环氧化杜仲橡胶的制备及其在丁苯橡胶/白炭黑复合材料中的应用
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摘要
以杜仲橡胶(EUG)的石油醚溶液为原料、过氧乙酸为环氧化试剂,通过乳液法工艺对EUG进行环氧化改性制备了环氧化EUG(EEUG),采用核磁共振波谱对EEUG进行了表征,研究了EEUG用量对丁苯橡胶/白炭黑复合材料加工性能、微观形态、物理机械性能和动态力学性能的影响。结果表明,用EEUG改性丁苯橡胶/白炭黑复合体系时,可以明显改善白炭黑在丁苯橡胶基体中的分散情况,降低白炭黑引起的延迟硫化效应,减轻Payne效应,提高其硫化胶的力学性能、耐磨性能及压缩疲劳性能;改性后的丁苯橡胶/白炭黑硫化胶的动态力学性能明显提高,其储能模量增大,滞后损失减少;但是当EEUG用量较大时改性效果不佳。
Epoxidized eucommia ulmoides gum(EEUG) was prepared by epoxidation modification of eucommia ulmoides gum(EUG) via emulsion method used EUG-petroleum ether solution as raw material and peracetic acid as epoxidation reagent. EEUG was characterized by nuclear magnetic resonance spectroscopy. The effects of amount of EEUG on processing properties, microscopic morphology, physical and mechanical properties and dynamic mechanical properties of styrene-butadiene rubber(SBR)/silica composites were researched. The results showed that EEUG could improve dispersion of silica significantly in SBR matrix and decrease the vulcanization delay caused by silica. Meanwhile, Payne effect was reduced and mechanical properties, wear resistance and compression fatigue were improved obviously due to introduction of EEUG. In addition, the composites modified with EEUG got better dynamic mechanical properties, higher storage modulus and lower lag loss. However, the modified effect became worse when too much EEUG was used.
Epoxidized eucommia ulmoides gum(EEUG) was prepared by epoxidation modification of eucommia ulmoides gum(EUG) via emulsion method used EUG-petroleum ether solution as raw material and peracetic acid as epoxidation reagent. EEUG was characterized by nuclear magnetic resonance spectroscopy. The effects of amount of EEUG on processing properties, microscopic morphology, physical and mechanical properties and dynamic mechanical properties of styrene-butadiene rubber(SBR)/silica composites were researched. The results showed that EEUG could improve dispersion of silica significantly in SBR matrix and decrease the vulcanization delay caused by silica. Meanwhile, Payne effect was reduced and mechanical properties, wear resistance and compression fatigue were improved obviously due to introduction of EEUG. In addition, the composites modified with EEUG got better dynamic mechanical properties, higher storage modulus and lower lag loss. However, the modified effect became worse when too much EEUG was used.
引文
[1] 张继川,薛兆弘,严瑞芳,等.天然高分子材料——杜仲胶的研究进展[J].高分子学报,2011(10):1105-1117.
[2] 李春霞,辛振祥,夏琳.天然杜仲橡胶在橡塑方面的研究进展[J].特种橡胶制品,2014,35(1):78-80.
[3] Fisher H L.Conversion of rubber into thermoplastic products with properties similar to gutta percha,balata,and shellac[J].Industrial and Engineering Chemistry,1927,19 (12):1325-1333.
[4] 朱峰,岳红,祖恩峰,等.新型功能材料杜仲胶的研究与应用[J].安徽大学学报,2005,29(3):89-94.
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[6] Bac N V,Mihailov M,Terlemezyan L.On the stability of na-tural rubber latex acidified by acetic acid and subsequent epoxidation by peracetic acid[J].European Polymer Journal,1991,27(6):557-563.
[7] Burfield D R,Lim K L,Law K S.Epoxidation of natural rubber latices:Methods of preparation and properties of modified rubbers[J].Journal of Applied Polymer Science,1984,29(5):1661-1673.
[8] Gan L H,Ng S C.Kinetic studies of the performic acid epoxidation of natural rubber latex stabilized by cationic surfactant[J].European Polymer Journal,1986,22(7):573-576.
[9] Gelling I R.Modification of natural rubber latex with peracetic acid[J].Rubber Chemistry Technology,1985,58(1):86-96.
[10] Xia Lin,Wang Yan,Ma Zhenguo,et al.Preparation of epoxidized eucommia ulmoides gum and its application in styrene-butadiene rubber(SBR)/silica composites[J].Polymers for Advanced Technology,2017,28(1):94-101.
[11] 杜军,袁仲雪.材料配合与混炼加工橡胶部分[M].北京:化学工业出版社,2003:106.
[12] 赵金义,毕雪玲,周丽玲,等.硅烷偶联剂改性白炭黑在丁苯橡胶中的应用[J].青岛科技大学学报,2004,25(2):160-162.
[13] 郝书峰,郑治祥,范卫青,等.沉淀法白炭黑的表面改性及其性能研究[J].硅酸盐通报,2011,30(3):529-533.
[14] Cayre O,Paunov N,Velev O D.Fabrication of asymmetrically coated colloid particles by micro contact printing techniques[J].Journal of Materials and Chemistry,2003,13(2):2445-2450.
[15] 宋成芝,车永兴,张志广,等.硅烷偶联剂对炭黑/白炭黑增强丁腈橡胶填料网络结构及动态性能的影响[J].合成橡胶工业,2011,34(2):128-132.
[16] Sengloyluan K,Sahakaro K,Dierkes W K.Silica-reinforced tire tread compounds compatibilized by using epoxidized natural rubber[J].European Polymer Journal,2014,51(1):69-79.
[17] 王彦,王颖悟,夏琳,等.杜仲橡胶的水相-有机相法提取及其结构表征[J].橡胶工业,2017,64(11):650-654.
[18] 王彦,夏琳,辛振祥.环氧化杜仲胶改性丁苯橡胶/白炭黑复合材料的制备与性能[J].合成橡胶工业,2018,41(2):115-119.
[19] 梁宁宁.杜仲胶的环氧化改性及其超疏水复合材料的制备[D].青岛:青岛科技大学,2015.
[20] 杨凤,王芳,方庆红,等.乳液法环氧化改性天然杜仲胶[J].高分子材料科学与工程,2015,31(5):56-61.
[21] Xu Tiwen,Jia Zhixin,Luo Yuanfang,et al.Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites[J].Applied Surface Science,2015,328(2):306–313.
[22] 栗磊,丁乃秀,周海妮,等.白炭黑分散剂对集成橡胶性能的影响[J].橡胶工业,2014,61(6):341-345.
[2] 李春霞,辛振祥,夏琳.天然杜仲橡胶在橡塑方面的研究进展[J].特种橡胶制品,2014,35(1):78-80.
[3] Fisher H L.Conversion of rubber into thermoplastic products with properties similar to gutta percha,balata,and shellac[J].Industrial and Engineering Chemistry,1927,19 (12):1325-1333.
[4] 朱峰,岳红,祖恩峰,等.新型功能材料杜仲胶的研究与应用[J].安徽大学学报,2005,29(3):89-94.
[5] Xia Lin,Wang Yan,Ma Zhenguo,et al.The organic-aqueous extraction of natural eucommia ulmoides rubber and its properties and application in car radial tires[J].Advances in Polymer Technology,2017,36(3):295-300.
[6] Bac N V,Mihailov M,Terlemezyan L.On the stability of na-tural rubber latex acidified by acetic acid and subsequent epoxidation by peracetic acid[J].European Polymer Journal,1991,27(6):557-563.
[7] Burfield D R,Lim K L,Law K S.Epoxidation of natural rubber latices:Methods of preparation and properties of modified rubbers[J].Journal of Applied Polymer Science,1984,29(5):1661-1673.
[8] Gan L H,Ng S C.Kinetic studies of the performic acid epoxidation of natural rubber latex stabilized by cationic surfactant[J].European Polymer Journal,1986,22(7):573-576.
[9] Gelling I R.Modification of natural rubber latex with peracetic acid[J].Rubber Chemistry Technology,1985,58(1):86-96.
[10] Xia Lin,Wang Yan,Ma Zhenguo,et al.Preparation of epoxidized eucommia ulmoides gum and its application in styrene-butadiene rubber(SBR)/silica composites[J].Polymers for Advanced Technology,2017,28(1):94-101.
[11] 杜军,袁仲雪.材料配合与混炼加工橡胶部分[M].北京:化学工业出版社,2003:106.
[12] 赵金义,毕雪玲,周丽玲,等.硅烷偶联剂改性白炭黑在丁苯橡胶中的应用[J].青岛科技大学学报,2004,25(2):160-162.
[13] 郝书峰,郑治祥,范卫青,等.沉淀法白炭黑的表面改性及其性能研究[J].硅酸盐通报,2011,30(3):529-533.
[14] Cayre O,Paunov N,Velev O D.Fabrication of asymmetrically coated colloid particles by micro contact printing techniques[J].Journal of Materials and Chemistry,2003,13(2):2445-2450.
[15] 宋成芝,车永兴,张志广,等.硅烷偶联剂对炭黑/白炭黑增强丁腈橡胶填料网络结构及动态性能的影响[J].合成橡胶工业,2011,34(2):128-132.
[16] Sengloyluan K,Sahakaro K,Dierkes W K.Silica-reinforced tire tread compounds compatibilized by using epoxidized natural rubber[J].European Polymer Journal,2014,51(1):69-79.
[17] 王彦,王颖悟,夏琳,等.杜仲橡胶的水相-有机相法提取及其结构表征[J].橡胶工业,2017,64(11):650-654.
[18] 王彦,夏琳,辛振祥.环氧化杜仲胶改性丁苯橡胶/白炭黑复合材料的制备与性能[J].合成橡胶工业,2018,41(2):115-119.
[19] 梁宁宁.杜仲胶的环氧化改性及其超疏水复合材料的制备[D].青岛:青岛科技大学,2015.
[20] 杨凤,王芳,方庆红,等.乳液法环氧化改性天然杜仲胶[J].高分子材料科学与工程,2015,31(5):56-61.
[21] Xu Tiwen,Jia Zhixin,Luo Yuanfang,et al.Interfacial interaction between the epoxidized natural rubber and silica in natural rubber/silica composites[J].Applied Surface Science,2015,328(2):306–313.
[22] 栗磊,丁乃秀,周海妮,等.白炭黑分散剂对集成橡胶性能的影响[J].橡胶工业,2014,61(6):341-345.
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