Meiran Xie

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Name: 谢美然; Xie, MeiRan

Organization: East China Normal University , China

Department: Department of Chemistry

Title: Professor(PhD)

TOPICS

Polymer

Stimuli Responsive Polymers Polyesters Stimuli Responsive Polymers Photo Responsive Polymers

Chemicals
References

A high-performance dielectric block copolymer with a self-assembled superhelical nanotube morphology

Co-reporter:Wenmei Liu;Jie Chen;Dandan Zhou;Xiaojuan Liao;Ruyi Sun

Polymer Chemistry (2010-Present) 2017 vol. 8(Issue 4) pp:725-734

Publication Date(Web):2017/01/24

DOI:10.1039/C6PY01571A

A block copolymer consisting of functional polynorbornene (PNBE) and polyacetylene (PA) segments was synthesized by tandem metathesis polymerization, and self-assembled into a superhelical nanotube morphology from achiral building blocks. Bearing insulated PNBE and conductive PA segments with unique nanostructures, the block copolymers displayed high dielectric permittivities of 25–29, low dielectric losses of 0.03–0.04, and excellent stored/released energy densities of 2.0–1.9/1.7–1.2 J cm−3 under the breakdown fields of 270–200 MV m−1, due to strong dipolar and nanointerfacial polarizations as well as stereoregular chain microstructure contributions. This strategy provided a new way for the development of advanced nanodielectric materials.

Double-stranded block copolymer with dual-polarized linker for improving dielectric and electrical energy storage performance

Co-reporter:Jie Chen, Cheng Long, Hongfei Li, Huijing Han, Ruyi Sun, Meiran Xie

Polymer 2017 Volume 127(Volume 127) pp:

Publication Date(Web):3 October 2017

DOI:10.1016/j.polymer.2017.09.011

•The double-stranded ionic block copolymers are synthesized and self-assembled into the hollow sphere nanostructure.•The block copolymers display high dielectric constant, low dielectric loss, and enhanced energy density.•The excellent dielectric properties of copolymers are attributed to the multiple polarizations and regular nanostructure.The double-stranded block copolymers containing ionic conductive and strong polar segments were synthesized by ring-opening metathesis polymerization, and self-assembled into the hollow sphere nanostructure. These block copolymers displayed high dielectric constant of 25, low dielectric loss of 0.02, enhanced stored/released energy density of 2.60/2.38 J cm−3 at 245 MV m−1, and good charge-discharge efficiency of 91.5%, which were much better than those of double-stranded block copolymers without the strong polar substituents on the aromatic linker. The excellent dielectric properties of copolymers were attributed to the combination of strong dipolar, ionic, and interfacial polarizations, as well as the well-defined nanostructure to effectively inhibit the leakage current of the conductive domains by the insulating blocks.Download high-res image (309KB)Download full-size image

Metathesis cyclopolymerization of substituted 1,6-heptadiyne and dual conductivity of doped polyacetylene bearing branched triazole pendants

Co-reporter:

Journal of Polymer Science Part A: Polymer Chemistry 2017 Volume 55(Issue 3) pp:485-494

Publication Date(Web):2017/02/01

DOI:10.1002/pola.28430

ABSTRACTThe branched triazole group is synthesized by click chemistry via a controlled approach of slow addition of AB2 compound to a B2 core, and used as the substituent for 1,6-heptadiyne monomer. Metathesis cyclopolymerization of monomer is performed well in dichloromethane without the weakly coordinating additive, indicating that the branched triazole itself can stabilize the living propagating chain, to generate branched triazole pendant-contained polyacetylene with trans-double bonds and five-membered ring repeating units along the conjugated backbone. The LiTFSI doped polyacetylenes display ionic conductivities of 2.5–1.8 × 10−6 S cm−1; by further doping with iodine, polyacetylenes show the improved ionic and electronic conductivities of 1.3 × 10−5 and 2.1 × 10−7 S cm−1 at 30 °C, respectively. Therefore, these doped polyacetylenes may act as the new electrolyte materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 485–494

Multiple polarizations and nanostructure of double-stranded conjugated block copolymer for enhancing dielectric performance

Co-reporter:Jie Chen, Hongfei Li, Huijing Han, Ruyi Sun, Meiran Xie

Materials Letters 2017 Volume 208(Volume 208) pp:

Publication Date(Web):1 December 2017

DOI:10.1016/j.matlet.2017.05.033

•The double-stranded conjugated triblock metathesis copolymers were synthesized.•The copolymers self-assembled into well-defined nanostructure.•The dipolar, electronic, and interfacial polarizations were combined.•The copolymers displayed excellent dielectric properties.The double-stranded conjugated triblock copolymers are synthesized by tandem metathesis cyclopolymerization and ring-opening metathesis polymerization. They display high permittivity of 28–26, low dielectric loss of 0.06–0.02, and good stored/released energy density of 2.96–2.89/2.58–2.75 J cm−3 at 245 MV m−1 accompanied with the excellent charge-discharge efficiency of 87.2–95.2% when the copolymers self-assemble into a core-shell nanostructure, which are better than those of both homopolymer and copolymers without nanostructure.Download high-res image (273KB)Download full-size image

Synthesis and conductivity of hyperbranched poly(triazolium)s with various end-capping groups

Co-reporter:Jianhua Wu, Jie Chen, Junfang Wang, Xiaojuan Liao, Meiran Xie and Ruyi Sun

Polymer Chemistry 2016 vol. 7(Issue 3) pp:633-642

Publication Date(Web):17 Nov 2015

DOI:10.1039/C5PY01735A

A series of novel hyperbranched poly(triazolium)s with different terminal groups were synthesized by alkylation and anion exchange reactions of the corresponding hyperbranched poly(triazole)s, which were obtained from an AB2-type monomer via Cu(I)-catalyzed azide–alkyne cycloaddition polymerization. The hyperbranched poly(triazolium)s showed high thermal stability with decomposition temperatures of 328–361 °C, and good flexibility, with glass transition temperatures (Tg) ranging from −6.2 to −14.9 °C. Among them, an oligo(ethylene glycol)-terminated hyperbranched poly(triazolium) presented the lowest Tg of −14.9 °C, the highest ionic conductivity (7.70 × 10−6 S cm−1 at 30 °C and 1.02 × 10−3 S cm−1 at 110 °C) and a wide electrochemical stability window of 6.0 V. Therefore, these hyperbranched poly(triazolium)s could act as new electrolyte materials.

Synthesis of triazole-dendronized polyacetylenes by metathesis cyclopolymerization and their conductivity

Co-reporter:Junfang Wang, Hongfei Li, Xiaojuan Liao, Meiran Xie and Ruyi Sun

Polymer Chemistry 2016 vol. 7(Issue 30) pp:4912-4923

Publication Date(Web):27 Jun 2016

DOI:10.1039/C6PY00724D

A series of dendronized polyacetylenes with trans-double bond and five-membered ring backbones were prepared by metathesis cyclopolymerization. The dendronized polymers had good thermal stability with a highest decomposition temperature of 330 °C, and excellent electrochemical stability with a broad electrochemical stability window of 6.0 V. Meanwhile, the flexibility of the dendronized pendants make the polymers have a rigid conjugated backbone exhibiting a lowest glass transition temperature of −22.2 °C. After doping with different ratios of LiTFSI, the ionic conductivity of the polymers was higher than that of their intrinsic ones, and the highest ionic conductivity of the polymers reached 4.3 × 10−6 S cm−1 at 30 °C.

Synthesis and properties of tricarbazole-functionalized poly(norbornene-dicarboximide)

Co-reporter:Jianhua Wu, Yanbin Fu, Wenmei Liu, Xiaojuan Liao, Meiran Xie, Ruyi Sun

European Polymer Journal 2016 Volume 76() pp:110-121

Publication Date(Web):March 2016

DOI:10.1016/j.eurpolymj.2016.01.037

•A series of poly(norbornene-dicarboximide)s were synthesized by ROMP.•Introducing various acceptors to tricarbazole can achieve different color emission.•The HOMO levels of polymers are close to the most common hole injection materials.•The LUMO level of polymer with the cyano group is very close to the material of Alq3.•Polymers possess high thermal stability with decomposition temperature over 400 °C.A series of poly(norbornene-dicarboximide)s with donor–acceptor pendants were synthesized by ring-opening metathesis polymerization, and their photophysical and thermal properties have been investigated. By linking different electron-withdrawing groups to electron-donating tricarbazole on the side chain of poly(norbornene) backbone, the polymers displayed various fluorescence emission color as purplish blue (418 nm), greenish blue (489 nm), green (515 nm), and orange yellow (594 nm). The fluorescence quantum yield of polymer bearing tricarbazole-aldehyde group in CHCl3 was reached to 0.42. The highest occupied molecular orbital level of polymers was close to −5.3 eV, and the lowest unoccupied molecular orbital varied between −2.34 and −3.02 eV. All polymers exhibited high thermal stability with decomposition temperature exceeding 400 °C.

Photocrosslinkable polynorbornene-based block copolymers with enhanced dielectric and thermal properties

Co-reporter:Hui-jing Han;Sha Zhang;Ru-yi Sun;Jian-hua Wu

Chinese Journal of Polymer Science 2016 Volume 34( Issue 3) pp:378-389

Publication Date(Web):2016 March

DOI:10.1007/s10118-016-1753-0

Block copolymers poly(endo-N-3,5-bis(trifluoromethyl)biphenyl-norbornene-pyrrolidine)-block-poly(exo-N-(cinnamoyloxyethyl)-7-oxanorborn-5-ene-2,3-dicarboximide) (endo-PTNP-b-exo-PCONBI) and poly(exo-N-3,5-bis(trifluoromethyl)biphenyl-norbornene-pyrrolidine)-block-poly(exo-N-(cinnamoyloxyethyl)-7-oxanorborn-5-ene-2,3-dicarboximide) (exo-PTNP-b-exo-PCONBI) were synthesized by ring-opening metathesis polymerization. The endo- or exo-PTNP served as the high dielectric functional chain, and exo-PCONBI acted as the crosslinking segment. The endo-PTNP-b-exo-PCONBI, in which endo-PTNP has a high content of trans double bond and adopts isotactic configuration, shows a dielectric constant (ε) of 15.5, whereas exo-PTNP-b-exo-PCONBI, in which exo-PTNP has 67% trans double bonds and atactic microstructure, displays relatively low ε of 7.1. The cinnamate groups in exo-PCONBI were crosslinked to form three-dimensional network by cycloaddition reaction under UV irradiation. Exposed to UV-light for 10 min, the cinnamate group in polymer films has a crosslinking conversion of 36%, as determined by UV-Vis absorption measurements. By photocrosslinking, the polymer film has an increased ε of 16.6, a dielectric loss of 0.03, an elevated glass-transition temperature of 137 °C, and an enhanced decomposition temperature of 405 °C, compared to those of polymer films without irradiation.

Nanostructured high-performance dielectric block copolymers

Co-reporter:Wenmei Liu, Xiaojuan Liao, Yawei Li, Qiuhua Zhao, Meiran Xie and Ruyi Sun

Chemical Communications 2015 vol. 51(Issue 83) pp:15320-15323

Publication Date(Web):26 Aug 2015

DOI:10.1039/C5CC05307B

A new type of insulating–conductive block copolymer was synthesized by metathesis polymerization. The copolymer can self-assemble into unique nanostructures of micelles or hollow spheres. It exhibits a high dielectric constant, low dielectric loss, and high stored/released energy density due to the strong dipolar and nano-interfacial polarization contributions.

Hyperbranched poly(triazole) with thermal and metal ion dual stimuli-responsiveness

Co-reporter:Jianhua Wu, Wenmei Liu, Huijing Han, Ruyi Sun, Meiran Xie and Xiaojuan Liao

Polymer Chemistry 2015 vol. 6(Issue 26) pp:4801-4808

Publication Date(Web):26 May 2015

DOI:10.1039/C5PY00710K

Oligo(ethylene glycol)-terminated hyperbranched poly(triazole) (hb-PTA-OEG) with thermal and metal ion dual stimuli-responsiveness was synthesized by Cu(I)-catalyzed azide–alkyne cycloaddition polymerization, which possessed a high molecular weight (Mn = 203 kDa) and good thermal properties (Td = 367 °C, Tg = −14.1 °C). Importantly, hb-PTA-OEG exhibited a relatively low cloud point (CP) temperature ranging from 34.4 to 31.1 °C as the concentration was increased from 0.02 to 2.0 wt%. Simultaneously, hb-PTA-OEG has the ability to coordinate with various metal ions, and the type of metal ions influenced the CP of hb-PTA-OEG solution to some extent as a result of their different association strengths with the polymer, particularly, Ag+ ion showed a conspicuous contribution to increasing the CP among the several selected ions. As a result, hb-PTA-OEG can act as an absorber of metal ions, and the selective absorption of Ag+ ion could be reached by tuning temperature.

A bridge-like polymer synthesized by tandem metathesis cyclopolymerization and acyclic diene metathesis polymerization

Co-reporter:Wei Song, Huijing Han, Jianhua Wu and Meiran Xie

Polymer Chemistry 2015 vol. 6(Issue 7) pp:1118-1126

Publication Date(Web):28 Oct 2014

DOI:10.1039/C4PY01229A

A facile synthesis of a novel bridge-like polymer was accomplished by the combined procedures of metathesis cyclopolymerization (MCP) and acyclic diene metathesis (ADMET) polymerization. A telechelic double-stranded polyacetylene (PA) with two terminal alkenyl groups was firstly prepared through the third generation Grubbs’ catalyst-mediated chain terminating MCP of bis(1,6-heptadiyne), containing a perylene bisimide (PBI) segment, in the presence of 1,4-bis(10-undecenyloxy)-cis-2-butene. A symmetrical triolefinic ether acted as the functional terminating agent, and was then utilized as the macromonomer in subsequent ADMET polymerization to yield the resultant bridge-like polymer, consisting of the nonconjugated polyolefin backbone and the separated pier-like double-stranded PA. The molecular weight of the product increased (25.2–122.4 kDa) as the reaction time was prolonged, and there was a relatively broad polydispersity index (PDI = 1.41–1.75). The bridge-like polymer can assemble into an ordered ladder-like architecture and a fence-like ribbon morphology, and displays excellent thermal stability, with a Td of above 300 °C and a high Tg between 175 and 189 °C, which is important for applications in devices.

Precisely designed perylene bisimide-substituted polyethylene with a high glass transition temperature and an ordered architecture

Co-reporter:Wei Song, Jianhua Wu, Guangda Yang, Huijing Han, Meiran Xie and Xiaojuan Liao

RSC Advances 2015 vol. 5(Issue 84) pp:68765-68772

Publication Date(Web):03 Aug 2015

DOI:10.1039/C5RA10049F

Acyclic diene metathesis polymerization of a structurally symmetrical perylene bisimide (PBI)-containing α,ω-diene has been performed, yielding an unsaturated polymer with increased molecular weight (Mn = 21.2–87.6 kDa) and decreased polydispersity index (PDI = 2.31–1.76) as the reaction time was prolonged. The subsequent hydrogenation of the as-synthesized polymer was readily accomplished, affording the desired polyethylene (PE) with a saturated backbone and precisely repeating substituted bulky PBI branches. This PBI-substituted PE derivative displayed high glass transition temperatures (Tg = 51.8–75.8 °C), a relatively wide range of light absorption (λ = 230–590 nm), and a highly ordered architecture, which should facilitate electron mobility and be suitable for utilization in optoelectronic devices. It can therefore serve as a superior model for simple construction of functional PE polymers with precisely repeating bulky branches and a soluble PBI polymer with an ordered architecture.

Metathesis Cyclopolymerization of 1,6-Heptadiyne Derivative toward Triphenylamine-Functionalized Polyacetylene with Excellent Optoelectronic Properties and Nanocylinder Morphology

Co-reporter:Mengfang Guo, Ruyi Sun, Huijing Han, Jianhua Wu, Meiran Xie, and Xiaojuan Liao

Macromolecules 2015 Volume 48(Issue 8) pp:2378-2387

Publication Date(Web):April 9, 2015

DOI:10.1021/acs.macromol.5b00379

Metathesis cyclopolymerization of 1,6-heptadiyne derivatives is readily utilized to synthesize triphenylamine-functionalized polyacetylenes (TPA-PAs) by a third-generation Grubbs catalyst, which selectively generated TPA-PAs with a five-membered ring and all-trans microstructure. The TPA pendants endowed PAs with good solubility and excellent optoelectronic properties (maximum absorption wavelength of 592–605 nm in CHCl3, HOMO level of around −5.04 eV, and energy bandgap of 1.82–1.77 eV). When bis-TPA side group was introduced into the PA backbone, the resultant polymer, poly(M2), displayed desirable oxidative stability (up to 30 days stored in THF) and high fluorescence quantum yield (up to 12.3%) in the family of PA derivatives. In addition, poly(M2) could spontaneously self-assemble into the nanocylinder architecture without requiring any tedious postsynthetic treatments. This is the first report that the rigid and immobile conjugated PA segment assembled into the novel cylindrical nanostructure with the aid of π–π interaction of TPA side group.

Ladder-like polyacetylene with excellent optoelectronic properties and regular architecture

Co-reporter:Wei Song, Huijing Han, Jianhua Wu and Meiran Xie

Chemical Communications 2014 vol. 50(Issue 85) pp:12899-12902

Publication Date(Web):29 Aug 2014

DOI:10.1039/C4CC05524A

Novel double-stranded polyacetylene with a perylene bisimide bridge has been efficiently synthesized by metathesis cyclopolymerization of bis(1,6-heptadiyne) derivatives, and exhibited good solubility, highly thermal and oxidative stability, low LUMO energy levels, narrow bandgaps, and regular ladder-like architecture.

Metathesis Cyclopolymerization of Imidazolium-Functionalized 1,6-Heptadiyne toward Polyacetylene Ionomer

Co-reporter:Wei Song, Huijing Han, Xiaojuan Liao, Ruyi Sun, Jianhua Wu, and Meiran Xie

Macromolecules 2014 Volume 47(Issue 18) pp:6181-6188

Publication Date(Web):September 9, 2014

DOI:10.1021/ma501217b

Metathesis cyclopolymerization (MCP) of ionic 1,6-heptadiyne is successfully applied to synthesize polyacetylene (PA) ionomer in different solvents especially in imidazolium-based ionic liquid (IL), and MCP of ionic monomer in the mixture of THF/IL proceeded in a controlled manner by the action of Grubbs second and third generation catalysts (Ru–II, Ru–III). The influence of catalysts and solvents on polymerization behavior and chain microstructure was investigated, and the results revealed that the isolated polymer yield could reach to 97% and 82% by Ru–III and Ru–II, respectively, in 1:2 THF/IL after optimization, and PAs incorporating imidazolium pendent contained ≥95% five-membered-ring structure and almost all trans-double bonds along the backbone. PAs formed in different solvents reflected significant variance in optical absorption properties, and a bathochromic shift effect was observed with the mixture of THF/IL.

Polymeric microstructures and dielectric properties of polynorbornenes with 3,5-bis(trifluoromethyl)biphenyl side groups by ring-opening metathesis polymerization

Co-reporter:Zewang You;Wei Song;Sha Zhang;Ouyue Jin

Journal of Polymer Science Part A: Polymer Chemistry 2013 Volume 51( Issue 22) pp:4786-4798

Publication Date(Web):

DOI:10.1002/pola.26901

ABSTRACT

exo-Polynorbornenes containing bis(trifluoromethyl)biphenyl side groups were synthesized by ring-opening metathesis polymerization using different Grubbs' catalysts, the microstructures of the polymer chains were established using NMR and IR spectroscopy. The influence of monomer and catalyst structures on chain microstructure was revealed and the correlation of properties with microstructure was investigated in detail. The exo-poly(N-3,5-bis(trifluoromethyl)biphenyl-norbornene-pyrrolidine) (exo-PTNP) and exo-poly(N-3,5-bis(trifluoromethyl)biphenyl-norbornene-dicarboximide) (exo-PTNDI) formed using Ru-I show a trans double bond bias of 67% and 83%, respectively, whereas the corresponding polymers formed using Ru-III have lower contents of trans double bond, 30% and 50%, respectively. Compared to the highly trans endo-PTNP formed using Ru-I, which is isotactic and has a dielectric constant of about 20, the endo-PTNP formed using Ru-III, the exo-PTNDIs and the exo-PTNPs formed using Ru-I and Ru-III all have different proportions of trans and cis double bonds, they are atactic and display relatively low dielectric constants, in the range 6 to 9. DSC measurements indicate some dependence of T_g, varying 161 to 221 °C, on tacticity and cis/trans ratios with higher trans contents tending towards higher T_g. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4786–4798

High dielectric performance of tactic polynorbornene derivatives synthesized by ring-opening metathesis polymerization

Co-reporter:Zewang You;Danyi Gao;Ouyue Jin;Xiaohua He

Journal of Polymer Science Part A: Polymer Chemistry 2013 Volume 51( Issue 6) pp:1292-1301

Publication Date(Web):

DOI:10.1002/pola.26497

Abstract

Functional polynorbornenes (PNBEs) containing pyrrolidine moiety and bis(trifluoromethyl)biphenyl side group were synthesized via ring-opening metathesis polymerization (ROMP), and the microstructure of polymer chain was characterized by NMR spectroscopy. Poly(N-3,5-bis(trifluoromethyl)biphenyl-norbornene-pyrrolidine) (PTNP) and poly(N-phenyl-norbornene-pyrrolidine) (PPNP) are supposed to have practically trans double bonds and adopt isotactic syn conformation, whereas poly(N-3,5-bis(trifluoromethyl)biphenyl-norbornene-dicarboximide) (PTNDI) has both trans and cis double bonds and atactic microstructure. PTNP, PTNDI, and PPNP have much different dielectric constants of 20, 7, and 3, respectively, which is attributed to both the polar 3,5-bis(trifluoromethyl)biphenyl group and the stereoregular chain structure. The existence of rigid pyrrolidine moiety has a positive contribution to form the tactic polymer chain during ROMP. Polymers are highly thermal stable up to ∼300 °C. Having good dielectric properties and thermal stability, these functional PNBEs are expected as the potential dielectric material in thin film capacitors. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Robust hybrid nanostructures comprising gold and thiol-functionalized polymer nanoparticles: facile preparation, diverse morphologies and unique properties

Co-reporter:Meiran Xie, Liang Ding, Zewang You, Danyi Gao, Guangda Yang and Huijing Han

Journal of Materials Chemistry A 2012 vol. 22(Issue 28) pp:14108-14118

Publication Date(Web):24 May 2012

DOI:10.1039/C2JM31228J

Nanohybrids are generated via covalent integration of Au nanoparticles (NPs) with thiol-functionalized crosslinked polymer NPs. The polymer NPs have been readily prepared by the controlled intramolecular crosslinking of long-chain highly branched polymers through the thiol–ene reaction in dilute solution, and the thiol groups on polymer NPs can be introduced and tailored by alternating the cross linkers with various thiol functionalities, which facilitates the further fabricatation of nanohybrids with different loadings of Au NPs. The structures and optical properties of these nanostructures are characterized by elemental analysis, IR, NMR, XPS, XRD, and UV-vis measurements. The morphologies of nanostructures are investigated via dynamic light scattering, atom force microscopy, transmission electron microscopy, and cryogenic transmission electron microscopy. The results reveal that the crosslinked polymer NPs have an average diameter of 45 nm, and Au NPs in the nanohybrids are isolated and distributed throughout the surface of the polymer NPs. When varying the concentrations, the hybrid nanostructures display diverse morphologies going through nanosphere, chainlike assembly and nanorod, accompanied with unique optical properties. Additionally, this type of hybrid nanostructure has high stability and recoverability in catalysis, and shows excellent efficiency for the reduction of nitro compounds.

Electromagnetic activation of a shape memory copolymer matrix incorporating ferromagnetic nanoparticles

Co-reporter:Dan Yang;Wei Huang;Xiaohua He

Polymer International 2012 Volume 61( Issue 1) pp:38-42

Publication Date(Web):

DOI:10.1002/pi.3188

Abstract

Modified magnetite (Fe₃O₄) was easily mixed in a matrix of a polynorbornene-based copolymer to realize a nanocomposite of organic polymer and inorganic metal oxide nanoparticles. The crystalline structure and the diameter of the modified Fe₃O₄ were evaluated with X-ray diffraction and atomic force microscopy, revealing the crystalline Fe₃O₄ nanoparticles in the nanometer size range with an average diameter of 55 nm, a value close to that indicated by dynamic light scattering (68 nm). The transition temperature of the composite of 51 °C was determined using differential scanning calorimetry and the thermal stability and dynamic mechanical properties of the easily formed composite were investigated using thermogravimetry and dynamic mechanical analysis. The shape memory effect was evaluated in terms of shape recovery rate and speed, while thermally and electromagnetically triggered shape memory properties were documented. The recovery time triggered by Fe₃O₄ is 186 s. Copyright © 2011 Society of Chemical Industry

Erratum to: Cyclodextrin-based hyperbranched polymers by acyclic diene metathesis polymerization of an ABn monomer: molecule design, synthesis, and characterization

Co-reporter:Ning Wang;Liang Ding

Journal of Polymer Research 2012 Volume 19( Issue 8) pp:

Publication Date(Web):2012 August

DOI:10.1007/s10965-012-9937-y

More insight into tandem ROMP and ADMET polymerization for yielding reactive long-chain highly branched polymers and their transformation to functional polymer nanoparticles

Co-reporter:Liang Ding, Guangda Yang, Meiran Xie, Danyi Gao, Jiahui Yu, Yiqun Zhang

Polymer 2012 Volume 53(Issue 2) pp:333-341

Publication Date(Web):24 January 2012

DOI:10.1016/j.polymer.2011.12.022

Tandem chain transfer ring-opening metathesis polymerization (ROMP-CT) and acyclic diene metathesis (ADMET) polymerization were carried out in a controlled one-pot procedure, and behaved noticeable differences in polymerization of monomers by different ruthenium catalysts, whereas there indeed had been two distinctly polymerization stages. In the first one, ROMP-CT of functional monomers was conducted in the presence of a symmetrical multi-olefin as chain transfer agent within various reaction time scales, yielding linear telechelic polymers. Next, ADMET polymerization of telechelic polymers was performed and generated a series of reactive long-chain highly branched polymers (LCHBPs) with acrylate and/or azobenzene groups having molecular weights of 8.5–47.9 kDa under varied conditions. LCHBPs were fully characterized by several techniques, and interestingly, UV–vis analysis displayed the specific peak at 278 nm, which offered a new evidence for the existence of internal acrylate structure on the LCHBP backbone, and supported the highly branched architecture of polymers. LCHBP containing a number of pendent acrylate groups was readily converted, by thiol-Michael addition click reaction, to novel thiol-functionalized intra-molecular crosslinked unimolecular polymer nanoparticles with diameter of 40–60 nm, which provided a facile method for post-functionalization of branched polymers.

Facile One-Pot Approach for Preparing Functionalized Polymeric Nanoparticles via ROMP

Co-reporter:Jingwei Liu;Yang Liao;Xiaohua He;Jiahui Yu;Liang Ding

Macromolecular Chemistry and Physics 2011 Volume 212( Issue 1) pp:55-63

Publication Date(Web):

DOI:10.1002/macp.201000416

POSS-enhanced shape-memory copolymer of polynorbornene derivate and polycyclooctene through ring-opening metathesis polymerization

Co-reporter:Dan Yang, Danyi Gao, Chi Zeng, Jisen Jiang, Meiran Xie

Reactive and Functional Polymers 2011 71(11) pp: 1096-1101

Publication Date(Web):November 2011

DOI:10.1016/j.reactfunctpolym.2011.08.009

Preparation of reactive block copolymers and their transformation to hollowed nanostructures

Co-reporter:Meiran Xie;Liya Zhang;Yang Liao;Liang Ding;Chi Zeng ;Zewang You

Journal of Polymer Science Part A: Polymer Chemistry 2011 Volume 49( Issue 23) pp:4955-4963

Publication Date(Web):

DOI:10.1002/pola.24951

Abstract

A novel polymeric hollow nanostructure was generated using micellar template method through a three-step procedure. First, the block copolymers were synthesized via ring-opening metathesis polymerization by sequentially adding monomers 7-oxanorborn-5-ene-exo-exo-2,3-dicarboxylic acid dimethyl ester and the mixture of norbornene and 2,3-bis(2-bromoisobutyryloxymethyl)-5-norbornene in chloroform, and also atom transfer radical polymerization of 4-(3-butenyl)styrene was carried out by using the as-obtained block copolymer poly(7-oxanorborn-5-ene-exo,exo-2,3-dicarboxylic acid dimethylester)-block-poly(norbornene-co-2,3-bis(2-bromoisobutyryloxymethyl)-5-norbornene as macroinitiator to afford a graft copolymer bearing poly(4-(3-butenyl)styrene) branch poly(7-oxanorborn-5-ene-exo,exo-2,3-dicarboxylic acid dimethylester)-block-poly(norbornene-co-2,3-bis(2-bromoisobutyryloxymethyl)-5-norbornene)-graft-poly(4-(3-butenyl)styrene). Second, the shell-crosslinked micelles were prepared by ruthenium-mediated ring-closing metathesis of poly(4-(3-butenyl)styrene) branches in intramicelle formed from the copolymers self-assembly spontaneously in toluene. Finally, the hollowed spherical nanoparticles were presented by removing the micellar copolymer backbone through the cleavage of the ester bonds away from the crosslinked network of branches. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Cleavable multiblock copolymer synthesized by ring-opening metathesis copolymerization of cyclooctene and macrocyclic olefin and its hydrolysis to give carboxyl-telechelic polymer

Co-reporter:Meiran Xie;Weizhen Wang;Liang Ding;Jingwei Liu;Dan Yang;Ling Wei;Yiqun Zhang

Journal of Polymer Science Part A: Polymer Chemistry 2010 Volume 48( Issue 2) pp:380-388

Publication Date(Web):

DOI:10.1002/pola.23795

Abstract

A novel cleavable multiblock copolymer was synthesized by ring-opening metathesis polymerization (ROMP) of cyclooctene (COE) and a flexible 27-membered macrocyclic olefin (MCO), which is acted as the spacer to collect the polymer structure block by block. MCO 2 was prepared via ring-closing metathesis of the long chain alkyldiene, and then 2 was well- conducted ROMP with COE to provide the multiblock copolymer [Poly(COE)-2]_m consisting of homo-Poly(COE) blocks and ring-opened 2 segments with different molecular weights (M_n = 30.0 – 249.6 × 10³) and polydispersity index (PDI) within 1.45–1.67 as variation of the feed ratio of COE to 2. The multiblock copolymer chain containing weak ester linkage can be cleaved under alkali condition to afford the carboxyl-telechelic Poly(COE) blocks with much lower molecular weights (M_n,h = 3.6–35.7 × 10³) and slight higher PDIs (1.65–1.88). The average block number on multiblock copolymer chain was obtained from the ratio of M_n to M_n,h and was reached up to the value of 7–16. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 380–388, 2010

New azo-chromophore-containing multiblock poly(butadiene)s synthesized by the combination of ring-opening metathesis polymerization and click chemistry

Co-reporter:Liang Ding, Liya Zhang, Dan Yang, Wei Huang, Meiran Xie, Yiqun Zhang

Polymer 2010 Volume 51(Issue 6) pp:1285-1292

Publication Date(Web):11 March 2010

DOI:10.1016/j.polymer.2010.02.001

A combination of ring-opening metathesis polymerization (ROMP) and click chemistry approach was utilized for the first time in preparation of multiblock copolymers. The dibromo-functionalized telechelic poly(butadiene) (PBD) was synthesized firstly by ROMP of 1,5-cyclooctadiene in the presence of a symmetrical difunctional chain transfer agent and transformed into diazido-telechelic PBD, which was then reacted with a dialkynyl-containing azobenzene chromophore via click reaction, producing novel multiblock PBDs collected by azobenzene groups and newly formed triazole moieties. The monomer and polymer were characterized by IR, UV–vis, LC/MS, and NMR techniques. The produced multiblock copolymers have molecular weights within 13.3 and 57.8 kDa, and their polydispersity indices ranging from 1.98 to 2.38 by gel permeation chromatography measurement. The multiblock PBDs containing azo chromophores and triazole moieties with or without hydrogen-bonding interreaction with 4,4′-dihydroxybiphenyl molecule exhibited different photoisomerization efficiency from trans to cis as observation in UV–vis spectroscopy. The morphologies of multiblock PBDs were also investigated by atom force microscopy.

A novel shape memory polynorbornene functionalized with poly(ɛ-caprolactone) side chain and cyano group through ring-opening metathesis polymerization

Co-reporter:Dan Yang, Wei Huang, Jiahui Yu, Jisen Jiang, Liya Zhang, Meiran Xie

Polymer 2010 Volume 51(Issue 22) pp:5100-5106

Publication Date(Web):15 October 2010

DOI:10.1016/j.polymer.2010.09.009

A novel functionalized norbornene-based copolymer with long poly(ɛ-caprolactone) side chain and cyano group was synthesized in the combination of ring-opening polymerization and ring-opening metathesis polymerization, which was characterized by means of 1H NMR, gel permeation chromatography, thermogravimetry, differential scanning calorimetry, wide-angle X-ray diffraction, and stress–strain measurements. The shape memory effect of the copolymer was evaluated by dynamical mechanical analysis, shape recovery ability, and shape recovery speed. Having the properties of the good shape fixity and the large shape recovery, the functionalized polynorbornene copolymer is expected to use as a potential shape memory material.

Efficient Synthesis of Long-Chain Highly Branched Polymers via One-Pot Tandem Ring-Opening Metathesis Polymerization and Acyclic Diene Metathesis Polymerization

Co-reporter:Liang Ding, Meiran Xie, Dan Yang, and Chunmei Song

Macromolecules 2010 Volume 43(Issue 24) pp:10336-10342

Publication Date(Web):December 2, 2010

DOI:10.1021/ma1020903

A facile one-pot synthesis of long-chain highly branched polymers (LCHBPs) was accomplished by a tandem ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polymerization procedure. A telechelic polymer with two terminal allyloxy groups and many pendent acrylates was first prepared through the first generation Grubbs catalyst-mediated chain transfer ROMP of 7-oxanorborn-5-ene-exo,exo-2,3-dicarboxylic acid bis(2-(acryloyloxy)ethyl) ester in the presence of a symmetrical multifunctional olefin 1,4-diallyloxy-cis-2-butene as chain transfer agent (CTA), and then utilized as an A2B2n-type macromonomer in subsequent ADMET polymerization between allyloxy and acrylate triggered by the most activated second generation Grubbs catalyst, yielding LCHBPs as the reacton time prolonged. The CTA, monomer, macromonomer, and the resulting LCHBPs were characterized by mass spectroscopy, elemental analysis, gel permeation chromatography with multiangle laser light scattering, NMR and matrix-assisted laser desorption ionization time-of-flight mass measurements. The LCHBPs have comparatively high molecular weights and relatively moderate polydispersity indices.

A novel amphiphilic AB2 star copolymer synthesized by the combination of ring-opening metathesis polymerization and atom transfer radical polymerization

Co-reporter:Jingwei Liu, Jinxin Li, Meiran Xie, Liang Ding, Dan Yang, Liya Zhang

Polymer 2009 50(22) pp: 5228-5235

Publication Date(Web):

DOI:10.1016/j.polymer.2009.09.029

Hyperbranched Azo-Polymers Synthesized by Acyclic Diene Metathesis Polymerization of an AB2 Monomer

Co-reporter:Liang Ding, Liya Zhang, Huijing Han, Wei Huang, Chunmei Song, Meiran Xie and Yiqun Zhang

Macromolecules 2009 Volume 42(Issue 14) pp:5036-5042

Publication Date(Web):June 24, 2009

DOI:10.1021/ma900412b

A novel hyperbranched azo-polymer was prepared by a ruthenium-based catalyst RuCl2(PCy3)(SIMes)(CHPh) using acyclic diene metathesis (ADMET) polymerization of an AB2 monomer, 4-undecylenyloxycarbonyl-4′-[bis(2-ethyl acrylate)amino]azobenzene, which was synthesized from the esterification reaction between N,N-bis(2-ethyl acrylate)aniline and 4-carboxy-4′-[bis(2-ethyl acrylate)amino]azobenzene. The monomer and polymer were characterized by mass spectrometer, elemental analysis, IR, UV−vis, and NMR measurements. The produced polymers have molecular weights within 5.83 and 23.5 kDa, and their polydispersity indices range from 1.73 to 1.86 by multiangle laser light scattering-gel permeation chromatography (MALLS−GPC). The hyperbranched azo-polymer underwent efficient photoisomerization from trans to cis as observation in UV−vis spectroscopy. The degree of branching (DB) was determined by using 1H NMR spectroscopy and the values ranged from 0.57 to 0.45.

Cyclic poly(-caprolactone) synthesized by combination of ring-opening polymerization with ring-closing metathesis, ring closing enyne metathesis, or click reaction

Co-reporter:Meiran Xie;Jiaxin Shi;Liang Ding;Jinxin Li;Huijing Han ;Yiqun Zhang

Journal of Polymer Science Part A: Polymer Chemistry 2009 Volume 47( Issue 12) pp:3022-3033

Publication Date(Web):

DOI:10.1002/pola.23390

Abstract

This article described the synthesis of cyclic poly(ε-caprolactone) (PCL) via ring-closing metathesis (RCM), ring closing enyne metathesis (RCEM), and “click” reaction of different difunctional linear PCL. Linear PCL precursors were prepared by ring-opening polymerization (ROP) of ε-caprolactone in bulk using 10-undecen-1-ol or propargyl alcohol as the initiator, followed by reacting with corresponding acyl chloride containing vinyl or azido end group. The subsequent end-to-end intramolecular coupling reactions were performed under high dilution conditions. The successful transformation of linear PCL precursor to cyclic PCL was confirmed by Gel permeation chromatography, ¹H NMR, and Fourier transform infrared measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3022–3033, 2009

Synthesis and Self-Assembly of Functionalized Cyclooctene Block Copolymers via ROMP

Co-reporter:Meiran Xie;Huijing Han;Weizhen Wang;Xiaohua He ;Yiqun Zhang

Macromolecular Chemistry and Physics 2008 Volume 209( Issue 5) pp:544-550

Publication Date(Web):

DOI:10.1002/macp.200700452

Well-Defined Brush Copolymers with High Grafting Density of Amphiphilic Side Chains by Combination of ROP, ROMP, and ATRP

Co-reporter:Meiran Xie, Jingya Dang, Huijing Han, Weizhen Wang, Jingwei Liu, Xiaohua He and Yiqun Zhang

Macromolecules 2008 Volume 41(Issue 23) pp:9004-9010

Publication Date(Web):November 4, 2008

DOI:10.1021/ma801408s

This work reports a facile strategy for the preparation of a novel well-defined brush copolymer with two different grafts distributed on the same unit along the backbone via combination of three controlled polymerization methods, ring-opening polymerization (ROP), ring-opening metathesis polymerization (ROMP), and atom transfer radical polymerization (ATRP) based on the synthesis of the heterotrifunctional inimer, 2-hydroxymethyl-3-(2-bromoisobutyryloxymethyl)-5-norbornene (NBE-OH/Br). ROP of ε-caprolactone initiated by NBE-OH/Br was carried out to generate macroinimer, norbornene-graft-poly(ε-caprolactone)/Br (NBE-g- PCL/Br). The grafting-through strategy was then employed to construct the polymer backbone, poly(norbornene)-graft-poly(ε-caprolactone)/Br (PNBE-g-PCL/Br) via ROMP of the norbornene-terminated macroinimer NBE-g-PCL/Br. Finally, the grafting-from route was used for the synthesis of amphiphilic grafted brush copolymer, poly(norbornene)-graft-poly(ε-caprolactone)/poly(2-(dimethylamino)ethyl methacrylate) (PNBE-g-PCL/PDMAEMA) by ATRP of 2-(dimethylamino)ethyl methacrylate using bromo-functionalized ROMP product PNBE-g-PCL/Br as macroinitiators, containing one hydrophobic PCL graft and one hydrophilic PDMAEMA graft on each unit of the backbone.

Ring-opening metathesis polymerization of functionalized cyclooctene by a ruthenium-based catalyst in ionic liquid

Co-reporter:Huijing Han;Fengxiang Chen;Jiahui Yu;Jingya Dang;Zhuo Ma;Yiqun Zhang

Journal of Polymer Science Part A: Polymer Chemistry 2007 Volume 45(Issue 17) pp:3986-3993

Publication Date(Web):17 JUL 2007

DOI:10.1002/pola.22152

This paper describes the synthesis of a novel monomer of 5-substituted cyclooctene with the pendant of imidazolium salt (7) and the ring-opening metathesis polymerization of the functionalized cyclooctenes (4 and 7) in CH₂Cl₂ and ionic liquid [bmim][PF₆] by a ruthenium-based catalyst RuCl₂(PCy₃)(SIMes)(CHPh) (2). The polymerization, which was carried out in ionic liquid, afforded improved control over the molecular weight (M_n) and polydispersity of the resultant products (PDI <1.4). Furthermore, to facilitate the GPC measurement for molecular weight of polymers, the charged polymers (poly-7) were hydrolyzed to give uncharged polymers (poly-4*) by removing the imidazolium pendant from the polymer chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3986–3993, 2007

New polyelectrolytes by ring-opening metathesis polymerization of norbornene derivatives with imidazolium functionalized oligo-alkylether pendant groups

Co-reporter:Lingdi Zheng, Fengxiang Chen, Meiran Xie, Huijing Han, Qing Dai, Yiqun Zhang, Chunmei Song

Reactive and Functional Polymers (January 2007) Volume 67(Issue 1) pp:19-24

Publication Date(Web):January 2007

DOI:10.1016/j.reactfunctpolym.2006.08.004

Amphiphilic ABA triblock copolymers via combination of ROMP and ATRP in ionic liquid: Synthesis, characterization, and self-assembly

Co-reporter:Meiran Xie, Yi Kong, Huijing Han, Jiaxin Shi, Liang Ding, Chunmei Song, Yiqun Zhang

Reactive and Functional Polymers (December 2008) Volume 68(Issue 12) pp:1601-1608

Publication Date(Web):December 2008

DOI:10.1016/j.reactfunctpolym.2008.09.001

Hybrid triazolium and ammonium ions-contained hyperbranched polymer with enhanced ionic conductivity

Co-reporter:Hongfei Li, Cuifang Wang, Xiaojuan Liao, Meiran Xie, Ruyi Sun

Polymer (10 March 2017) Volume 112() pp:

Publication Date(Web):10 March 2017

DOI:10.1016/j.polymer.2017.02.023

•Novel hyperbranched polymers consisting of hybrid triazolium and quaternary ammonium ions are synthesized.•They have higher ionic conductivity above 10−5 S cm−1 at 30 °C than that of similar polymers containing solely triazolium.•Therefore, this type of hyperbranched polymers could act as the new polyelectrolyte materials in energy device applications.Hyperbranched poly(triazole) with tertiary amine moiety and longer flexible polyethylene glycol (PEG) terminal group (hb-PTA-PEG) was synthesized by successive Cu(I)-catalyzed azide-alkyne cycloaddition polymerization, and the corresponding hyperbranched poly(triazolium)s containing hybrid quaternary ammonium ion, [hb-PTA-PEG]+[I]− and [hb-PTA-PEG]+[TFSI]−, were obtained after N-alkylation and anion exchange reactions. These hyperbranched polymers presented broad electrochemical stability window of above 6.0 V versus Ag+/Ag and 5.3 V versus Li+/Li, and displayed low glass transition temperature in the range of −13 to −37 °C, owing to the hyperbranched structure combined with the hybrid ionic moiety and longer flexible PEG end-group. The ionic [hb-PTA-PEG]+[TFSI]− showed superior ionic conductivity, which was above 10−5 S cm−1 at 30 °C.Download high-res image (156KB)Download full-size image

Ladder-like polyacetylene with excellent optoelectronic properties and regular architecture

Co-reporter:Wei Song, Huijing Han, Jianhua Wu and Meiran Xie

Chemical Communications 2014 - vol. 50(Issue 85) pp:NaN12902-12902

Publication Date(Web):2014/08/29

DOI:10.1039/C4CC05524A

Nanostructured high-performance dielectric block copolymers

Co-reporter:Wenmei Liu, Xiaojuan Liao, Yawei Li, Qiuhua Zhao, Meiran Xie and Ruyi Sun

Chemical Communications 2015 - vol. 51(Issue 83) pp:NaN15323-15323

Publication Date(Web):2015/08/26

DOI:10.1039/C5CC05307B

Robust hybrid nanostructures comprising gold and thiol-functionalized polymer nanoparticles: facile preparation, diverse morphologies and unique properties

Co-reporter:Meiran Xie, Liang Ding, Zewang You, Danyi Gao, Guangda Yang and Huijing Han