天然虾青素辅助Si-69改性白炭黑/天然橡胶复合材料的性能
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摘要
利用天然虾青素辅助偶联剂Si-69对白炭黑表面进行改性并制备了改性白炭黑/天然橡胶(NR)复合材料。借助橡胶加工分析仪、动态力学热分析、扫描电镜等方法研究了改性白炭黑/NR复合材料的结构与性能。结果表明,在硫化性能方面,相比于Si-69改性的白炭黑/NR胶料,天然虾青素辅助Si-69改性的白炭黑/NR胶料的焦烧时间和硫化时间均缩短,提高了橡胶的硫化速率;在物理力学性能方面,硫化胶的拉伸强度和定伸应力基本不变,回弹性和耐磨性增加,压缩疲劳温升降低;在动态黏弹性方面,硫化胶的Payne效应明显降低,填料的分散性改善;在动态力学性能方面,硫化胶的滚动阻力降低,玻璃化转变温度(T_g)提高。特别地,天然虾青素辅助Si-69改性的白炭黑能明显提高复合材料的耐热空气老化性能,并且随着天然虾青素用量的增加,耐老化性能进一步地提高。
The surface of silica was modified with natural astaxanthin-assisted coupling reagent(Si-69) to prepare modified silica/natural rubber(NR) composites. The structure and properties of modified silica/(NR) composites were characterized by rubber processing analyzer(RPA), dynamic mechanical analysis(DMA) and SEM. The results show that in the vulcanization performance, the natural astaxanthin-assisted Si-69 modified silica/NR compound has shorter scorch time and vulcanization time than Si-69 modified silica/NR compound, and the rubber vulcanization rate is accelerated; in terms of physical and mechanical properties, the tensile strength and the tensile stress of the vulcanizate are basically unchanged, the resilience and abrasion resistance are increased, and the temperature rise of compression fatigue is reduced; in terms of dynamic viscoelasticity, the Payne effect of the vulcanizates is significantly reduced, and the dispersibility of the filler is improved; in terms of dynamic mechanical properties, the rolling resistance of vulcanizates is lowered and the glass transition temperature(T_g) is increased. In particular, natural astaxanthin-assisted Si-69 modified silica can significantly improve the heat-resistant air aging performance of the composite, and as the amount of natural astaxanthin increases, the aging resistance is further improved.
The surface of silica was modified with natural astaxanthin-assisted coupling reagent(Si-69) to prepare modified silica/natural rubber(NR) composites. The structure and properties of modified silica/(NR) composites were characterized by rubber processing analyzer(RPA), dynamic mechanical analysis(DMA) and SEM. The results show that in the vulcanization performance, the natural astaxanthin-assisted Si-69 modified silica/NR compound has shorter scorch time and vulcanization time than Si-69 modified silica/NR compound, and the rubber vulcanization rate is accelerated; in terms of physical and mechanical properties, the tensile strength and the tensile stress of the vulcanizate are basically unchanged, the resilience and abrasion resistance are increased, and the temperature rise of compression fatigue is reduced; in terms of dynamic viscoelasticity, the Payne effect of the vulcanizates is significantly reduced, and the dispersibility of the filler is improved; in terms of dynamic mechanical properties, the rolling resistance of vulcanizates is lowered and the glass transition temperature(T_g) is increased. In particular, natural astaxanthin-assisted Si-69 modified silica can significantly improve the heat-resistant air aging performance of the composite, and as the amount of natural astaxanthin increases, the aging resistance is further improved.
引文
[1] 王梦蛟. 绿色轮胎的发展及其推广应用[J]. 橡胶工业, 2018, 65(1): 105-112.Wang M J. The development of green tires and its promotion and application[J]. China Rubber Industry, 2018, 65(1): 105-112.
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[3] Wang M J, Morris M D, Kutsovsky Y. Effect of fumed silica surface area on silicone rubber reinforcement[J]. Kautsch. Gummi Kunstst., 2008, 61: 107-117.
[4] Roland R. Rubber compound and tires based on such a compound: EP, 0501227A1[P]. 1992-09-02.
[5] Pattanawanidchai S, Loykulnant S, Sae-Oui P, et al. Development of eco-friendly coupling agent for precipitated silica filled natural rubber compounds[J]. Polym. Test., 2014, 34: 58-63.
[6] Choi S, Nah C, Lee S G, et al. Effect of filler-filler interaction on rheological behavior of natural rubber compounds filled with both carbon black and silica[J]. Polym. Int., 2003, 52: 23-28.
[7] Prasertsri S, Rattanasom N. Fumed and precipitated silica white reinforced natural rubber composites prepared from latex system: mechanical and dynamic properties[J]. Polym. Test., 2012, 31: 593-605.
[8] Etienne M, Walcarius A. Analytical investigation of the chemical reactivity and stability of aminopropyl-grafted silica in aqueous medium[J]. Talanta, 2003, 59: 1173-1188.
[9] Thammathadanukul V, O′haver J H, Harwell J H, et al. Comparison of rubber reinforcement using various surface-modified precipitated silicas[J]. J. Appl. Polym. Sci., 2015, 59:1741-1750.
[10] Zheng J, Han D, Ye X, et al. Chemical and physical interaction between silane coupling agent with long arms and silica and its effect on silica/natural rubber composites[J]. Polymer, 2018, 135: 200-210.
[11] 杨清芝. 实用橡胶工艺学[M]. 北京: 化学工业出版社, 2005.
[12] 孙连文. 大分子表面改性剂改性白炭黑对绿色轮胎胎面胶性能的影响研究[D]. 青岛: 青岛科技大学, 2015.Sun L W. Effects of silica modified by macromolecular modifiers on the properties of green tire tread[D]. Qingdao: Qingdao University of Science and Technology, 2015.
[13] Mohapatra S, Alex R, Nando G B. Cardanol grafted natural rubber: a green substitute to natural rubber for enhancing silica filler dispersion[J]. J. Appl. Polym. Sci., 2016, 133: 43057-43073.
[14] Matsuno T, Miki W. Biological functions and activities of animals carotenoids[J]. Pure Appl. Chem., 1991, 63:141-146.
[15] 李浩明, 高蓝. 虾青素的结构、功能与应用[J]. 精细化工, 2003, 20(1):32-37.Li H M, Gao L. Astaxanthin: chemical structure, biological functions and usage[J]. Fine Chemicals, 2003, 20(1): 32-37.
[16] Dufosse L. Microbial production of food grade pigments[J]. Food Technol. Biotechnol., 2006, 44: 313-321.
[17] Martin J F, Eduardo G, Barredo J L. Conversion of β-carotene into astaxanthin: two separate enzymes or a bifunctional hydroxylase-ketolase protein[J]. Microbial Cell Factories, 2008, 7: 1-10.
[18] 高桂玲, 成家杨, 马炯. 雨生红球藻和虾青素的研究[J]. 水产学报, 2014, 38(2):297-304.Gao G L, Cheng J Y, Ma J. Research review of haematococcus pluvialis and astaxathin[J]. Journal of Fisheries of China, 2014, 38(2): 297-304.
[19] Lee S H, Min D B. Effects, quenching mechanisms, and kinetics of carotenoids in chlorophyllsensitized photooxidation of soybean oil[J]. J. Agric. Food Chem., 1990, 38: 1630-1634.
[20] Johnson E A, Villa T G, Lewis M J. Phaffia rhodozyma as an astaxanthin source in salmonid diets[J]. Aquaculture, 1980, 20: 123-134.
[21] Johnson E A, Lewis M J, Grau C R. Pigmentation of egg yolks with astaxanthin from the yeast Phaffia rhodozyma[J]. Poultry Sci., 1980, 59: 1777-1782.
[22] 张芝庭, 张涛涛. 一种防治老年痴呆的产品及其制备方法:中国,104644698A[P]. 2015-05-27.
[23] 张惠元. 一种治疗便秘的中药制备方法: 中国,105664042A[P]. 2016-06-15.
[24] 傅正伟,靳远祥,王慧洁. 红发夫酵母虾青素在制备防治Ⅱ型糖尿病药物中的应用:中国,101313897A[P]. 2008-12-03.
[25] Todd L R. Method for retarding and preventing sunburn by UV light: US,6433025B1[P]. 2002-08-13.
[26] 王浩, 王仁伟. 一种富含天然虾青素的芝麻油及其制备方法:中国,105901165A[P]. 2016-08-31.
[27] 樊萍,任国谱,刘静萍. 含虾青素的乳制品及其制备方法:中国,102125093A[P]. 2011-07-20.
[28] 徐伦超. 一种具有延缓衰老功效的虾青素保健饮料:中国,105029570A[P]. 2015-11-11.
[29] 袁三平, 李璐. 含有天然虾青素的营养保健品: 中国,104187668A[P]. 2014-12-10.
[30] 刘建国,芳芳,石琨. 一种强化鲑鱼营养功能与色泽的养殖混合饲料与应用:中国,105831494A[P]. 2016-08-10.
[31] 鲁冰雪, 张振秀, 王文艳,等. 白炭黑用量对橡胶型氯化聚乙烯性能影响的研究[J]. 弹性体, 2011, 21(1): 54-57. Lu B X, Zhang Z X, Wang W Y, et al. Effect of silica loading on the properties of CM elastomer[J]. China Elastomerics, 2011, 21(1): 54-57.
[32] 傅明.新型多功能橡胶助剂的制备及其在橡胶/白炭黑复合材料中的应用[D]. 广州: 华南理工大学, 2015.Fu M. Preparation of novel multifunctional rubber additives and their application in rubber/silica composites[D]. Guangzhou:South China University of Technology, 2015.
[33] 杨清芝.实用橡胶工艺学[M].北京:化学工业出版社, 2005.
[34] 刘涛, 陈亚薇, 刘东,等. 填充橡胶的Payne效应[J]. 特种橡胶制品, 2015, 36(6): 76-81.Liu T, Chen Y W, Liu D, et al. Payne effect of rubber filling[J]. Special Purpose Rubber Products, 2015, 36(6): 76-81.
[35] 张建军, 任福君, 董兴旺. 低滚动阻力轿车轮胎胎面配方的材料选择[J]. 轮胎工业, 2014, 34(8): 480-487. Zhang J J, Ren F J, Dong X W. Material selection for tread of low rolling resistance passenger car tire[J]. Tire Industry, 2014, 34(8): 480-487.
[2] 崔凌峰,熊玉竹,戴骏,等. 改性白炭黑/天然橡胶复合材料的制备及性能[J]. 高分子材料科学与工程, 2017, 33(5): 158-163.Cui L F, Xiong Y Z, Dai J, et al. Preparation and characterization of modified silica/natural rubber composite material[J]. Polymer Materials Science & Engineering, 2017, 33(5): 158-163.
[3] Wang M J, Morris M D, Kutsovsky Y. Effect of fumed silica surface area on silicone rubber reinforcement[J]. Kautsch. Gummi Kunstst., 2008, 61: 107-117.
[4] Roland R. Rubber compound and tires based on such a compound: EP, 0501227A1[P]. 1992-09-02.
[5] Pattanawanidchai S, Loykulnant S, Sae-Oui P, et al. Development of eco-friendly coupling agent for precipitated silica filled natural rubber compounds[J]. Polym. Test., 2014, 34: 58-63.
[6] Choi S, Nah C, Lee S G, et al. Effect of filler-filler interaction on rheological behavior of natural rubber compounds filled with both carbon black and silica[J]. Polym. Int., 2003, 52: 23-28.
[7] Prasertsri S, Rattanasom N. Fumed and precipitated silica white reinforced natural rubber composites prepared from latex system: mechanical and dynamic properties[J]. Polym. Test., 2012, 31: 593-605.
[8] Etienne M, Walcarius A. Analytical investigation of the chemical reactivity and stability of aminopropyl-grafted silica in aqueous medium[J]. Talanta, 2003, 59: 1173-1188.
[9] Thammathadanukul V, O′haver J H, Harwell J H, et al. Comparison of rubber reinforcement using various surface-modified precipitated silicas[J]. J. Appl. Polym. Sci., 2015, 59:1741-1750.
[10] Zheng J, Han D, Ye X, et al. Chemical and physical interaction between silane coupling agent with long arms and silica and its effect on silica/natural rubber composites[J]. Polymer, 2018, 135: 200-210.
[11] 杨清芝. 实用橡胶工艺学[M]. 北京: 化学工业出版社, 2005.
[12] 孙连文. 大分子表面改性剂改性白炭黑对绿色轮胎胎面胶性能的影响研究[D]. 青岛: 青岛科技大学, 2015.Sun L W. Effects of silica modified by macromolecular modifiers on the properties of green tire tread[D]. Qingdao: Qingdao University of Science and Technology, 2015.
[13] Mohapatra S, Alex R, Nando G B. Cardanol grafted natural rubber: a green substitute to natural rubber for enhancing silica filler dispersion[J]. J. Appl. Polym. Sci., 2016, 133: 43057-43073.
[14] Matsuno T, Miki W. Biological functions and activities of animals carotenoids[J]. Pure Appl. Chem., 1991, 63:141-146.
[15] 李浩明, 高蓝. 虾青素的结构、功能与应用[J]. 精细化工, 2003, 20(1):32-37.Li H M, Gao L. Astaxanthin: chemical structure, biological functions and usage[J]. Fine Chemicals, 2003, 20(1): 32-37.
[16] Dufosse L. Microbial production of food grade pigments[J]. Food Technol. Biotechnol., 2006, 44: 313-321.
[17] Martin J F, Eduardo G, Barredo J L. Conversion of β-carotene into astaxanthin: two separate enzymes or a bifunctional hydroxylase-ketolase protein[J]. Microbial Cell Factories, 2008, 7: 1-10.
[18] 高桂玲, 成家杨, 马炯. 雨生红球藻和虾青素的研究[J]. 水产学报, 2014, 38(2):297-304.Gao G L, Cheng J Y, Ma J. Research review of haematococcus pluvialis and astaxathin[J]. Journal of Fisheries of China, 2014, 38(2): 297-304.
[19] Lee S H, Min D B. Effects, quenching mechanisms, and kinetics of carotenoids in chlorophyllsensitized photooxidation of soybean oil[J]. J. Agric. Food Chem., 1990, 38: 1630-1634.
[20] Johnson E A, Villa T G, Lewis M J. Phaffia rhodozyma as an astaxanthin source in salmonid diets[J]. Aquaculture, 1980, 20: 123-134.
[21] Johnson E A, Lewis M J, Grau C R. Pigmentation of egg yolks with astaxanthin from the yeast Phaffia rhodozyma[J]. Poultry Sci., 1980, 59: 1777-1782.
[22] 张芝庭, 张涛涛. 一种防治老年痴呆的产品及其制备方法:中国,104644698A[P]. 2015-05-27.
[23] 张惠元. 一种治疗便秘的中药制备方法: 中国,105664042A[P]. 2016-06-15.
[24] 傅正伟,靳远祥,王慧洁. 红发夫酵母虾青素在制备防治Ⅱ型糖尿病药物中的应用:中国,101313897A[P]. 2008-12-03.
[25] Todd L R. Method for retarding and preventing sunburn by UV light: US,6433025B1[P]. 2002-08-13.
[26] 王浩, 王仁伟. 一种富含天然虾青素的芝麻油及其制备方法:中国,105901165A[P]. 2016-08-31.
[27] 樊萍,任国谱,刘静萍. 含虾青素的乳制品及其制备方法:中国,102125093A[P]. 2011-07-20.
[28] 徐伦超. 一种具有延缓衰老功效的虾青素保健饮料:中国,105029570A[P]. 2015-11-11.
[29] 袁三平, 李璐. 含有天然虾青素的营养保健品: 中国,104187668A[P]. 2014-12-10.
[30] 刘建国,芳芳,石琨. 一种强化鲑鱼营养功能与色泽的养殖混合饲料与应用:中国,105831494A[P]. 2016-08-10.
[31] 鲁冰雪, 张振秀, 王文艳,等. 白炭黑用量对橡胶型氯化聚乙烯性能影响的研究[J]. 弹性体, 2011, 21(1): 54-57. Lu B X, Zhang Z X, Wang W Y, et al. Effect of silica loading on the properties of CM elastomer[J]. China Elastomerics, 2011, 21(1): 54-57.
[32] 傅明.新型多功能橡胶助剂的制备及其在橡胶/白炭黑复合材料中的应用[D]. 广州: 华南理工大学, 2015.Fu M. Preparation of novel multifunctional rubber additives and their application in rubber/silica composites[D]. Guangzhou:South China University of Technology, 2015.
[33] 杨清芝.实用橡胶工艺学[M].北京:化学工业出版社, 2005.
[34] 刘涛, 陈亚薇, 刘东,等. 填充橡胶的Payne效应[J]. 特种橡胶制品, 2015, 36(6): 76-81.Liu T, Chen Y W, Liu D, et al. Payne effect of rubber filling[J]. Special Purpose Rubber Products, 2015, 36(6): 76-81.
[35] 张建军, 任福君, 董兴旺. 低滚动阻力轿车轮胎胎面配方的材料选择[J]. 轮胎工业, 2014, 34(8): 480-487. Zhang J J, Ren F J, Dong X W. Material selection for tread of low rolling resistance passenger car tire[J]. Tire Industry, 2014, 34(8): 480-487.
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