天然虾青素改性白炭黑/天然橡胶复合材料的制备与性能
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摘要
采用天然虾青素对白炭黑表面进行物理改性,并与天然橡胶(NR)制备成复合材料。利用RPA、DMA、SEM等测试手段对天然虾青素改性白炭黑/天然橡胶复合材料的结构与性能进行表征。结果表明,在硫化特性方面,与未采用天然虾青素改性白炭黑相比,采用天然虾青素改性白炭黑所得胶料的焦烧时间和工艺正硫化时间均缩短,促进了橡胶的硫化过程;在物理力学性能方面,所得硫化胶的拉伸强度基本不变,回弹性和耐磨性明显增加,压缩生热降低;在动态黏弹性方面,所得硫化胶的Payne效应明显降低,填料的分散性在一定程度上得到改善;在动态力学性能方面,所得硫化胶的滚动阻力降低,玻璃化转变温度提高。特别地,在耐老化方面,天然虾青素改性白炭黑/天然橡胶复合材料的耐热空气老化性能明显提高。
The surface of silica was physically modified with natural astaxanthin and composited with natural rubber. The structure and properties of natural astaxanthin-modified silica/natural rubber composites were characterized by RPA, DMA and SEM. The results showed that compared with the modified silica without natural astaxanthin in the vulcanization characteristics, the scorch time and the positive vulcanization time of the rubber obtained by using natural astaxanthin-modified silica were shortened, which promoted the vulcanization process of rubber. In terms of physical and mechanical properties, the tensile strength of the obtained vulcanizate was substantially unchanged, the resilience and abrasion resistance were significantly increased and the compression heat generation was lowered. In terms of dynamic viscoelasticity, the Payne effect of the obtained vulcanizate was significantly reduced and the dispersibility of the filler was improved to some extent. In terms of dynamic mechanical properties,the rolling resistance of the obtained vulcanizate was lowered and the glass transition temperature was increased. In particular, in terms of aging resistance, the heat-resistant air aging performance of the natural astaxanthin-modified silica/natural rubber composite material was remarkably improved.
The surface of silica was physically modified with natural astaxanthin and composited with natural rubber. The structure and properties of natural astaxanthin-modified silica/natural rubber composites were characterized by RPA, DMA and SEM. The results showed that compared with the modified silica without natural astaxanthin in the vulcanization characteristics, the scorch time and the positive vulcanization time of the rubber obtained by using natural astaxanthin-modified silica were shortened, which promoted the vulcanization process of rubber. In terms of physical and mechanical properties, the tensile strength of the obtained vulcanizate was substantially unchanged, the resilience and abrasion resistance were significantly increased and the compression heat generation was lowered. In terms of dynamic viscoelasticity, the Payne effect of the obtained vulcanizate was significantly reduced and the dispersibility of the filler was improved to some extent. In terms of dynamic mechanical properties,the rolling resistance of the obtained vulcanizate was lowered and the glass transition temperature was increased. In particular, in terms of aging resistance, the heat-resistant air aging performance of the natural astaxanthin-modified silica/natural rubber composite material was remarkably improved.
引文
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[10] MOVAHED S O, ANSARIFAR A, SONG M. Effect of silanized silica nanofiller on tack and green strength of selected filled rubbers[J].Polymer International, 2010, 58(4):424-429.
[11] KATSUMATA T, ISHIBASHI T, KYLE D. A sub-chronic toxicity evaluation of a natural astaxanthin-rich carotenoid extract of Paracoccus carotinifaciens, in rats[J]. Toxicology Reports, 2014, 1:582-588.
[12]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 Haoming, GAO Lan. Astaxanthin:chemical structure, biological functions and usage[J]. Fine Chemicals, 2003, 20(1):32-37.
[13] DUFOSSE L. Microbial production of food grade pigment[J]. Food Technology&Biotechnology, 2006, 44(3):313-321.
[14] MARTIN J F, GUDINA E, BARREDO J L. Conversion ofβ-carotene into astaxanthin:two separate enzymes or a bifunctional hydroxylaseketolase protein?[J]. Microbial Cell Factories. 2008, 7(1):1-10.
[15]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 Guiling, CHENG Jiayang, MA Jiong. Research review of Haematococcus pluvialis and astaxathin[J]. Journal of Fisheries of China, 2014, 38(2):297-304.
[16] LEE S H, MIN D B. Effects, quenching mechanisms, and kinetics of carotenoids in chlorophyll-sensitized photooxidation of soybean oil[J].Journal of agricural&food Chemistry, 1990, 38(8):1630-1634.
[17] JOHNSON E A, VILLA T G, LEWIS M J. Phaffia rhodozyma as an astaxantin source in samonid diets[J]. Aquaculture, 1980, 20(2):123-134.
[18] JOHNSON E A, LEWIS M J, GRAU C R. Pigmentation of egg yolks with astaxanthin from the yeast phaffia rhodozyma[J]. Poultry Science,1980, 59(8):1777-1782.
[19] GUERIN M, HUNTLEY M E, OLAIZOLA M. Haematococcus astaxanthin:applications for human health and nutrition[J]. Trends in Biotechnology, 2003, 21(5):210-216.
[20]张惠元.一种治疗便秘的中药制备方法:CN105664042A[P]. 2016-06-15.ZHANG Huiyuan. Chinese medicine preparation method for treating constipation:CN105664042A[P]. 2016-06-15.
[21]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:CN101313897[P]. 2008-12-03.FU Zhengwei, JIN Yuanxiang, WANG HuiJie. Application of phaffia rhodozyma astaxanthin in preparing medicament for preventing and controlling typeⅡdiabetes:CN101313897A[P]. 2008-12-03.
[22] TODD L R. Method for retarding and preventing sunburn by UV light:US6433025B1[P]. 2002-08-13.
[23]王浩,王仁伟.一种富含天然虾青素的芝麻油及其制备方法:CN105901165A[P]. 2016-08-31.WANG Hao, WANG Renwei. Antioxidant sesame mixed oil and a preparing method thereof:CN105901165A[P]. 2016-08-31.
[24]樊萍,任国谱,刘静萍,等.含虾青素的乳制品及其制备方法:CN102125093A[P]. 2011-07-20.FAN Ping, REN Guopu., LIU Jingping, et al. Dairy products containing astaxanthin and their preparation methods:CN 102125093A[P]. 2011-07-20.
[25]徐伦超.一种具有延缓衰老功效的虾青素保健饮料:CN105029570A[P]. 2015-11-11.XU Lunchao. Astaxanthin health drink with anti-aging effect:CN105029570A[P]. 2015-11-11.
[26] SOON P J, HEE C J, KYUNG K Y, et al. Astaxanthin decreased oxidative stress and inflammation and enhanced immune response in humans[J]. Nutrition&Metabolism, 2010, 7(1):18-28.
[27]刘建国,苏芳,石琨,等.一种强化鲑鱼营养功能与色泽的混合饲料与应用:CN105831494A[P]. 2016-08-10.LIU Jianguo, SU Fang, SHI Kun, et al. Rainbow trout nutrition enhancer and application thereof:CN105831494A[P]. 2016-08-10.
[2]徐云慧,李培培,张兆红,等.废白土在天然橡胶中的应用性能[J].化工进展, 2011, 30(9):2035-2040.XU Yunhui, LI Peipei, ZHANG Zhaohong, et al. Application of waste clay in natural rubber[J]. Chemical Industry and Engineering Progress,2011,30(9):2035-2040.
[3]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 Lingfeng, XIONG Yuzhu, DAI Jun, et al. Preparation and characterization of modified silica/natural rubber composite material[J]. Polymer Materials Science and Engineering, 2017, 33(5):158-163.
[4]刘吉文,许海燕,吴驰飞.环氧天然橡胶接枝高分散白炭黑增强天然橡胶复合材料的制备及表征[J].高分子学报, 2008(2):123-128.LIU Jiwen, XU Haiyan, WU Chifei. Preparation and characterization of the natural rubber composites reinforced by epoxy natural rubber grafted silica with good dispersibility[J]. Acta Polymerica Sinica, 2008(2):123-128.
[5]潘其维,王兵兵,周瑛,等.一种硅烷偶联剂的合成及其在白炭黑/天然橡胶复合材料中的应用[J].高分子学报, 2014(2):202-209.PAN Qiwei, WANG Bingbing, ZHOU Ying, et al. Synthesis of a silane coupling agent and its application in silica/NR composites[J]. Acta Polymerica Sinica, 2014(2):202-209.
[6] WAHBA L, D'ARIENZO M, DONETTI R, et al. In situ sol-gel obtained silica-rubber nanocomposites:influence of the filler precursors on the improvement of the mechanical properties[J]. RSC Advances, 2013, 3(17):5832-5844.
[7] QU L, YU G, XIE X, et al. Effect of silane coupling agent on filler and rubber interaction of silica reinforced solution styrene butadiene rubber[J]. Polymer Composites, 2013, 34(10):1575-1582.
[8] OSTAD‐MOVAHED S, ANSARIFAR A, SONG M. Effects of different interphases on the mechanical properties of cured silanized silicafilled styrene-butadiene/polybutadiene rubber blends for use in passenger car tire treads[J]. Journal of Applied Polymer Science, 2010,113(3):1868-1878.
[9] DOHI H, HORIUCHI S. Locating a silane coupling agent in silicafilled rubber composites by EFTEM[J]. Langmuir, 2007, 23(24):12344-12349.
[10] MOVAHED S O, ANSARIFAR A, SONG M. Effect of silanized silica nanofiller on tack and green strength of selected filled rubbers[J].Polymer International, 2010, 58(4):424-429.
[11] KATSUMATA T, ISHIBASHI T, KYLE D. A sub-chronic toxicity evaluation of a natural astaxanthin-rich carotenoid extract of Paracoccus carotinifaciens, in rats[J]. Toxicology Reports, 2014, 1:582-588.
[12]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 Haoming, GAO Lan. Astaxanthin:chemical structure, biological functions and usage[J]. Fine Chemicals, 2003, 20(1):32-37.
[13] DUFOSSE L. Microbial production of food grade pigment[J]. Food Technology&Biotechnology, 2006, 44(3):313-321.
[14] MARTIN J F, GUDINA E, BARREDO J L. Conversion ofβ-carotene into astaxanthin:two separate enzymes or a bifunctional hydroxylaseketolase protein?[J]. Microbial Cell Factories. 2008, 7(1):1-10.
[15]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 Guiling, CHENG Jiayang, MA Jiong. Research review of Haematococcus pluvialis and astaxathin[J]. Journal of Fisheries of China, 2014, 38(2):297-304.
[16] LEE S H, MIN D B. Effects, quenching mechanisms, and kinetics of carotenoids in chlorophyll-sensitized photooxidation of soybean oil[J].Journal of agricural&food Chemistry, 1990, 38(8):1630-1634.
[17] JOHNSON E A, VILLA T G, LEWIS M J. Phaffia rhodozyma as an astaxantin source in samonid diets[J]. Aquaculture, 1980, 20(2):123-134.
[18] JOHNSON E A, LEWIS M J, GRAU C R. Pigmentation of egg yolks with astaxanthin from the yeast phaffia rhodozyma[J]. Poultry Science,1980, 59(8):1777-1782.
[19] GUERIN M, HUNTLEY M E, OLAIZOLA M. Haematococcus astaxanthin:applications for human health and nutrition[J]. Trends in Biotechnology, 2003, 21(5):210-216.
[20]张惠元.一种治疗便秘的中药制备方法:CN105664042A[P]. 2016-06-15.ZHANG Huiyuan. Chinese medicine preparation method for treating constipation:CN105664042A[P]. 2016-06-15.
[21]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:CN101313897[P]. 2008-12-03.FU Zhengwei, JIN Yuanxiang, WANG HuiJie. Application of phaffia rhodozyma astaxanthin in preparing medicament for preventing and controlling typeⅡdiabetes:CN101313897A[P]. 2008-12-03.
[22] TODD L R. Method for retarding and preventing sunburn by UV light:US6433025B1[P]. 2002-08-13.
[23]王浩,王仁伟.一种富含天然虾青素的芝麻油及其制备方法:CN105901165A[P]. 2016-08-31.WANG Hao, WANG Renwei. Antioxidant sesame mixed oil and a preparing method thereof:CN105901165A[P]. 2016-08-31.
[24]樊萍,任国谱,刘静萍,等.含虾青素的乳制品及其制备方法:CN102125093A[P]. 2011-07-20.FAN Ping, REN Guopu., LIU Jingping, et al. Dairy products containing astaxanthin and their preparation methods:CN 102125093A[P]. 2011-07-20.
[25]徐伦超.一种具有延缓衰老功效的虾青素保健饮料:CN105029570A[P]. 2015-11-11.XU Lunchao. Astaxanthin health drink with anti-aging effect:CN105029570A[P]. 2015-11-11.
[26] SOON P J, HEE C J, KYUNG K Y, et al. Astaxanthin decreased oxidative stress and inflammation and enhanced immune response in humans[J]. Nutrition&Metabolism, 2010, 7(1):18-28.
[27]刘建国,苏芳,石琨,等.一种强化鲑鱼营养功能与色泽的混合饲料与应用:CN105831494A[P]. 2016-08-10.LIU Jianguo, SU Fang, SHI Kun, et al. Rainbow trout nutrition enhancer and application thereof:CN105831494A[P]. 2016-08-10.