马来酸接枝稀土异戊橡胶的制备及结构表征
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摘要
采用溶液接枝改性法制备了马来酸接枝异戊橡胶(IR-g-MA)。通过红外光谱(FTIR)和核磁共振氢谱(~1H-NMR)表征接枝产物结构,采用化学滴定法测试产物的接枝率。通过不同引发剂活性的比较,发现在己烷溶剂中,过氧化氢对孟烷引发剂具有良好的溶解性,接枝反应活性较高。根据改性前后产物的结构分析,探讨了自由基接枝机理,研究认为马来酸基团接枝在异戊橡胶的侧甲基碳原子上。
Maleic acid grafted polyisoprene rubber(IR-g-MA)was prepared by solution grafting modification reaction.The molecular structures of IR-g-MA were characterized by the measurement method of FTIR and ~1H-NMR and the grafting ratio of MIR was determined by chemical titration method.Comparison of the activities of different initiators,it was found that the grafting activity of the p-menthane hydroperoxide initiator with good solubility was higher in the hexane solvent.The related modification reaction mechanism was presumed by analysis of the structure of IR and IR-g-MA.The grafting reaction follows the radical grafting reaction mechanism,and MA is grafted onto the side methyl carbon atoms of the IR molecular chain.
Maleic acid grafted polyisoprene rubber(IR-g-MA)was prepared by solution grafting modification reaction.The molecular structures of IR-g-MA were characterized by the measurement method of FTIR and ~1H-NMR and the grafting ratio of MIR was determined by chemical titration method.Comparison of the activities of different initiators,it was found that the grafting activity of the p-menthane hydroperoxide initiator with good solubility was higher in the hexane solvent.The related modification reaction mechanism was presumed by analysis of the structure of IR and IR-g-MA.The grafting reaction follows the radical grafting reaction mechanism,and MA is grafted onto the side methyl carbon atoms of the IR molecular chain.
引文
[1]刘洪涛,刘晓洪,周彦豪,等.橡胶化学接枝改性的研究进展[J].特种橡胶制品,2005,26(3):58-61.
[2]BRYDSON J A.橡胶化学[M].王梦姣,戴辉松,曾泽新,等译.北京:化学工业出版社,1985:153-181.
[3]董智贤,周彦豪.马来酸酐接枝天然橡胶的制备及应用研究[J].弹性体,2010,20(2):10-15.
[4]曾铮,任文坛,徐驰,等.接枝天然橡胶对纤维素纤维增强天然橡胶复合材料的增容作用[J].合成橡胶工业,2009,32(1):38-41.
[5]ZENG Z,REN W T,XU C,et al.Maleated natural rubber prepared through mechanochemistry and its coupling effects on natural rubber/cotton fiber composites[J].Journal Polymer Research,2010,17(2):213-219.
[6]CARONE JR E,KOPCAK U,GONVALVES M C,et al.In situ compatibilization of polyamide 6/natural rubber blends with maleic anhydride[J].Polymer,2000,41(15):5929-5935.
[7]NAKASON C,KACSMAN A,HOMSIN S,et al.Rheological and curing behavior of reactive blending.I.maleated natural rubber-cassava starch[J].Journal of Applied Polymer Science,2001,81:2803-2813.
[8]TRIPATHY A R,MORIN J E,WILLIAMS D E,et a1.Anovel approach to improving the mechanical properties in recycled vulcanized natural rubber and its mechanism[J].Macromolecules,2002,35(12):4616-4627.
[9]魏福庆,刘义,王卓妮,等.马来酸酐和苯乙烯接枝改性对天然橡胶/聚丙烯共混物物理机械性能的影响[J].合成橡胶工业,2007,30(1):17-20.
[10]NAKASON C,SAIWARI S,KAESAMAN A.Thermoplastic vulcanizates based on maleated natural rubber/polypropylene blends:Effect of blend ratios on rheological,mechanical,and morphological properties[J].Polymer Engineering&Science,2006,46(5):594-600.
[11]NAKAR A K,DE S K,BHOWMICK A K.Thermoplastic elastomeric composition based on maleic anhydridegrafted ground rubber tire[J].Journal of Applied Polymer Science,2002,84(2):370-378.
[12]MACHADO A V,COVAS J A,VAN DUIN M.Effect of polyolefin structure on maleic anhydride grafting[J].Polymer,2001,42(8):3549-3655.
[13]董智贤,周彦豪,谭丽霞,等.马来酸溶液法接枝改性天然橡胶的研究[J].弹性体,2004,14(5):1-5.
[14]NAKASON C,KAESAMAN A,SUPASANTHITIKUL P.The grafting of maleic anhydride onto natural rubber[J].Polymer Testing,2004,23(1):35-41.
[15]SWALAO J,PHINYOCHEEP P.Influence of styrene on grafting efficiency of maleic anhydride onto natural rubber[J].Journal of Applied Polymer Science,2005,95(1):28-38.
[16]何丽霞.马来酸酐接枝稀土异戊橡胶接枝率的测试方法[J].功能高分子学报,2015,28(1):57-61.
[17]ZHANG L,NI X F,SUN W L,et al.Polymerization of isoprene catalyzed by neodymium heterocyclic Schiff base complex[J].Chinese Chemical Letter,2008,19(6):734-738.
[18]金钟,罗筑,向坤,等.马来酸酐接枝天然橡胶的研究进展[J].弹性体,2015,25(1):91-96.
[2]BRYDSON J A.橡胶化学[M].王梦姣,戴辉松,曾泽新,等译.北京:化学工业出版社,1985:153-181.
[3]董智贤,周彦豪.马来酸酐接枝天然橡胶的制备及应用研究[J].弹性体,2010,20(2):10-15.
[4]曾铮,任文坛,徐驰,等.接枝天然橡胶对纤维素纤维增强天然橡胶复合材料的增容作用[J].合成橡胶工业,2009,32(1):38-41.
[5]ZENG Z,REN W T,XU C,et al.Maleated natural rubber prepared through mechanochemistry and its coupling effects on natural rubber/cotton fiber composites[J].Journal Polymer Research,2010,17(2):213-219.
[6]CARONE JR E,KOPCAK U,GONVALVES M C,et al.In situ compatibilization of polyamide 6/natural rubber blends with maleic anhydride[J].Polymer,2000,41(15):5929-5935.
[7]NAKASON C,KACSMAN A,HOMSIN S,et al.Rheological and curing behavior of reactive blending.I.maleated natural rubber-cassava starch[J].Journal of Applied Polymer Science,2001,81:2803-2813.
[8]TRIPATHY A R,MORIN J E,WILLIAMS D E,et a1.Anovel approach to improving the mechanical properties in recycled vulcanized natural rubber and its mechanism[J].Macromolecules,2002,35(12):4616-4627.
[9]魏福庆,刘义,王卓妮,等.马来酸酐和苯乙烯接枝改性对天然橡胶/聚丙烯共混物物理机械性能的影响[J].合成橡胶工业,2007,30(1):17-20.
[10]NAKASON C,SAIWARI S,KAESAMAN A.Thermoplastic vulcanizates based on maleated natural rubber/polypropylene blends:Effect of blend ratios on rheological,mechanical,and morphological properties[J].Polymer Engineering&Science,2006,46(5):594-600.
[11]NAKAR A K,DE S K,BHOWMICK A K.Thermoplastic elastomeric composition based on maleic anhydridegrafted ground rubber tire[J].Journal of Applied Polymer Science,2002,84(2):370-378.
[12]MACHADO A V,COVAS J A,VAN DUIN M.Effect of polyolefin structure on maleic anhydride grafting[J].Polymer,2001,42(8):3549-3655.
[13]董智贤,周彦豪,谭丽霞,等.马来酸溶液法接枝改性天然橡胶的研究[J].弹性体,2004,14(5):1-5.
[14]NAKASON C,KAESAMAN A,SUPASANTHITIKUL P.The grafting of maleic anhydride onto natural rubber[J].Polymer Testing,2004,23(1):35-41.
[15]SWALAO J,PHINYOCHEEP P.Influence of styrene on grafting efficiency of maleic anhydride onto natural rubber[J].Journal of Applied Polymer Science,2005,95(1):28-38.
[16]何丽霞.马来酸酐接枝稀土异戊橡胶接枝率的测试方法[J].功能高分子学报,2015,28(1):57-61.
[17]ZHANG L,NI X F,SUN W L,et al.Polymerization of isoprene catalyzed by neodymium heterocyclic Schiff base complex[J].Chinese Chemical Letter,2008,19(6):734-738.
[18]金钟,罗筑,向坤,等.马来酸酐接枝天然橡胶的研究进展[J].弹性体,2015,25(1):91-96.