Polymer Chemistry
·
2016
·Vol. 7
·期 40
·6202-6210
·
IF 5.687
Yaochen Zheng,Shengying Cai,Li Peng,Yu Jin,Han Xu,Zhulin Weng,Zhengguo Gao,Bo Zhao,Chao Gao
We have coined a new term, group interval-controlled polymers (GICPs), to describe the unique structure of macromolecules with a tunable functional group interval. The precise control of a polymer main chain structure itself is still a big challenge, let alone the purposeful control of group interval simultaneously. Here, we successfully synthesized a series of epoxy GICPs via one-step UV-triggered thiol–yne polymerization of commercial glycidyl propargyl ether and dithiols at 0 °C. Subsequently, α,ω-thiols of each epoxy GICP were capped by two allyl glycidyl ethers via a thiol–ene click reaction, affording a stable product. Their unique group interval-controlled chemical structures were confirmed by a combination of nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and pyrene-fluorescent probe tests. Moreover, the epoxy groups within the GICPs were highly reactive and could be further functionalized and turned into a diverse range of customized groups such as azide, tertiary amino, thioester, and hydroxyl, etc. Therefore, a series of GICPs with designed functional groups are readily achieved on a large scale. Our work presents a reliable synthetic methodology for GICPs, paving a new way for the precise structure control of artificial macromolecules.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
MACROMOLECULES
·
2022
·
IF 6.057
Yujian Liu,Yongyao Lei,Yougen Chen
The current contribution presents the synthesis of poly[oligo(ethylene glycol) sorbate]s (PREGmSs) by the t-Bu-P4-catalyzed group transfer polymerization (GTP) method, their postpolymerization modification at the backbone double bond, and thermoresponsive properties in aqueous solution. Four oligo(ethylene glycol) sorbate monomers (REGmSs), including 2-(2-methoxyethoxy)ethyl sorbate (MeEG2S), 2-(2-(2-methoxyethoxy)ethoxy)ethyl sorbate (MeEG3S), 2-(2-(2-ethoxyethoxy)ethoxy)ethyl sorbate (EtEG3S), and 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethyl sorbate (MeEG4S), are newly designed to study the thermoresponsive properties of their related polymers. The t-Bu-P4-catalyzed GTP of REGmS only proceeds in a 1,4-regioselective addition manner to quantitatively produce the backbone trans-rich (ca. 80%) PREGmS. The complete hydrogenation and epoxidation of the backbone double bonds result in hydrogenated and epoxidized polymers (PREGmS-H2 and PREGmS-epoxy, respectively), which have different main-chain structures and rigidity from their parent PREGmS. Given the 1,4-substituted structure of a sorbate monomer, the chemical structure determination of PREGmS-H2 by 13C NMR spectra demonstrates that the above polymers have an erythro-rich (ca. 60%) structure in diastereochemistry and a diisotactic/disyndiotactic ratio around 1:1 in stereoregularity. The thermoresponsive properties of PREGmS, PREGmS-H2, and PREGmS-epoxy in aqueous solutions are studied in detail from various aspects in terms of polymer mass concentration, molecular weight, length and end group of the oligo(ethylene glycol) side chain, and main-chain structure by turbidity, 1H NMR spectroscopy, and dynamic light scattering (DLS) methods, which are discussed below.
研究领域:
高分子化学
·
材料科学
✓ 已验证
DOI
高影响因子
LIQUID CRYSTALS
·
2021
·
IF 0
Peng Wei,Hejuan Lou,Yifeng Zhang,Wei Zhang,Yawei Bian,Yumin Xia,Yanping Wang,Yimin Wang
In this study, three novel main-chain liquid-crystal polyurethanes based on mesogenic diol 4,4ʹ-bis(6-hydroxyhexoxy)biphenyl (BP6), azo diol 4,4ʹ-bis(6-hydroxyhexyloxy)-azobenzene (BHHAB) and 4,4ʹ-diisocyanato-3,3ʹ-dimethylbiphenyl (DMBDI) were synthesised via polyaddition method. The chemical structure, thermal properties, liquid-crystal behaviour and microstructure were fully characterised by FTIR, 1HNMR, UV spectrum, Differential scanning calorimetry (DSC), Thermogravimetric analyzer (TGA), Polarizing optical microscope (POM) and X-ray diffraction techniques. The resulted polyurethanes showed strong UV absorption at 313 nm ascribed to π–π* transition of azo group. All of the polyurethanes showed multiple transitions on DSC curve, which could be ascribed to crystal, melting and isotropization transitions combined with the POM observation. The thermal degradation of the polymers occurred at much higher temperatures (325–331°C) than the melting ones (144–154°C), making the melt processing feasible. The polyurethane showed semicrystalline structure based on diffraction and DSC results. The obtained polyurethanes exhibited smectic mesophase as verified by variable temperature WAXD results, and the mesophase temperature range was more than 25°C based on the POM observation. The obtained polyurethanes could be potentially used in optical and smart intelligence material area.
研究领域:
材料科学
·
高分子化学
✓ 已验证
DOI
JOURNAL OF APPLIED POLYMER SCIENCE
·
2020
·Vol. 137
·期 45
·49413
·
IF 2.52
Ziyue Yang,Dongcheng Sun
A facile method for preparing supramolecular waterborne polyurethane (WPU) based on quadruple hydrogen bonds (4H-WPU) is reported. Herein, 4H-WPU with quadruple hydrogen bonds in main chain were synthesized by poly (1,4-buthylene-neopentylene adipate glycol) as soft segment, 2-ureido-4[1H]-pyrimidinone (UPy) functionalized monomer, isophorone diisocyanate, 2,2-Bis(hydroxymethyl)propionic acid (hydrophilic monomer), isophorondiamine, triethylamine (neutralizer), and monoethanolamine (blocking agent) as hard segment. The molecular weight of 4H-WPU was controlled around 18,000 consistently. The properties of 4H-WPU with different content of hydrophilic group, hard segment, and UPy units were characterized and the results could provide the reference for preparing supramolecular WPU with high mechanical and self-healing performance while maintaining dispersion stability. The tensile strength of 4H-WPU was 10 times of the blank sample. The healing time of scratched 4H-WPU film was inversely proportional to the content of UPy- functionalized monomer and the shortest healing time is 2.5 hr at 80°C. Mechanical performance of healed films can be restored to more than 90%.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF POLYMER RESEARCH
·
2022
·Vol. 29
·期 11
·1-12
·
IF 3.061
Yan Huixuan,He Yifan,Yao Liru,Wang Xiuxiu,Zhang Xinyu,Zhang Yuhe,Han Dongxu,Li Chensha,Sun Liguo,Zhang Jianqi
Thiol-acrylate main-chain liquid-crystalline elastomers (MC-LCEs) are currently widely used in LCE application research work. The current preparations of thiol-acrylate MC-LCE materials generally based on two-step thiol-acrylate Michael addition and photopolymerization (TAMAP). By this methodology, the permanently programmed monodomain of LCE matrices were achieved via a second-step photopolymerization reaction of the excess acrylate groups after the first step of "click" reaction of thiol-acrylate Michael-addition, in which the initial LCE networks were synthesized, and the stress-aligning process. In order to overcome the limitations of TAMAP in the preparations of LCE materials or LCE devices with special requirements of dimensions, components or structures, etc., for the first time we developed a way of two-step thiol-acrylate Michael addition and thermal polymerization (TAMAT). The second-step polymerization reaction of the excess acrylate groups was implemented by thermal initiation approach. Under the action of the selected thermal-initiator and appropriate temperature condition, the thiol-acrylate MC-LCEs could be prepared with well quality and reproducibility by TAMAT, and had consistent structure, properties and performances with those prepared by TAMAP, thus confirmed the high effectiveness and practicability of TAMAT methodology in the preparations of thiol-acrylate MC-LCE materials.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Yuxin Kong,Shijie Wang,Yuxiang Li,Guangjiu Pan,Yusuf Bulut,Sen Zhang,Guobi Chai,Ziang Wu,Hongmei Qin,Wu Fan,Qingwen Liu,Zonhan Wei,Han Young Woo,Peter Müller-Buschbaum,Stephan V. Roth,Qidong Zhang,Wei Ma
Donor (D)–acceptor (A) copolymer-based organic mixed ionic–electronic conductors (OMIECs) exhibit intrinsic environmental stability for they have tailored energy levels. However, their figure-of-merit (μC*) is still falling behind the D–D polymers because of morphology deterioration during the electrochemical doping process. Herein, we developed two D–A copolymers with precisely regulated backbone curvature, namely PTBT-P and PTTBT-P. Compared to the curved PTBT-P and previously reported copolymers, PTTBT-P better keeps its backbone linear, leading to a long-range ordered doping morphology, which is revealed by the in operando X-ray technique. This optimized doping morphology enables a significantly improved operando charge mobility (μ) of 2.44 cm2 V–1 s–1 and a μC* value of 342 F cm–1 V–1 s–1, one of the highest values in D–A copolymer based on OECTs. Besides, we fabricated PTTBT-P-based electrochemical random-access memories and achieved ideal and robust conductance modulation. This study highlights the critical role of backbone curvature control in the optimization of doping morphology for efficient and robust organic electrochemical devices.
研究领域:
材料科学
·
有机电子学
✓ 已验证
DOI
PubMed
高影响因子
Biomaterials Science
·
2024
·
IF 5.8
Jianglong Xia,Wanying Wang,Xiaoxiong Jin,Jing Zhao,Jiaoyu Chen,Ning Li,Shanshan Xiao,Dongjun Lin,Ziyuan Song
Anionic synthetic polypeptides are promising candidates as standalone bone-targeting drug carriers. Nevertheless, the structure–property relationship of the bone-targeting ability of polypeptides remains largely unexplored. Herein we report the optimization of the in vitro and in vivo bone-targeting ability of poly(glutamic acid)s (PGAs) by altering their chain lengths and backbone chirality. PGA 100-mers exhibited higher hydroxyapatite affinity in vitro, but their rapid macrophage clearance limited their targeting ability. Shorter PGA was therefore favored in terms of in vivo bone targeting. Meanwhile, the backbone chirality showed less significant impact on the in vitro and in vivo targeting behavior. This study highlights the modulation of structural parameters on the bone-targeting performance of anionic polypeptides, shedding light on the future design of polypeptide-based carriers.
研究领域:
药学
·
材料科学
·
生物材料
✓ 已验证
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Xi Bin Yue,Ying Jie Liu,Li Wei Lai,Xi Hao Wang,Hui Peng,Qiu Gen Zhang,Ai Mei Zhu,Qing Lin Liu
Improving the microphase separation structure of membranes is considered an effective strategy to solve the trade-off problem, which can increase the conductivity and reduce the swelling. This article designs poly(aryl alkylene) AEMs with different aryl backbone chains (biphenyl, p-terphenyl and m-terphenyl), with the goal of examining the effect of spatial structure main chains on the membrane performance. It is found that the membrane (m-QTPNP) has a better microphase separation structure and a conductivity of 143.5 mS cm −1 (80 °C) via SAXS, TEM and AFM. Due to the lower IEC (2.23 meq g −1 ), m-QTPNP has a good anti-swelling performance. During tensile testing, the elongation at break of m-QTPNP can reach 105.5% (wet state). Moreover, due to the obvious microphase separation, the attack of OH − on the quaternized groups is reduced, and m-QTPNP has a conductivity retention rate of 95.5% (80 °C, 2 M NaOH, 1560 h). In addition, the peak power density (PPD) of the H 2 /O 2 single cell equipped with m-QTPNP can reach 749 mW cm −2 (80 °C). After 90 h of durability testing, the voltage decayed to 92.2%, with a decay rate of 0.54 mV h −1 .
研究领域:
材料科学
·
能源化学
·
高分子化学
✓ 已验证
DOI
高影响因子
MACROMOLECULES
·
2017
·
IF 5.835
Yang Cai,Jianmin Lu,Gaifeng Jing,Wantai Yang,Bingyong Han
A series of prepolymers were treated with CF3SO3H to cationically cyclize adjacent diene–styrene/diene–diene units into main-chain cyclic units. Diene–diphenylethylene alternating copolymers synthesized using anionic copolymerization were first cyclized completely without intermolecular linking reactions. The cyclization produced much higher Tg values (approximately 200 °C) than those of cyclized random diene–styrene copolymers (approximately 130 °C). To eliminate the number of spacer carbons between cyclic repeating units, poly(1-phenyl-1,3-butadiene) (PPB) was used as a prepolymer in cationic cyclization. The Tg increased substantially from 200 to 271 °C as the 3,4-structure content increased from 8% to 80%. The cyclized PPB with high 3,4-structure content is the highest Tg hydrocarbon polymer yet reported. All results indicated that the backbone rigidity of the cyclic hydrocarbon polymer can be drastically increased by reducing the number of spacer carbons and increasing carbon sharing between cyclic repeating units.
研究领域:
材料科学
·
聚合物化学
✓ 已验证
DOI
高影响因子
MACROMOLECULES
·
2022
·
IF 6.057
Jianing Zhou,Jinxian Yang,Muhammad Waqas Ishaq,Lianwei Li
Exploring the difference in the topology–structure–conformation relationship for linear and cyclic graft polymers is an interesting topic. In this work, two libraries of linear graft (l-PPA-g-PS, with a linear backbone) and cyclic graft (c-PPA-g-PS, with a cyclic backbone) polystyrenes with low ratios of the backbone-to-sidechain contour length (rc, from 1.26 to 6.22) and various grafting densities (σ, from 0.16 to 0.86) have been studied as models. Atomic force microscopy (AFM) characterization has indicated ellipsoidal and spherical morphologies for both l-PPA-g-PS and c-PPA-g-PS with no significant difference. By comparing the absolute (Mw,abs) and apparent (Mw,app) molar masses, it is found that Mw,abs/Mw,app varies from 1.5 to 3.5 and gradually increases with σ. By measuring gh1/2 (gh1/2 = Rh,graft/Rh,linear), it is found that the two topologies have different compactness of conformation. By following the temperature-dependent interchain aggregation in cyclohexane, it is found that the cyclic backbone feature can suppress the interchain association and be more susceptible to graft density than linear graft polymers. The present study has clearly showed that the cyclic graft topology can potentially display unique structural and conformational properties, which can be attributed to the topological advantages such as more compact conformation and significant isotropic features.
研究领域:
聚合物科学
·
材料科学
·
物理化学
✓ 已验证
DOI
高影响因子
MACROMOLECULES
·
2019
·
IF 5.997
Bingjie Zhao,Kun Wei,Lei Wang,Sixun Zheng
3,13-Di(cyclic carbonate) double decker silsesquioxane, a new difunctional polyhedral oligomeric silsesquioxane (POSS), was successfully synthesized. By using this POSS macromer, the organic–inorganic poly(hydroxyl urethanes) (PHUs) were synthesized with POSS cages in the main chains. Compared to the neat PHU, the organic–inorganic PHUs displayed improved thermomechanical properties. The organic–inorganic PHUs were microphase-separated, and the main-chain POSS cages were self-assembled into the nanodomains in the size of 10–30 nm. It was found that the POSS nanodomains acted as the nano-cross-linking points of physically cross-linked networks. Although the linear organic–inorganic PHUs were soluble in common organic solvents, they were capable of displaying the thermomechanical properties similar to cross-linked PHU elastomers. Owing to the physical cross-linking, the organic–inorganic PHUs were endowed with shape memory properties. In the meantime, the organic–inorganic PHUs can be reprocessed at elevated temperature; the tensile mechanical strength can be recovered up to 90%. The reprocessing properties resulted from the transcarbamoylation reaction of hydroxyurethane structural units other than the disintegration of POSS nanodomains at elevated temperature. The reprocessing properties can be utilized to program the original shapes of shape memory polymers.
研究领域:
材料科学
·
高分子化学
·
纳米技术
·
有机-无机杂化材料
·
智能聚合物
·
力学性能
✓ 已验证
DOI
高影响因子
MACROMOLECULES
·
2019
·
IF 5.997
Song Guan,Wei Wen,Zhenzhong Yang,Aihua Chen
By taking advantage of strong liquid crystallization ordering and photo dimerization of the mesogen stilbene, we propose large-scale synthesis of nanowires of stilbene-containing block copolymers by polymerization induced hierarchical self-assembly. The interior of nanowires is in the type of liquid crystal (LC) structure with highly ordered smectic LC layers, which are perpendicular to the long axis. The alternative striped structure consists of the polymethacrylate backbone and stilbene-containing side chain. The approach is general toward stilbene-containing block copolymer LC nanowires, irrelevant with the composition of stabilizer blocks. The nanowires become robust with the layered structure preserved after cross-linking via dimerization upon UV irradiation. The nanowires reported here may provide one-dimensional model blocks toward superstructures, which can be used in the fields of electric nanoconductors, functional additives, etc.
研究领域:
材料科学
·
纳米技术
·
高分子化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）