ATRP法制备纤维素-油脂-糠醛热塑性弹性体及性能表征
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摘要
通过"从主链接枝"原子转移自由基聚合(ATRP)法,采用分步聚合策略,成功制备了一种乙基纤维素接枝嵌段共聚物乙基纤维素-g-甲基丙烯酸月桂酯-b-甲基丙烯酸四氢糠基酯(EC-g-P(LMA-b-THFMA))。对聚合物的热力学性能研究发现:共聚物中存在两个热转变,分别发生在-35℃和49～56℃时,表明该共聚物存在微相分离;机械性能分析表明该共聚物具有优异的热塑性弹性体行为,伸长率为89%～147%,拉伸强度为1.7～9.5 MPa。循环拉伸机械性能研究表明EC-g-P(LMA-b-THFMA200)的弹性恢复系数高达92%以上。乙基纤维素接枝共聚物的机械性能具有明显的增强作用,较线性聚合物P(LMA-b-THFMA)的机械强度提高了1.36倍。
The grafted block copolymers, ethyl cellulose-g-lauryl methacrylate-b-tetrahydrofurfuryl methacrylate(EC-g-P(LMA-b-THFMA)) was successfully prepared via "grafting from" atom transfer radical polymerization(ATRP) through two-step polymerization strategy. Thermal property analysis showed that this copolymer had two thermal transitions(-35 ℃ and 49-56 ℃), indicating of the presence of microphase separation in the copolymer. Mechanical property analysis showed that the copolymer had excellent thermoplastic elastomer behavior with the elongation of 89%-147% and tensile strength of 1.7-9.5 MPa. The cycilic tensile mechanical properties analysis indicated that the elastic recovery of EC-g-P(LMA-b-THFMA200) was more than 92%. Compared with the linear block polymer P(LMA-b-THFMA), it could be found that the introduction of cellulose significantly enhanced the mechanical properties of graft copolymer. The mechanical strength of graft copolymer was increased by 1.36 times while compared with that of P(LMA-b-THFMA).
The grafted block copolymers, ethyl cellulose-g-lauryl methacrylate-b-tetrahydrofurfuryl methacrylate(EC-g-P(LMA-b-THFMA)) was successfully prepared via "grafting from" atom transfer radical polymerization(ATRP) through two-step polymerization strategy. Thermal property analysis showed that this copolymer had two thermal transitions(-35 ℃ and 49-56 ℃), indicating of the presence of microphase separation in the copolymer. Mechanical property analysis showed that the copolymer had excellent thermoplastic elastomer behavior with the elongation of 89%-147% and tensile strength of 1.7-9.5 MPa. The cycilic tensile mechanical properties analysis indicated that the elastic recovery of EC-g-P(LMA-b-THFMA200) was more than 92%. Compared with the linear block polymer P(LMA-b-THFMA), it could be found that the introduction of cellulose significantly enhanced the mechanical properties of graft copolymer. The mechanical strength of graft copolymer was increased by 1.36 times while compared with that of P(LMA-b-THFMA).
引文
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[2]JIANG F,WANG Z,QIAO Y,et al. A novel architecture toward third-generation thermoplastic elastomers by a grafting strategy[J]. Macromolecules,2013,46(12):4772-4780.
[3]HERMIS I,JIMMY W M A,HADJICHRISTIDIS N. Regular comb polystyrenes and graft polyisoprene/polystyrene copolymers with double branches("centipedes"). Quality of(1,3-phenylene)bis(3-methyl-1-phenylpentylidene)dilithium initiator in the presence of polar additives[J]. Macromolecules,1998,31(19):6697-6701.
[4]SCHNEIDER Y,LYND N A,KRAMER E J,et al. Novel elastomers prepared by grafting n-butyl acrylate from polyethylene macroinitiator copolymers[J]. Macromolecules,2009,42(22):8763-8768.
[5]SHEN D,YU H,HUANG Y. Densely grafting copolymers of ethyl cellulose through atom transfer radical polymerization[J]. Journal of Polymer Science Part A:Polymer Chemistry,2005,43(18):4099-4108.
[6]YU J,WANG C,WANG J,et al. In situ development of self-reinforced cellulose nanocrystals based thermoplastic elastomers by atom transfer radical polymerization[J]. Carbohydr Polym,2016,141:143-150.
[7]YU J,LIU Y,LIU X,et al. Integration of renewable cellulose and rosin towards sustainable copolymers by "grafting from" ATRP[J]. Green Chemistry,2014,16(4):1854-1864.
[8]LIU Y,LI Y,CHEN H,et al. Water-induced shape-memory poly(D,L-lactide)/microcrystalline cellulose composites[J]. Carbohydrate Polymers,2014,104(1):101-108.
[9]卢传巍,刘少锋,王春鹏,等. 基于纤维素-糠醛-油脂的热塑性材料的合成和性能表征[J]. 林产化学与工业,2017,37(6):43-48. LU C W,LIU S F,WANG C P,et al. Synthesis and characterization of thermoplastic materials derived from cellulose,furfural and grease[J]. Chemistry and Industry of Forest Products,2017,37(6):43-48.
[10]YU J,WANG J,WANG C,et al. UV-absorbent lignin-based multi-arm star thermoplastic elastomers[J]. Macromolecular rapid communications,2015,36(4):398-404.
[11]LIU Y,YAO K,CHEN X,et al. Sustainable thermoplastic elastomers derived from renewable cellulose,rosin and fatty acids[J]. Polymer Chemistry,2014,5(9):3170-3181.
[12]AND D P C,MANDAL B M. Triblock thermoplastic elastomers with poly(lauryl methacrylate) as the center block and poly(methyl methacrylate) or poly(tert-butyl methacrylate) as end blocks. Morphology and thermomechanical properties[J]. Macromolecules,2006,39(26):9192-9200.
[13]YU J,LU C,WANG C,et al. Sustainable thermoplastic elastomers derived from cellulose,fatty acid and furfural via ATRP and click chemistry[J]. Carbohydrate Polymers,2017,176:83-90.
[14]YOO P J,AND K Y S,HONG H L. Short- and long-range interactions in thin films of polymer blends in microchannels[J]. Macromolecules,2002,35(8):3205-3212.