纤维素接枝共聚物对聚乳酸结晶性能和拉伸流变性能的影响
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摘要
通过熔融缩聚法制备出含有聚乳酸支链的纤维素接枝共聚物(OLA-g-C),并采用溶液共混法制备一系列聚乳酸(PLA)/OLA-g-C共混物以及对比样聚乳酸/微晶纤维素(MCC)共混物.扫描电镜(SEM)结果表明聚乳酸支链的存在可以提高纤维素在PLA基体中的分散性,抑制团聚现象的出现.在非等温结晶过程中,OLA-g-C和MCC的加入都可以促进PLA的结晶,但是OLA-g-C的促进效果优于MCC,这与OLA-g-C在基体中的分散性良好有关.在等温结晶过程中OLA-g-C可以同时提高PLA的结晶度以及结晶速率,但对其成核机理和生长方式无明显影响.偏光显微镜(POM)观察的结果进一步证明OLA-g-C可以作为成核剂,有效地缩短基体的结晶时间,提高PLA的结晶能力.但是,OLA-g-C的加入却降低了体系的拉伸黏度,这与体系的缠结作用有关.
The polylactic acid(PLA) grafted cellulose copolymer(OLA-g-C) was synthesized by melt copolycondensation of lactic acid with microcrystalline cellulose(MCC),then PLA/OLA-g-C blends and contrast samples PLA/MCC blends were prepared by solution mixing. The results of scanning electron microscopy(SEM) showed that the existence of PLA side chains improved the dispersion of cellulose in PLA matrix and inhibited the agglomeration. In non-isothermal crystallization process,OLA-g-C and MCC both promoted the crystallization ability of PLA,but the promotion effect of OLA-g-C was better than MCC due to the well dispersion of OLA-g-C in PLA matrix. In isothermal crystallization process,OLA-g-C can accelerate the crystallization rate and improve the crystallinity simultaneously,but had no influence on the growth geometry and nucleation type of the crystal of PLA. The results of polarized optical microscopy(POM) further proved that OLA-g-C as the nucleating agent,reduced crystallization time,and enhanced the crystallization ability of PLA. However,the elongational viscosity decreased with the addition of OLA-g-C,which related to the entanglement between OLA-g-C and PLA matrix.
The polylactic acid(PLA) grafted cellulose copolymer(OLA-g-C) was synthesized by melt copolycondensation of lactic acid with microcrystalline cellulose(MCC),then PLA/OLA-g-C blends and contrast samples PLA/MCC blends were prepared by solution mixing. The results of scanning electron microscopy(SEM) showed that the existence of PLA side chains improved the dispersion of cellulose in PLA matrix and inhibited the agglomeration. In non-isothermal crystallization process,OLA-g-C and MCC both promoted the crystallization ability of PLA,but the promotion effect of OLA-g-C was better than MCC due to the well dispersion of OLA-g-C in PLA matrix. In isothermal crystallization process,OLA-g-C can accelerate the crystallization rate and improve the crystallinity simultaneously,but had no influence on the growth geometry and nucleation type of the crystal of PLA. The results of polarized optical microscopy(POM) further proved that OLA-g-C as the nucleating agent,reduced crystallization time,and enhanced the crystallization ability of PLA. However,the elongational viscosity decreased with the addition of OLA-g-C,which related to the entanglement between OLA-g-C and PLA matrix.
引文
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2 Mohanty A K,Misra M,Hinrichsen G.Macromol Mater Eng,2000,276-277(1):1-24
3 Zhao Y,Wang Z,Wang J,Mai H,Yan B,Yang F.J Appl Polym Sci,2004,91(4):2143-2150
4 Kaito T,Myoui A,Takaoka K,Saito N,Nishikawa M,Tamai N,Ohgushi H,Yoshikawa H.Biomaterials,2005,26(1):73-79
5 Lim L T,Auras R,Rubino M.Prog Polym Sci,2008,33(8):820-852
6 Liu Ruilai(刘瑞来),Han Jing(韩静),Chen Xiujuan(陈秀娟),Lei Shenghong(雷声宏),Liu Haiqing(刘海清).Acta Polymerica Sinica(高分子学报),2012,(3):291-298
7 Chen Lu(陈璐),Tang Songchao(唐颂超),Xia Ji(夏季),Pu Wenliang(蒲文亮),Li Rui(李瑞).Acta Polymerica Sinica(高分子学报),2013,(8):1006-1012
8 Saeidlou S,Huneault M A,Li H,Park C B.Prog Polym Sci,2012,37(12):1657-1677
9 Tsuji H,Fukui I.Polymer,2003,44(10):2891-2896
10 Bhardwaj R,Mohanty A K.Biomacromolecules,2007,8(8):2476-2484
11 Li H,Huneault M A.Polymer,2007,48(23):6855-6866
12 Fukushima K,Murariu M,Camino G,Dubois P.Polym Degrad Stab,2010,95(6):1063-1076
13 Suryanegara L,Nakagaito A N,Yano H.Compos Sci Technol,2009,69(7-8):1187-1192
14 Tsuji H,Wada T,Sakamoto Y,Sugiura Y.Polymer,2010,51(21):4937-4947
15 Lan Xiaorong(兰小蓉),Wu Feng(吴枫),Ji Deyun(季得运),Feng Jianmin(冯建民),Liu Zhengying(刘正英),Yang Mingbo(杨鸣波).Acta Polymerica Sinica(高分子学报),2013,(8):949-955
16 Zou Guoxiang(邹国享),Zhang Xin(张鑫),Li Bingjian(李炳健),Zhao Caixia(赵彩霞),Li Jinchun(李锦春).Acta Polymerica Sinica(高分子学报),2012,(9):952-957
17 Liu B,Du Z,Wang X,Xin F,Liu W.Polym Compos,2015,36(11):2123-2134
18 Xu Z,Niu Y,Wang Z,Li H,Yang L,Qiu J,Wang H.ACS Appl Mater Inter,2011,3(9):3744-3753
19 Zhong Y,Zhang Y,Yang J,Li W,Wang Z,Xu D,Chen S,Ding Y.Sci China Chem,2013,56(2):181-194
20 Bai J,Wang J,Wang W,Fang H,Xu Z,Chen X,Wang Z.ACS Sustain Chem Eng,2016,4(1):273-283
21 Lehermeier H J,Dorgan J R.Polym Eng Sci,2001,41(12):2172-2184
22 Wang L,Jing X,Cheng H,Hu X,Yang L,Huang Y.Ind Eng Chem Res,2012,51(30):10088-10099
23 Wang Y,Yang L,Niu Y,Wang Z,Zhang J,Yu F,Zhang H.J Appl Polym Sci,2011,122(3):1857-1865
24 Fang H,Zhang Y,Bai J,Wang Z,Wang Z.RSC Adv,2013,3(23):8783-8795
25 Fang H,Zhang Y,Bai J,Wang Z.Macromolecules,2013,46(16):6555-6565
26 Xu H,Fang H,Bai J,Zhang Y,Wang Z.Ind Eng Chem Res,2014,53(3):1150-1159
27 Mayumi A,Kitaoka T,Wariishi H.J Appl Polym Sci,2006,102(5):4358-4364
28 Yan C,Zhang J,Lv Y,Yu J,Wu J,Zhang J,He J.Biomacromolecules,2009,10(8):2013-2018
29 Zhang Y,Li X,Yang Y,Lan A,He X,Yu M.RSC Adv,2014,4(65):34584-34590
30 Isogai A,Atalla R H.Cellulose,1998,5(4):309-319
31 Luan Y,Wu J,Zhan M,Zhang J,Zhang J,He J.Cellulose,2013,20(1):327-337
32 Dai L,Xiao S,Shen Y,Qin S B,He J.B Korean Chem Soc,2012,33(12):4122-4126
33 Teramoto Y,Nishio Y.Polymer,2003,44(9):2701-2709
34 Pei A,Zhou Q,Berglund L A.Compos Sci Technol,2010,70(5):815-821
35 Dobreva T,Perea J M,Pérez E,Benavente R,García M.Polym Compos,2010,31(6):974-984
36 Song Y,Tashiro K,Xu D,Liu J,Bin Y.Polymer,2013,54(13):3417-3425
37 Pan P,Kai W,Zhu B,Dong T,Inoue Y.Macromolecules,2007,40(19):6898-6905
38 Zhang J,Tashiro K,Tsuji H,Domb A J.Macromolecules,2008,41(4):1352-1357
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40 Rahaman M H,Tsuji H.J Appl Polym Sci,2013,129(5):2502-2517
41 Zhang Ruijing(张瑞静),Shao Chunguang(邵春光),Li Qian(李倩),Wang Mingyou(王明友),Zhang Doudou(张豆豆),Zhang Yang(张阳),Liu Chenggang(刘成刚),Hong Shiming(洪时明),Shen Changyu(申长雨).Acta Polymerica Sinica(高分子学报),2013,(8):1085-1091
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43 Dorgan J R,Janzen J,Clayton M P,Hait S B,Knauss D M.J Rheol,2005,49(3):607-619