二醋酸纤维素与增塑剂熔融体系的制备与表征
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摘要
为大幅降低二醋酸纤维素(CDA)的熔融温度,利用哈克转矩流变仪分别制备了CDA/1-乙基-3-甲基咪唑醋酸盐([EMIM]Ac)、CDA/二甲基亚砜(DMSO)和CDA/[EMIM]Ac/DMSO 3种体系,分析了这3种体系制备过程中温度及转矩与时间的关系,并利用X射线衍射仪、热重分析和流变仪等研究了这3种体系的结构与性能。研究结果表明:离子液体[EMIM]Ac对CDA具有良好的增塑作用,CDA/[EMIM]Ac体系可形成均一相态;DMSO对CDA增塑作用较弱,CDA在DMSO中既不能溶解也不能熔融,其以溶胀态分散在CDA/DMSO体系中;以DMSO代替部分[EMIM]Ac,不仅可降低成本,更能促进[EMIM]Ac的增塑作用;CDA/[EMIM]Ac及CDA/[EMIM]Ac/DMSO 2种体系的热分解温度虽远低于原料CDA,但又远高于它们各自的熔融流动温度,熔融加工稳定性好。
Cellulose diacetate( CDA) has high melting temperature,and is an important derivative of cellulose. In order to significantly reduce the melt processing temperature of CDA,the systems of CDA /1-ethyl-3-methylimidazolium acetate( [EMIM]Ac), CDA / dimethyl sulfoxide( DMSO) and CDA /[EMIM]Ac / DMSO were prepared in HAAKE rheocord. The curves of temperature-time and torque-time in the process of three systems were analyzed,respectively. The structures and performances of the systems were investigated by XRD,TGA and rheometer,respectively. The results show that,ionic liquid[EMIM]Ac is so effective as a plasticizer for CDA that the plasticizing melting system of CDA /[EMIM]Ac is a homogeneous one. The plasticizing effect of DMSO to CDA is weak. CDA can neither dissolve nor melt in DMSO,and it can scatter in the plasticizing system of CDA / DMSO in the swollen state. Replacing of part of [EMIM]Ac with DMSO can not only reduce costs,but also promote plasticizing effect of [EMIM]Ac. The melt processing stability of the plasticizing melting systems of CDA /[EMIM]Ac and CDA /[EMIM]Ac / DMSO is good because their thermal decomposition temperature is well above their melt flow temperature,although their thermal decomposition temperature are lower than that of raw CDA.
Cellulose diacetate( CDA) has high melting temperature,and is an important derivative of cellulose. In order to significantly reduce the melt processing temperature of CDA,the systems of CDA /1-ethyl-3-methylimidazolium acetate( [EMIM]Ac), CDA / dimethyl sulfoxide( DMSO) and CDA /[EMIM]Ac / DMSO were prepared in HAAKE rheocord. The curves of temperature-time and torque-time in the process of three systems were analyzed,respectively. The structures and performances of the systems were investigated by XRD,TGA and rheometer,respectively. The results show that,ionic liquid[EMIM]Ac is so effective as a plasticizer for CDA that the plasticizing melting system of CDA /[EMIM]Ac is a homogeneous one. The plasticizing effect of DMSO to CDA is weak. CDA can neither dissolve nor melt in DMSO,and it can scatter in the plasticizing system of CDA / DMSO in the swollen state. Replacing of part of [EMIM]Ac with DMSO can not only reduce costs,but also promote plasticizing effect of [EMIM]Ac. The melt processing stability of the plasticizing melting systems of CDA /[EMIM]Ac and CDA /[EMIM]Ac / DMSO is good because their thermal decomposition temperature is well above their melt flow temperature,although their thermal decomposition temperature are lower than that of raw CDA.
引文
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[3]SCOTT M,RAHMAN M,BRAZEL C.Application of ionic liquids as low-volatility plasticizers for PMMA[J].European Polymer Journal,2003,39(10):1947-1953.
[4]LI Z X,LIU N,YAO Y B,et al.Thermal behavior of cellulose diacetate melt using ionic liquids as plasticizers[J].RSC Advances,2015,5(2):901-907.
[5]LIU N,ZHANG J W,WANG H P.Plasticization of cellulose diacetate by ionic liquid[J].Advances in Materials Research,2014,936:1002-1006.
[6]朱庆松,韩小进,程春祖,等.壳聚糖在4种咪唑型离子液体中溶解性的研究[J].高分子学报,2011(10):1173-1179.ZHU Qingsong,HAN Xiaojin,CHENG Chunzu,et al.Study on dissolubility of chitosan in four kinds of imidazole-based ionic liquids[J].Acta Polymerica Sinica,2011(10):1173-1179.
[7]孙玉山,徐纪刚,李昭锐,等.新溶剂法纤维素纤维开发概况与展望[J].纺织学报,2014,35(2):126-132.SUN Yushan,XU Jigang,LI Zhaorui,et al.Development survey and outlook of new solvent process regenerated cellulose fibers[J].Journal of Textile Research,2014,35(2):126-132.
[8]HERMANUTZ F,GAHR F,UERDINGEN E,et al.New developments in dissolving and processing of cellulose in ionic liquids[J].Macromol Symposia,2008,262(1):23-27.
[9]李常清,徐梁华,王晓玲,等.残余溶剂DMSO对PAN纤维结构及热性能的影响[J].高分子材料科学与工程,2003,19(4):89-91.LI Changqing,XU Lianghua,WANG Xiaoling,et al.Effect of the remains of dimethyl sulfoxide on the structure and thermal properties of pan precursor[J].Polymer Materials Science and Engineering,2003,19(4):89-91.
[10]许爱荣.阴离子功能化离子液体对生物质原料组分的溶解及选择性分离[D].兰州:兰州大学,2010:89-91.XU Airong.The dissolution and selective seperation for the biomass components with anion-functionalized ionic liquids[D].Lanzhou:Lanzhou University,2010:89-91.
[11]李晓俊.纤维素与聚丙烯腈在离子液体中的溶解于纺丝研究[D].上海:东华大学,2015:41.LI Xiaojun.Study on dissolving and spinning process of cellulose and polyacrylonitrile in ionic liquids[D].Shanghai:Donghua University,2015:41.
[12]郑伟,程博闻,臧洪俊,等.纤维素/氯代-1-丁基-3-甲基咪唑([BMIM]Cl)体系流变性能的研究[J].人造纤维,2007(6):2-5.ZHENG Wei,CHENG Bowen,ZANG Hongjun,et al.Study on rheological property of cellulose/[BMIM]Cl[J].Artificial Fibre,2007(6):2-5.
[13]闫红芹.纤维素/离子液体溶液流变行为的研究[J].纺织学报,2009,30(12):9-12.YAN Hongqin.Study on rheological property of cellulose/ionic liquids[J].Journal of Textile Research,2009,30(12):9-12.