华东师范大学化学与分子工程学院谢美然教授

rongshuxia

谢美然教授 博士生导师
化学与分子工程学院
化学与分子工程学院
联系电话： 021-54340058（O） 办公时间： 周一至周六
传 真： 021-54340058 主页网址： /s/1496/t/17194/main.jspy
办公地点： 化学院419室 电子邮箱： mrxie@chem.ecnu.edu.cn
通讯地址： 上海市闵行区东川路500号


研究方向
    催化聚合新方法，光电纳米高性能聚合物材料。


研究兴趣
        烯烃/炔烃易位聚合及可控聚合，金属卡宾催化剂，聚合物纳米结构的构筑与性能，光电功能高分子，高性能聚合物，杂化橡胶等。


研究课题
主持国家自然科学基金面上项目：
(1) “烯-炔易位聚合构筑有规立构的纳米介电聚合物”(No.21574041)
(2) “离子液体中易位环化聚合及共轭聚乙炔离聚物结构和导电性研究” (No.21374030)
(3) “新型钒卡宾络合物催化易位聚合与聚合物微结构”(No.21074036)
(4) “离子液体负载钌络合物催化环烯烃开环易位聚合”(No.20474017)


主持“杜仲综合利用技术─国家地方联合工程实验室”开放基金重点项目“杜仲胶易位改性和杂化橡胶性能研究”(2016KFR0128)；中国博士后科学基金项目“新型脂环族液体环氧化合物的合成及其在电子封装中的应用”；上海市科委项目“释药可控的顺铂纳米胶束”(No.0952nm05300, 子课题)，上海市科委国际合作项目“超稳定、多功能磁性纳米胶束在癌症早期诊疗中的应用研究”(No.10410710000, 子课题)；横向与企业研发项目“固体核磁共振波谱和动态力学分析的深度测试”(2015FWR0052)，“硅铝粉填充聚合物材料的性能改进研究”(No.48071940)，“羽毛球用PC/ABS材料复合增强”(2015FWR0093)等课题。
    参加国家自然科学基金项目“离心成纤酚醛纤维的起始树脂结构、成纤工艺参数及固化条件对纤维耐热性、耐焰性的影响”(No.50973030)，“梯度共聚物梯度结构的理论与实验表征”(No.20474018)；国家自然科学基金重点项目“高分子共聚物的分子设计和共聚合方法”(No.2934010)；奥地利科学基金会(Fonds zur Förderung der wissenschaftlichen Forschung，FWF)项目“Syntheses and evaluations of heterogeneous catalytic systems based on molybdenum and ruthenium complex for ring-opening metathesis polymerization”；中科院重点项目(No.9904)；湖南省自然科学基金项目“超强吸水性树脂的结构与性能”；广东省自然科学基金项目 (No.980327)；上海市科委纳米专项“医用磁性纳米复合形状记忆聚合物的制备及性质研究”(No.0852nm 03200)，上海市科委科技项目“功能化超小MnO纳米粒的制备及T1造影性能研究”(No.44503510)；高等学校博士学科点专项科研基金 (No.20090076120005)；闵行区校合作项目“可负载癌症药物的新型高分子载体的研制”(No.48100270) 的部分研究工作，以及企业委托研发项目“涂料用聚酯-聚氨酯性能的测定和咨询”(No.48300470)和“光敏垫材料研制”的主要工作。在国内外核心刊物上发表论文80余篇（其中1区、2区及IF3.0以上50多篇），申请和授权发明专利10多件。

社会兼职
        华东师范大学化学院高分子学科组长，教工第四党支部书记。化学院学术委员会、教学委员会和学位委员会委员。湖南“【杜仲综合利用技术】国家-地方联合工程实验室”兼职教授，上海市闵行区领军人才评审专家，闵行区工商联非公有制企业科技顾问，宁波黄泰机电有限公司技术顾问‚上海兰澳生物科技有限公司技术顾问等。
        J Am Chem Soc, Macromolecules‚ Polym Chem, Macromol Rapid Commun, Organometallics‚ React Funct Polym‚ Eur Polym J‚ PolymAdv Tech, Polym Int‚ J Mater Sci, J Appl Polym Sci‚ J Macromol Sci –Pure Appl Chem‚ Science in China Series B: Chem等国内外知名学术刊物论文审稿人。国家自然科学基金项目通讯评议人。

研究论文：
75. Hongfei Li,Cuifang Wang, Xiaojuan Liao,Meiran Xie*, Ruyi Sun*. Hybrid triazolium and ammonium ions-contained hyperbranched polymer with enhanced ionic conductivity, Polymer, 2017, 112, 297-305 (2区).
74. Jie Chen and Meiran Xie*. Synthesis of Ionic Ladderphane-Derived Triblock Copolymer for Dielectric and Electrical Energy Storage Applications, IEEE Transactions on Dielectrics and Electrical Insulation, 2017, 24, accepted.
73. Wenmei Liu, Jie Chen, Dandan Zhou, Xiaojuan Liao,Meiran Xie* and Ruyi Sun*. High-performance dielectric block copolymer with self-assembled superhelical nanotube morphology, Polym. Chem., 2017, 8, 725-734 (2区).
72.  Jianhua Wu, Hongfei Li,Dandan Zhou, Xiaojuan Liao, Meiran Xie,* Ruyi Sun*. Metathesis Cyclopolymerization of Substituted 1,6-Heptadiyne and Dual Conductivity of Doped Polyacetylene Bearing Branched Triazole Pendants, J. Polym. Sci., Part A: Polym. Chem., 2017, 55, 485-494 (3区).
71.  Jianhua Wu, Cuifang Wang, Dandan Zhou, Xiaojuan Liao, Meiran Xie,* Ruyi Sun*. Branched 1,2,3-Triazolium-Functionalized Polyacetylene with Enhanced Conductivity, Macromol. Rapid Commun. 2016, 37,2017-2022 (1区).
70.  Jie Chen, Dandan Zhou, Cuifang Wang, Xiaojuan Liao,Meiran Xie* and Ruyi Sun*. High-performance dielectric ionic ladderphane-derived triblock copolymer with a self-assembled unique nanostructure, RSC Adv., 2016, 6, 88874-88885 (2区).
69  Ruyi Sun,* Hari Krishna Bisoyi, Meiran Xie, Quan Li. Photo and redox dual-stimuli-directed reversible disassembly and reassembly of linear supramolecular polymer formed by orthogonal host-guest molecular recognition, Dyes and Pigments, 2016, 132, 336-341 (2区).
68.  Junxia Chang, Qiuhua Zhao, Le Kang, Haimei Li, Meiran Xie, and Xiaojuan Liao*. Multiresponsive Supramolecular Gel Based on Pillararene-Containing Polymers, Macromolecules, 2016, 49, 2814-2820 (1区).
67.  Junfang Wang, Hongfei Li,Xiaojuan Liao, Meiran Xie* and Ruyi Sun*. Synthesis of triazole-dendronized polyacetylenes by metathesis cyclopolymerization and their conductivity, Polym. Chem., 2016, 7, 4912-4923 (2区).
66.  Jianhua Wu, Yanbin Fu, Wenmei Liu, Xiaojuan Liao, Meiran Xie*, Ruyi Sun*. Synthesis and properties of tricarbazole-functionalized poly(norbornene-dicarboximide), Eur. Polym. J., 2016, 76, 110-121 (3区).
65. Huijing Han, Sha Zhang, Ruyi Sun, Jianhua Wu, Meiran Xie* and Xiaojuan Liao*. Photocrosslinkable Polynorbornene-based Block Copolymer with Enhanced Dielectric and Thermal Properties, Chinese J. Polym. Sci., 2016, 34, 378-389.
64.  Jianhua Wu, Jie Chen, Junfang Wang, Xiaojuan Liao, Meiran Xie* and Ruyi Sun*. Synthesis and conductivity of hyperbranched poly(triazolium)s with various end-capping groups, Polym. Chem., 2016, 7, 633–642 (2区).
63.  Ruyi Sun*, Meiran Xie. Light driven bent linear supramolecular polymer, Tetrahedron, 2015, 71, 3216-3220 (3区).
62.  Xiaojuan Liao,* Lei Guo, Junxia Chang, Sha Liu, Meiran Xie, Guosong Chen*. Thermoresponsive AuNPs Stabilized by Pillararene-Containing Polymers,Macromol. Rapid Commun. 2015, 36, 1492-1497 (1区).
61.  Wenmei Liu, Xiaojuan Liao, Yawei Li, Qiuhua Zhao, Meiran Xie* and Ruyi Sun*. Nanostructured high-performance dielectric block copolymer, Chem. Commun., 2015, 51, 15320-15323 (1区).
60.  Wei Song, Jianhua Wu, Guangda Yang, Huijing Han, Meiran Xie* and Xiaojuan Liao*. Precisely designed perylene bisimide-substituted polyethylene with a high glass transition temperature and an ordered architecture, RSC Adv., 2015, 5, 68765-68772 (2区).
59.  Jianhua Wu, Wenmei Liu, Huijing Han, Ruyi Sun, Meiran Xie* and Xiaojuan Liao*. Hyperbranched poly(triazole) with thermal and metal ion dual stimuli-responsiveness, Polym. Chem., 2015, 6, 4801-4808 (2区).
58.  Mengfang Guo, Ruyi Sun, Huijing Han, Jianhua Wu, Meiran Xie*, and Xiaojuan Liao*. Metathesis Cyclopolymerization of 1,6-Heptadiyne Derivative toward Triphenylamine-Functionalized Polyacetylene with Excellent Optoelectronic Properties and Nanocylinder Morphology, Macromolecules, 2015, 48, 2378-2387 (1区).
57.  Wei Song, Huijing Han, Jianhua Wu, Meiran Xie*. A bridge-like polymer synthesized by tandem metathesis cyclopolymerization and acyclic diene metathesis polymerization, Polym. Chem., 2015, 6, 1118-1126 (2区).
56.  Wei Song, Huijing Han, Xiaojuan Liao, Ruyi Sun, Jianhua Wu, Meiran Xie*. Metathesis Cyclopolymerization of Imidazolium-Functionalized 1,6-Heptadiyne toward Polyacetylene Ionomer, Macromolecules, 2014, 47, 6181-6188 (1区).
55.  Wei Song, Huijing Han, Jianhua Wu, Meiran Xie*. Ladder-like polyacetylene with excellent optoelectronic properties and regular architecture, Chem. Commun., 2014, 50(85), 12899-12902 (1区).
54.  Zewang You, Wei Song, Sha Zhang, Ouyue Jin, Meiran Xie*. Polymeric Microstructures and Dielectric Properties of Polynorbornenes with 3,5-Bis(trifluoromethyl)biphenyl Side Groups by Ring-Opening Metathesis Polymerization, J. Polym. Sci., Part A: Polym. Chem., 2013, 51, 4786-4798 (3区).
53.  谢美然*, 韩会景, 金瓯悦, 杜春霞.含POSS侧基的非环二烯烃易位聚合及离子型杂化聚合物表征, 化学学报, 2013, 71, 1441-1445.
52.  Wuqiong Sun, Xiaohua He,* Chunyan Gao, Xiaojuan Liao, Meiran Xie, Shaoliang Lin* and Deyue Yan. Novel amphiphilic and photo-responsive ABC 3-miktoarm star terpolymers: synthesis, self-assembly and photo-responsive behavior, Polym. Chem., 2013, 4, 1939-1949 (2区).
51.  Zewang You, Danyi Gao, Ouyue Jin, Xiaohua He, Meiran Xie*. High Dielectric Performance of Tactic Polynorbornene Derivatives Synthesized by Ring-Opening Metathesis Polymerization, J. Polym. Sci., Part A: Polym. Chem., 2013, 51, 1292-1301 (3区).
50.  Xiaohua He, Liang Zhong, Xiaomeng Wu, Xin Cai, Meiran Xie, Shaoliang Lin, Deyue Yan. Synthesis and Self-Assembly of Amphiphilic Brush-Dendritic-Linear Poly[poly(ethylene glycol) methyl ether methacrylate]-b-Polyamidoamine-b-Poly(e-caprolactone) Copolymers, J. Polym. Sci., Part A: Polym. Chem., 2012, 50, 2841-2853 (3区).
49.  Ning Wang, Liang Ding, Meiran Xie*. Cyclodextrin-based hyperbranched polymers by acyclic diene metathesis polymerization of an ABn monomer: molecule design, synthesis, and characterization, J. Polym. Res., 2012, 19, 9863, 9937.
48.  Meiran Xie*, Liang Ding, Zewang You, Danyi Gao,Guangda Yang, Huijing Han. Robust Hybrid Nanostructures Comprising Gold and Thiol-Functionalized Polymer Nanoparticles: Facile Preparation, Diverse Morphologies and Unique Properties, J. Mater. Chem., 2012, 22, 14108-14118 (1区).
47.  Liang Ding, Guangda Yang, Meiran Xie*, Danyi Gao, Jiahui Yu*, Yiqun Zhang. More Insight into Tandem ROMP and ADMET Polymerization for Yielding Reactive Long-Chain Highly Branched Polymers and Their Transformation to Functional Polymer Nanoparticles, Polymer, 2012, 53, 333-341 (2区).
46.  Dan Yang, Wei Huang, Xiaohua He, Meiran Xie*. Electromagnetic activation of shape memory copolymer matrix by incorporating ferromagnet, Polym. Int., 2012, 61, 38-42.
45.  Xiaohua He*, Xiaomeng Wu, Chunyan Gao, Kai Wang, Shaoliang Lin, Wei Huang, Meiran Xie, Deyue Yan. Synthesis and self-assembly of a hydrophilic, thermo-responsive poly(ethylene oxide) monomethyl ether-block-poly(acrylic acid)-block-poly(N-isopropylacrylamide) copolymer to form micelles for drug delivery, React. Funct. Polym., 2011,71, 544-552 (2区).
44.  Meiran Xie*, Liya Zhang, Yang Liao,Liang Ding, Chi Zeng, Zewang You. Preparation of Reactive Block Copolymers and Their Transformation to Hollowed Nanostructures, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 4955-4963 (3区).
43.  Jingwei Liu, Yang Liao, Xiaohua He, Jiahui Yu*,Liang Ding, Meiran Xie*. Facile One-Pot Approach for Preparing Functionalized Polymeric Nanoparticle via Ring-Opening Metathesis Polymerization, Macromol. Chem. Phys., 2011, 212, 55-63 (3区).
42.  Dan Yang, Danyi Gao, Chi Zeng, Jisen Jiang, Meiran Xie*. POSS-enhanced shape-memory copolymer of polynorbornene derivate and polycyclooctene through ring-opening metathesis polymerization, React. Funct. Polym., 2011, 71, 1096-1101 (2区).
41.  Liang Ding, Meiran Xie*, Dan Yang, Chunmei Song. Efficient Synthesis of Long-Chain Highly Branched Polymers via One-Pot Tandem Ring-Opening Metathesis Polymerization and Acyclic Diene Metathesis Polymerization, Macromolecules, 2010, 43, 10336-10342 (1区).
40.  Meiran Xie*, Weizhen Wang, Liang Ding, Jingwei Liu, Dan Yang, Ling Wei, Yiqun Zhang. Cleavable Multiblock Copolymer Synthesized by Ring-Opening Metathesis Copolymerization of Cyclooctene and Macrocyclic Olefin and Its Hydrolysis to Give Carboxyl-Telechelic Polymer, J. Polym. Sci., Part A: Polym. Chem., 2010, 48, 380-388 (3区).
39.  Liya Zhang, Chunmei Song,Jiahui Yu*, Dan Yang, Meiran Xie*. One-Pot Synthesis of Polymeric Nanoparticle by Ring-Opening Metathesis Polymerization, J. Polym. Sci., Part A: Polym. Chem., 2010, 48, 5231-5238 (3区).
38.  Liang Ding, Liya Zhang, Kongrong Duan, Dan Yang, Meiran Xie*, Yiqun Zhang. New Azo-Chromophore-Containing Multiblock Poly(butadiene)s Synthesized by the Combination of Ring-Opening Metathesis Polymerization and Click Chemistry, Polymer, 2010, 51, 1285-1292 (2区).
37.  Dan Yang, Wei Huang,Jiahui Yu*,Jisen Jiang, Liya Zhang, Meiran Xie*.A novel shape memory polynorbornene functionalized with poly(ε-caprolactone) side chain and cyano group through ring-opening metathesis polymerization, Polymer, 2010, 51, 5100-5106 (2区).
36.  董文进, 姜继森*, 谢美然. 形状记忆聚(乳酸-乙醇酸) (PLLGA)的制备及性能研究, 化学学报, 2010, 68, 2243-2249.
35.  Meiran Xie*, Huijing Han, Liang Ding, Jiaxin Shi. Promotion of Atom Transfer Radical Polymerization and Ring-Opening Metathesis Polymerization in Ionic Liquids, Polymer Reviews,2009, 49, 315-338 (1区).
34.  Liang Ding, Liya Zhang, Huijing Han, Wei Huang, Chunmei Song, Meiran Xie*, Yiqun Zhang. Hyperbranched Azo-Polymers Synthesized by Acyclic Diene Metathesis Polymerization of an AB2 Monomer, Macromolecules, 2009, 42, 5036-5042 (1区).
33.Meiran Xie*, Jiaxin Shi, Liang Ding, Jinxin Li, Huijing Han, Yiqun Zhang.Cyclic Poly(ε-Caprolactone) Synthesized by Combination of Ring-Opening Polymerization with Ring-Closing Metathesis, Ring Closing Enyne Metathesis, or ‘‘Click’’ Reaction, J. Polym. Sci., Part A: Polym. Chem., 2009, 47, 3022-3033 (3区).
32.  Jingwei Liu, Jinxin Li, Meiran Xie*, Liang Ding, Dan Yang, Liya Zhang. A novel amphiphilic AB2 star copolymer synthesized by the combination of ring-opening metathesis polymerization and atom transfer radical polymerization, Polymer, 2009, 50, 5228-5235 (2区).
31.  谢美然*, 韩会景, 孔毅, 李金欣, 张以群. 两亲性三嵌段共聚物的合成及其自组装行为研究, 高分子学报, 2009, (4), 345-351.
30.  谢美然*, 党靖雅, 史佳鑫, 韩会景, 宋春梅, 黄炜, 张以群. 结构规整的高密度两亲性接枝聚合物刷的合成及其自组装, 化学学报, 2009, 67(8), 869-874.
29.  谢美然*, 马卓, 韩会景, 史佳鑫, 王伟珍, 李金欣, 张以群. 含吡啶配体的钌催化剂合成及离子液体中开环易位聚合反应研究, 高等学校化学学报, 2009, 30, 396-402.
28.  宋春梅*, 薛海丽, 李建奇, 余亦华, 彭敏, 钱雯, 杜冰, 谢美然, 陈群. 端氨基聚(醚-氨酯-酰胺)配体及磁共振成像造影剂研究,高分子学报, 2009, (3), 278-283.
27. Wei Huang*, Shujing Li, Chunping Du, Meiran Xie, Yiqun Zhang, Jie Yin. Synthesis and characterization of new cardo poly(bisbenzoxazole)s containing fluorenylidene unit, Eur. Polym. J., 2009, 45, 3187-3195 (3区).
26. Xiaohua He, Wuqiong Sun, Deyue Yan, Meiran Xie, Yiqun Zhang. Synthesis and Characterization of Side-Chain Liquid Crystalline ABC Triblock Copolymers with p-Methoxyazobenzene Moieties by Atom Transfer Radical Polymerization, J. Polym. Sci., Part A: Polym. Chem., 2008, 46, 4442-4450 (3区).
25. Wei Huang*, Jie Yin, Feng Guo, Yiqun Zhang, Meiran Xie, Xiaohua He. Synthesis and characterization of new cardo poly(bisbenzothiazole-urea)s containing bulky pendant groups, Eur. Polym. J., 2008, 44, 3599-3607 (3区).
24. Ying Shi, Xuelian Qin, Yumei Guo, Meiran Xie, Yiqun Zhang*. The Effect of Activation/Deactivation Processes on the Microcomposition and Microsequence Structure of Controlled/Living Copolymers, Macromol. Theory Simul., 2008, 17, 130-136 (3区).
23.  Meiran Xie*, Jingya Dang, Huijing Han, Weizhen Wang, Jingwei Liu, Xiaohua He, Yiqun Zhang. Well-Defined Brush Copolymers with High Grafting Density of Amphiphilic Side Chains by Combination of ROP, ROMP, and ATRP, Macromolecules, 2008, 41, 9004-9010 (1区).
22.  Meiran Xie*, Huijing Han, Weizhen Wang, Xiaohua He, Yiqun Zhang. Synthesis and Self-assembly of Functionalized Cyclooctene Block Copolymer via ROMP, Macromol. Chem. Phys., 2008, 209, 544-550 (3区).
21.  Meiran Xie*, Yi Kong, Huijing Han, Jiaxin Shi, Liang Ding, Chunmei Song, Yiqun Zhang. Amphiphilic ABA triblock copolymers via combination of ROMP and ATRP in ionic liquid: Synthesis, characterization, and self-assembly, React. Funct. Polym., 2008, 68, 1601-1608 (2区).
20.  韩会景, 刘经纬, 黄炜, 宋春梅, 张以群, 谢美然*. 含咪唑离子盐的环辛烯在离子液体中开环易位聚合的微观研究, 高分子学报, 2008, (5), 492-496.
19.  党靖雅, 陈凤香, 韩会景, 贺小华, 张以群, 谢美然*. 离子液体负载钌络合物的合成及其催化环烯烃开环易位聚合, 高分子学报, 2008, (4), 343-349.
18. Xiaohua He,* Liyuan Liang, Meiran Xie, Yiqun Zhang, Shaoliang Lin, Deyue Yan. Synthesis of Novel Linear PEO-b-PS-b-PCL Triblock Copolymers by the Combination of ATRP, ROP, and a Click Reaction, Macromol. Chem. Phys. 2007, 208, 1797-1802 (3区).
17.  Huijing Han,Fengxiang Chen,Jiahui Yu,Jingya Dang, Zhuo Ma,Yiqun Zhang,Meiran Xie*. Ring-Opening Metathesis Polymerization of Functionalized Cyclooctene by a Ruthenium-Based Catalyst in Ionic Liquid, J. Polym. Sci. Part A: Polym. Chem., 2007, 45, 3986-3993 (3区).
16.  Lingdi Zheng, Fengxiang Chen, Meiran Xie*, Huijing Han, Qing Dai, Yiqun Zhang, Chunmei Song. New polyelectrolytes by ring-opening metathesis polymerization of norbornene derivatives with imidazolium functionalized oligoalkylether pendant groups, React. Funct. Polym., 2007, 67, 19-24 (2区).
15.  Fengxiang Chen, Yi Kong, Huijing Han, Yiqun Zhang, Meiran Xie*. 2,3-Dimethyl-1-[2-(4-pyridyloxy)ethyl]imidazol-1-ium hexafluorophosphate, Acta Cryst.,2007, E63, o1136-o1137.
14.  Aihua Zhu, Zhi Wang, Meiran Xie, Yiqun Zhang*. Synthesis of imidazole end-capped poly(n-butyl methacrylate)s via atom transfer radical polymerization with a functional initiator containing imidazolium group, e-polymers, 2007, no.009, 1-9.
13.陈凤香, 史佳鑫, 韩会景, 党靖雅, 孔毅, 谢美然*. 7-氧杂降冰片烯的官能化及其开环易位聚合, 高分子学报, 2007, (4), 383-388.
12.  国玉梅，许风铃，谢美然，贺小华，宋春梅，张以群*. 活化/失活对原子转移自由基共聚产物微观结构的影响, 高分子学报，2007, (8), 752-756.
11.  Zhonggang Wang*, Meiran Xie, Yunfeng Zhao. Synthesis and properties of novel liquid ester-free reworkable cycloaliphatic diepoxides for electronic packaging application. Polymer, 2003, 44, 923-929 (2区).
10.  Meiran Xie, Zhonggang Wang*. Synthesis and properties of a novel cycloaliphatic epoxide, Macromol. Rapid Commun., 2001, 22, 620-623 (1区).
9.  Meiran Xie, Zhonggang Wang*, Yunfeng Zhao. Synthesis and properties of novel liquid cycloaliphatic trifunctional epoxide, J. Polym. Sci. Part A: Polym. Chem., 2001, 39, 2799-2804 (3区).
8.  谢美然, 王忠刚*, 赵云峰.双官能团液体脂环族环氧化合物的合成与性能,高分子学报, 2001, (4), 517-522.
7.  Rui Chen, Meiran Xie, Qing Wu, Shang-an Lin*. High molecular weight atactic polypropylene synthesized with (pentamethylcyclopentadienyl)tribenzyl titanium activated with MAO, J. Polym. Sci. Part A: Polym. Chem., 2000, 38, 411-415 (3区).
6.  谢美然, 伍青, 林尚安*. 单茂钛/MAO体系催化乙烯/丙烯共聚合研究:Ⅰ乙烯-丙烯共聚物的合成及聚合反应规律研究, 高分子学报, 2000, (6), 774-778.
5.  谢美然, 伍青, 林尚安*. 单茂钛/MAO 体系催化乙烯/丙烯共聚合研究:Ⅱ乙烯-丙烯共聚物的核磁共振分析, 高分子学报, 2000, (6), 779-782.
4.  谢美然, 伍青, 林尚安*. 单茂钛/MAO 体系催化乙烯/丙烯共聚合研究: Ⅲ乙烯-丙烯共聚物的表征与结构分析, 高分子学报, 2000, (6), 783-787.
3.  陈蕊, 谢本恒, 谢美然, 伍青*, 林尚安. 合成高相对分子质量无规弹性聚丙烯的研究,石油炼制与化工, 2000, 31, 51-54.
2.  谢美然, 伍青*. 用茂金属催化体系合成聚丙烯弹性体研究的进展, 高分子通报, 1999, (1), 44-50.
1.  Meiran Xie, Qing Wu, Shang-an Lin*. Synthesis of high-molecular-weight elastomeric polypropylene with half-titanocene/MAO catalyst, Macromol. Rapid Commun., 1999, 20, 167-169 (1区).

beifaxian

聚合物介电材料，因其耐电压击穿强度高、柔性好和成本低廉的特性，在储能电容器中扮演重要角色。但是，传统的商品化介电聚合物，如BOPP，由于介电常数（2.2）低，不能满足高储能密度或小型化储存和转换设备的要求。全聚合物基“分子复合物”，是一种将导电结构（如聚噻吩、聚苯胺、聚乙炔等）通过共价键连接在绝缘的聚合物链上，形成含纳米导电域的全有机聚合物材料。由于绝缘的聚合物链分割包裹导电域并使其结构纳米化，在电场中电荷能够在绝缘-导电域间的纳米界面上积累，从而增强有益的界面极化，增大材料的介电常数；此外，由于相邻导电域间的电荷传导渗透被抑制，降低了漏电流密度，所以最大击穿电压和储能密度仍能保持较高水平。这些优势，使得“分子复合物”在可穿戴电子器件、储能电容器及有机薄膜晶体管等领域有着广阔的应用前景。

  为了提高聚合物的介电常数和储能密度，近年来，华东师范大学化学与分子工程学院谢美然教授课题组利用开环易位聚合（ROMP）、易位环化聚合（MCP）和串联式ROMP-MCP方法，可控合成了一系列具有规整纳米组装结构的双缆（double-stranded）聚降冰片烯、双缆聚乙炔及烯-炔嵌段共聚物（Chem. Commun. 2014, 50, 12899-12902; Macromolecules 2014, 47, 6181-6188; Polym. Chem. 2015, 6, 1118-1126; Macromolecules 2015, 48, 2378-2387; Chem. Commun. 2015, 51, 15320-15323; RSC Adv. 2016, 6, 88874-88885; Polym. Chem. 2017, 8, 725-734; IEEE Transactions on Dielectrics and Electrical Insulation, 2017, 24, 689-696; Mater. Lett. 2017, 208, 95-97; Polymer 2017, 127, 259-268），通过引入极性基团、离子基团、共轭链和结构纳米化，实现了聚合物组成、形貌和极化作用的有效调控及介电储能性的增强。

  在此基础上，谢美然教授与上海交通大学上海市电气绝缘与热老化重点实验室黄溢兴教授等合作，利用易位聚合方法合成了一种基于杂化联双缆聚降冰片烯吡咯烷离子-聚乙炔共轭结构的导电-绝缘嵌段共聚物PBNPF-b-PBHPF-(b-PTNP)2（图1），在溶液中自组装成含杂化导电域的全聚合物基“分子复合物”。比较共聚物薄膜的纳米结构，可以看出，由氯仿溶液得到的聚合物膜，是由无规纳米颗粒组成；而由四氢呋喃溶液制备的聚合物膜，是由形貌规整的纳米空心球紧密堆积而成（图2）。相比无规纳米结构，结构规整的纳米空心球中绝缘区域将导电域有效分隔和形貌纳米化（图3），有利于降低介电损耗，改善介电性能。

图1. 基于杂化联双缆结构的导电-绝缘性嵌段共聚物示意图.

图2. 由 CHCl3 (a,c) 和 THF (b,d)溶液制备的PBNPF30-b-PBHPF30-(b-PTNP100)2 薄膜的SEM (a,b) 和 TEM (c,d) 图像.

图3. 全聚合物基“分子复合物”PBNPF-b-PBHPF-(b-PTNP)2 电容器示意图.

  对聚乙炔链段掺杂不同含量的碘单质，来调控纳米导电域的电导率，研究其对“分子复合物”介电性能的影响。在未掺杂碘单质时，共聚物的介电常数在100Hz时为31，当掺杂聚乙炔摩尔量2.5%的碘时，介电常数增加到33.5；随着碘含量提高，介电常数继续增加并随着碘含量的增多而变缓。掺碘量低于60%，介电损耗在100 Hz频率下仅从0.04增加到0.05；当掺碘量超过60%，介电损耗在102-104 Hz处明显增大（图4）。

图4. 由THF 溶液制备嵌段共聚物PBNPF30-b-PBHPF30-(b-PTNP200)2 薄膜掺杂不同碘含量的介电常数(a)和介电损耗(b).

  由于掺碘量增加，漏电流密度会快速增大，导致击穿强度下降，降低最大储能密度。碘含量低于5%时，最大击穿强度降低幅度小。掺碘量分别为0、2.5和5%，其最大储能密度依次为9.95、8.79和8.99 J/cm3。在最大击穿强度下，三种聚合物膜的储能密度和能量转换效率的综合性能，高于近期文献报道的其它全聚合物介电材料（图5）。

图5. 由THF溶液制备碘掺杂 PBNPF30-b-PBHPF30-(b-PTNP200)2 薄膜的储能密度随电场强度的变化(a); PBNPF30-b-PBHPF30-(b-PTNP200)2 薄膜在场强为370 MV m-1、场强为320 MV m-1和掺碘量2.5%、场强为300 MV m-1和掺碘量5%以及文献中其它聚合物介电材料在场强为400 MV m-1的能量密度和效率(b).

  文于近期以“Rational Design and Modification of High-k Bis(double-stranded) Block Copolymer for High Electrical Energy Storage Capability”为题发表（Chem. Mater. 2018, 30, 1102-1112），第一作者为博士生陈杰，通讯作者为黄兴溢教授和谢美然教授。研究工作得到了国家自然科学基金（No.21574041, 21704025, 21374030）的资助。

  论文链接：https://pubs.acs.org/doi/10.1021/acs.chemmater.7b05042

xiaofengliu

2018年自然科学基金面上项目-模块化成环新方法和环形聚合物结构与性能调控
批准号        21871091        学科分类        生物微量元素化学 ( B010402 )
负责人        谢美然        职称                单位名称        华东师范大学
资助金额        65万元        项目类别        面上项目        起止年月        2019年01月01日 至 2022年12月31日

yiqun

华东师范大学Macromolecules：串联易位聚合诱导自组装成纳米结构嵌段共聚物及可控三唑二酮改性增强介电性能

格拉布催化剂引发的开环易位聚合（ROMP）和易位环化聚合（MCP）是实用、高效的可控聚合技术，其广泛用于合成各种结构明确的聚合物。由聚降冰片烯链段和聚乙炔链段组成的嵌段共聚物，就很容易通过一锅串联ROMP-MCP合成，并且展现出与商用聚合物电容器薄膜相比较高的介电常数和储存/释放的能量密度。这些共聚物能够自组装成不同的纳米结构，如纳米毛细管、空心球纳米结构、超螺旋纳米管和核-壳纳米粒子等，而且导电聚乙炔嵌段是包裹在绝缘聚降冰片烯嵌段中的，有利于制备聚合物分子复合材料以进一步改善介电性能。但是与传统的有机/无机复合材料相比，多数情况下基于这些自组装结构的聚合物材料的介电常数仍较低，难以满足设备的最佳操作要求。为了弥补这一缺陷，一种方法是通过化学修饰将极性分子直接连接到纳米结构的表面，以增加偶极子极化而不损坏组装体内的导电区域。1,2,4-三唑啉-3,5-二酮（TAD）是一种典型的极性分子，然而目前基于TAD的点击化学反应很少用于修饰自组装，尤其是全聚合物纳米结构。

近日，华东师范大学谢美然教授与李亚巍副教授合作，通过串联ROMP-MCP合成得到嵌段共聚物，该聚合物能够在选择性溶剂中自组装成核-壳纳米结构。通过调节TAD进料量可以对嵌段共聚物进行可控修饰，使得在壳中的聚降冰片烯骨架上首先发生TAD与双键的Alder-ene反应，然后在核中带有五元环的聚乙炔（PA）主链上发生级联Alder-ene和Diels-Alder反应。研究发现，含有不同量的脲唑基团的改性嵌段共聚物展现出增强的介电常数（16.2到20.3）和更低的介电损耗（从0.031 到0.009）。该成果以题为"Tandem Metathesis Polymerization-Induced Self-Assembly to Nanostructured Block Copolymer and the Controlled Triazolinedione Modification for Enhancing Dielectric Properties"发表在高分子领域著名期刊Macromolecules上。

本文中，作者通过MCP和串联ROMP-MCP分别合成得到了无规共聚物PSHD-co-PEHD和嵌段共聚物PTNP-b-PSHD。对于PSHD-co-PEHD聚合物，利用4-(3-三氟甲基苯基)-1,2,4-三唑啉-3,5-二酮（FTAD）进行改性时，能够得到含有不饱和六元环的级联Alder-ene和Diels-Alder加成物。对于PTNP-b-PSHD聚合物，当FTAD/双键比率增加到0.5以上时，才能够引发级联的Alder-ene和Diels-Alder反应。当利用FTAD改性共聚物后，介电常数从16.2增加到20.3，而介电损耗从0.031降低到0.009。因此，表明基于TAD点击反应的选择性后功能化作为嵌段共聚物的一种可靠合成途径，在设计功能材料方面具有巨大的应用潜力。

文献链接：Tandem Metathesis Polymerization-Induced Self-Assembly to Nanostructured Block Copolymer and the Controlled Triazolinedione Modification for Enhancing Dielectric Properties (Macromolecules 2018, DOI: 10.1021/acs.macromol.8b01645)