填充PP复合材料力学性能与熔融结晶的研究[J].塑料科技,2007,4(35):32~35。
[34]梁基照. PP/ EPDM/玻璃微珠复合材料挤出流动性的研究[J].橡胶工业,2005 ,52(6):329~332。
[35]张成森,曾黎明.空心玻璃微珠填充改性双马来酰胺树脂复合材料耐热性能的研究[J]。塑料工业,2006,34(11):17~19.
[36]原沁波,赵鸣.超细煤矸石作天然橡胶补强填充剂的性能研究[D],太原理工大学,2004
[37]卓存诚,铝酸酯偶联剂在塑料复合材料中的应用[J],福建师大福清分校学报,1996,31:63~66
[38]刘廷华.聚合物成型机械[M].北京:中国轻工业出版社.2005,5:29~42
[2]唐晓徽,刘永新.煤矸石的综合利用[J].河北化工,2007,30(4):27~29
[3]刘新,赵晓龙.煤炭开采副产品煤矸石的危害及其治理[J].科技情报开发与经济,2007,17(25):131~132
[4]陈小玲.淮南矿区煤矸石综合利用与途径[J].淮南师范学院学报,2006,8:133~135
[5]曾小梅.我国煤矸石的综合利用现状[J].山东煤炭科技,2005,(2):8~10
[6]李海珍,姜有.煤矸石的综合利用[J].煤炭技术,1999,(10):25~26
[7]石磊,等.煤矸石的综合利用[J].煤化工,2005,(4):15~18
[8]常万林.煤矸石的综合利用[J].河北煤炭,2002,(3):6~8
[9]邵群,等.矸石粉组成及其与橡胶的相容性研究[J].煤炭加工与综合利用,1997,(2):25~27
[10]沁心波、赵鸣.超细煤矸石矿粉作天然橡胶补强填充剂的性能研究,能源环境保护,2004.18(1):27~30
[11]郭玉文.SBS现状及其在塑料改性方面的应用[J].市场研究,2006,6:29~30
[12] E.S.Metzler.New developments in Kraton G thermoplastic elas-tomers[J].Rubber World.1988,10:38~39
[13]李文波,赵艳芬. SBS的化学改性及其[J].应用广东橡胶,2001,8:2~6
[14]韩丙勇,等.二嵌段SB对SBS性能的影响[J].洽成橡胶工业,2002,25(4):245~24
[15] D.C.Huang,R.C.C.Tsiang. Effects of Tetrahydrofuran as a Structure Modifier in Preparation of SBS Thermoplastic Block Copolymer in Cyclohexane [J]. Journal of Applied Polymer Science. 1996,61:333~341
[16] Gregor Radonjie,et al.. Compatibilization of Polypropylene/Polysryrene Blends with Poly(styrene-b-butadience-B-styrene) Block opolymer[J]. Journal of Applied Polymer Science. 1988,69:2625~2639
[17] U.Plawky , et al. The RaleofStyrene-EthylenelButylene-Styrene Triblock Copolymer as Impact Modifier in Palypropylene-Polyethyle-ne Blends[J]. Journal of Applied Polymer Science. 1996,59:1891~1896
[18] Hanqiao Feng, et al. Compatibiiization effect of graft copolymer on immiscible polymerblends.Polymer[J]. 1998,39:1787~1792
[19]张仕飚,等.热塑性弹性体SBS的改性研究[J].河北工业科技,2004,21(4):3～6
[20]辛浩波,等. .塑料合金及塑橡共混改性(M).北京,中国轻工业出版社,2000,674～700
[21]方少明,等.SBS/EVA改性PP力学性能的研究[J].弹性体,2001,11(6):9～11
[22]韩萍,等. PP/SBS/OMMT复合材料的结构和形态[J].合成树脂及塑料,2006,23(3):63～66
[23]康永锋. PS/PE合金的研究[J].石化技术与应用,2000,18(5):269~271
[24]刘新民. PS/SBS共混体系的性能研究[J].医用塑料,2003,4:18~22
[25]王奇观,等. PVC/EVA/SBS共混体系研究[J].化学研究,2000,l1(1):43~44
[26]甄健. PVC/SBS共混改性波纹套线管的研制[J].塑料加工,2001,34(6):36~37
[27]陈晓浪,等.ABS/PBT/弹性体三元共混合金的研究[J].塑料工业,2005,33(6):16~18
[28]林寅福,等.橡胶改性道路沥青及其微观结构[J].合成橡胶工业,2000,23 (3):196~199
[29]郭玉文. SBS现状及其在塑料改性方面的应用[J].当代石油石化,2006,14(7):29~31
[30]李晓湘,陈志堂,李国斌,煤矸石粉用于橡胶补强的研究[J],云南化工,1998,1:27~30
[31] Koopman M, et al. Compression testing of hollow microspheres (microballoons) to obtain mechanical properties[J]. Scripta Materialia , 2004, 50:593~596.
[32] Nikhil G, et al. Compressionproperties of syntactic foams: effect of cenosphere radius ratio and specimen aspect ratio[J]. Composites: Part A , 2004,35:103~111.
[33]薛颜彬.玻璃微珠填充PP复合材料力学性能与熔融结晶的研究[J].塑料科技,2007,4(35):32~35。
[34]梁基照. PP/ EPDM/玻璃微珠复合材料挤出流动性的研究[J].橡胶工业,2005 ,52(6):329~332。
[35]张成森,曾黎明.空心玻璃微珠填充改性双马来酰胺树脂复合材料耐热性能的研究[J]。塑料工业,2006,34(11):17~19.
[36]原沁波,赵鸣.超细煤矸石作天然橡胶补强填充剂的性能研究[D],太原理工大学,2004
[37]卓存诚,铝酸酯偶联剂在塑料复合材料中的应用[J],福建师大福清分校学报,1996,31:63~66
[38]刘廷华.聚合物成型机械[M].北京:中国轻工业出版社.2005,5:29~42