LANGMUIR
·
2024
·
IF 3.7
Guangzeng Luo,Zhilu Gao,Cuiping Zhou,Yintan Huang,Shuangshuang Hu,Yifan Hu,Chuanyong Zong,Lan Lei,Hui Li
Well-tailored construction of icephobic surfaces with mechanical robustness and investigation of the structure–property relationships at the molecular level are highly desirable. Herein, a series of norbornene-based fluorinated polyolefin copolymers (FPOR-x) with varying norbornenyl dodecafluoroheptyl ester (NDFHE) molar fractions (0–100 mol %) were well-designed and fabricated via living ring-opening metathesis polymerization (ROMP) employing NDFHE and norbornenyl pentafluorophenyl ester (NPFPE) as the soft and hard segments, respectively. The mechanical and icephobic properties of the fluorinated copolymers can be regulated by adjusting the soft NDFHE contents. As a result, the well-designed norbornene-based copolymers exhibited a wide range of tunable mechanical properties, including tensile strength ranging from 0.2 to 26.4 MPa, elastic modulus ranging from 0.6 to 593.7 MPa, and breaking elongations ranging from 5718.7% to 3.7%, correlating with the proportion of soft NDFHE content. Furthermore, the synergistic interplay between soft and hard segments, particularly the hardness in the majority and softness in the minority or vice versa, could achieve a significant difference in the local modulus and enhance the propagations of cracks within the three-phase regions (soft regions/hard regions/ice), ultimately leading to a significant reduction in ice shear strength. Notably, FPOR-25% with a tensile strength of 12.0 MPa and an elastic modulus of 227.5 MPa exhibited a remarkably low ice shear strength of 57.7 kPa. This study not only highlights the relationship between the polymer molecular structure and surface icephobic properties but also breaks the limitations of icephobic surfaces with a low modulus.
研究领域:
材料科学
·
高分子化学
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产品关联
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Yi Zhao,Ruichen Liu,Kai Jing,Li Wang,Xiangwen Zhang,Guozhu Li
Tetracyclo[6,2,1,01,7,13,6]dodecene (TCD) is conventionally synthesized by continuous heating of norbornene (NBE) and dicyclopentadiene (DCPD), in which the synthesis rate and isomer selectivity are hardly improved under such near equilibrium conditions. In this study, an alternative thermochemical synthesis technique using direct electric heating is present. Alternate heating and cooling of the reaction mixture can be rapidly realized by programmable electric current flowing in the reactor tube. The reaction has been switched in a timely fashion between high temperature and low temperature at a given speed. At a high temperature, the active intermediate of cyclopentadiene (CPD) quickly forms. Rapid cooling ensures the nonequilibrium kinetic control of CPD copolymerization for increasing the selectivity. The energy cost is reduced by lowering the average temperature. As optimized by the Bayesian method, the operating conditions of oscillating heating (e.g., amplitude, frequency, pressure, and so on) are determined to precisely match the time scales of fast generation and directed consumption of CPD. The oscillating heating method leads to a high yield of endo,exo-TCD (62.4% versus 11.6% by the conventional continuous-heating method). High-energy-density fuels with good low-temperature fluidity are prepared using hydrogenated TCD as the key component.
研究领域:
化学工程
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2024
·
IF 8.4
Ting Wang,Yu Wang,Wei You
Polycyclic norbornene derivatives, dicyclopentadiene (DCPD) and tricyclopentadiene (TCPD), have rigid structures with ease of accessibility and high chemical reactivity . After vinylic-addition polymerization, the resultant polynorbornenes (PNBs) possess high thermal stability, excellent mechanical integrity, and chemical inertness due to the retention of the rigid polycyclic norbornene motifs along the polymer backbones. Herein, we first report polycyclic PNBs composing DCPD or TCPD and an alkyl-bromide-substituted norbornene as comonomers to prepare high performance anion-exchange membranes (AEMs). The two double bonds in DCPD/TCPD can be used for vinylic-addition polymerization and thiol-ene click cross-linking reactions, respectively. By comparing with previously reported cross-linked PNB AEMs without polycyclic structures, it is unambiguously confirmed that the involvement of DCPD/TCPD significantly improved the mechanical strength (the stress-at-break of 34 MPa vs 28 MPa), the hydroxide conductivity (212 mS cm −1 vs 199 mS cm −1 at 90 °C), and the alkaline stability (93 % vs 81 % conductivity remaining after treating in 1 M KOH at 80 °C for 1200 h). The successful application of the AEMs with excellent durability for over 500 h prove that the involvement of polycyclic structures is a convenient strategy to enhance the performance of aromatic-free AEMs.
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2024
·Vol. 141
·期 36
·e55920
·
IF 2.7
Yi Yang,Yin Lu,Kan Zhang
In this study, we designed and synthesized a series of norbornene-furan functionalized benzoxazine monomers ( HPAP-fa , HPAMP-fa , and HPTM-fa ) by regulating the bridge length in benzoxazine structure in order to improve the comprehensive performance of norbornene-furan functionalized benzoxazine system. This research systematically examined the impact of flexible segments on the structural information, polymerization behaviors, thermal stability, and flame retardancy of resulting polybenzoxazines. Initially, the structural characteristics of benzoxazine were confirmed through nuclear magnetic resonance, Fourier-transform infrared (FT-IR), and HR-MS. Subsequently, the polymerization mechanisms of each benzoxazine monomer were investigated utilizing differential scanning calorimeter and in situ FT-IR analyses. Finally, the thermal stability and flame-retardant properties were investigated by TGA and micro-combustion calorimetry measurements. Consequently, HPAP-fa exhibited the lowest polymerization temperature and the corresponding poly(HPAP-fa) showed very high thermal stability ( T d5 of 392°C and T d10 of 437°C) as well as excellent flame retardancy (HRC of 83.7 J g −1 K −1 ), which shows a significant improvement compared to poly(HPTM-fa) . As a result, the modulation of bridge segments within the monomer represents a viable approach towards enhancing the holistic efficacy of norbornene-furan functionalized benzoxazine systems.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Xinyue Zhang,Yuan Yao,Yingying Cao,Xin Tan,Xiaomin Fang,Yanqiang Zhang
The high strain energy of the three-membered ring can increase the combustion calorific value of space fuels. At present, the cyclopropanation of alkenes is the bottleneck to obtain highly-energy three-member-ring fuels. In this article, Pd single-site catalysts (SSCs) were prepared to catalyze the cyclopropanation of norbornene. Pd2+ on the SSCs enhanced the adsorption of CH2N2 through electrostatic interaction, efficiently forming metal carbene. The conversion and selectivity of norbornene cyclopropanation reached 99.9% and 96.9%, which are much higher than those of commercial Pd/C (conversion 42.3%, selectivity 80.8%). In addition, the obtained tricyclooctane shows excellent properties (density 0.93 g/cm3, calorific value 42.75 MJ/kg) to be a promising high-performance rocket fuel. This work provides an efficient method for the synthesis of cyclopropane-based space fuels from alkenes.
研究领域:
化学
·
材料科学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY COMMUNICATIONS
·
2020
·
IF 1.943
Haibin Yuan,Hui Liu,Fen You,Xiaochao Shi
Palladium complexes bearing new tridentate quinolino-based [N − NN ox ] ligands were synthesized and tested for the polymerization of norbornene. Upon activation of MAO, all the palladium complexes showed high catalytic activities for the vinyl-addition polymerization of norbornene up to 11.5 × 10 6 g of PNB (mol of Pd) −1 h −1 . The structure–activity relationships in the polymerization of norbornene, namely steric and electric effects of the ligands, were carefully investigated.
研究领域:
有机化学
·
高分子化学
✓ 已验证
DOI
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2026
·
IF 3.1
Peng Zhao,Li Li,Yize Chen,Yuqiao Zhang,Long Zhang,Jianhua Li,Min Sun,Jianing Hui,Shun Li,Jianming Zhang
The escalating requirements of high-frequency wireless communication and advanced semiconductor packaging necessitate the development of polymeric materials with superior thermal stability and low dielectric loss. In this work, we present the development of a norbornene (NB)-derived epoxy system, synthesized using 5-Ethylidene-2-norbornene (ENB) and phenol as the key staring materials. The resulted ENB-phenol diglycidyl ether (ENBDE) was then cured with conventional commercial bisphenol-A (BPA) diglycidyl ether (DGEBA) epoxy resin at various ratios (ENBDE-DGEBA). Owing to the intrinsically rigid, low-polarity cyclic structure of NB, the introduction of ENBDE into the DGEBA results in the thermosets with significantly improved thermal resistance (glass-transition temperatures exceeding 230°C), excellent thermo-oxidative stability, and exceptionally decreased dielectric loss (~0.0064 at 10 GHz). These standalone properties, combined with favorable moisture resistance and good mechanical property, identify this newly designed ENBDE polymer can be used as a highly promising electronic material for next-generation high-frequency and high-speed electronic applications.
✓ 已验证
DOI
高影响因子
Marine Drugs
·
2017
·Vol. 15
·期 7
·223
·
IF 3.503
Na Li,Huanhuan Wang,Xiaosai Qu,Yu Chen
ROMP is an effective method for preparing functional polymers due to its having characteristics of “living” polymerization and rapid development of catalysts. In the present work, poly(norbornene-methylamine), a mimic of chitosan, was synthesized via ROMP reaction. The amino-protected product, 5-norbornene-2-(N-methyl)-phthalimide, was prepared by a reaction of 5-norbornene-2-methylamine with phthalic anhydride, which was then subjected to the ROMP reaction in the presence of Hoveyda-Grubbs 2nd catalyst to afford poly(norbornene-(N-methyl)-phthalimide). The target product, poly(norbornene-methylamine), was obtained by deprotection reaction of poly(norbornene-(N-methyl)-phthalimide). The products in each step were characterized by FTIR and1H-NMR, and their thermal stabilities were determined by TG analysis. The effects of molar ratio between monomer ([M]/[I]) and catalyst on the average relative molecular weight (Mn¯) and molecular weight distribution of the produced polymer products were determined by gel permeation chromatography (GPC). It was found that theMn¯of poly(norbornene-(N-methyl)-phthalimide) was controllable and exhibited a narrow polydispersity index (PDI) (~1.10). The synthesis condition of 5-norbornene-2-(N-methyl)-phthalimide was optimized by determining the yields at different reaction temperatures and reaction times. The highest yield was obtained at a reaction temperature of 130 °C and a reaction time of 20 min. Our work provides a new strategy to synthesize polymers with controllable structures and free –NH2groups via ROMP.Keywords:ROMP;poly(norbornene-methylamine);controllable;living polymerization;chitosan
研究领域:
高分子化学
·
生物材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
EUROPEAN POLYMER JOURNAL
·
2023
·
IF 6
Yi Yang,Yin Lu,Kan Zhang
Highly thermally stable polymeric materials synthesized from renewable resources are highly desirable in many high-performance fields due to the sustainable development of human beings. Herein, a new norbornene-containing monobenzoxazine thermosetting resin ( HPTM-fa ) exhibiting very high thermal stability has been prepared using natural bio-resourced tyramine and furfurylamine as starting materials. The structural details of HPTM-fa were characterized by FT-IR, NMR as well as high-resolution mass spectroscopies. The polymerization behaviors of cross-linkable norbornene , oxazine ring, and furan groups in HPTM-fa were investigated by DSC and in situ FT-IR analyses. In addition, the polybenzoxazine thermoset derived from this newly obtained bio-based mono-benzoxazine resin showed very high thermal stability with a T d5 of 413 °C and a glass transition temperature of 290 °C. The outstanding performance of thermoset based on HPTM-fa evidences its potential applications in the design of highly thermally stable polymeric materials.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER ENGINEERING AND SCIENCE
·
2024
·Vol. 64
·期 7
·3289-3302
·
IF 3.2
Xian Wang,Zehan Zhang,Feng Gao,Xuelian He
Surface chemical grafting modifications of carbon fibers (CFs) using 5-(triethoxysilyl)norbornene (TOS), norbornene carboxylic acid tert-butyl ester (NB-TBE), and 5-norbornene-2,3-dicarboxylic anhydride (NA) improved interfacial interactions between CFs and poly(dicyclopentadiene) (PDCPD) resin. The ring-opening metathesis polymerization (ROMP) of DCPD, catalyzed by Grubbs catalyst II, enabled the fabrication of PDCPD/CF layered composite materials with resin and fibers tightly adhered. The optimal composite exhibited remarkable mechanical properties, with a tensile strength of 654.6 MPa and flexural strength of 510.7 MPa. Excellent thermal stability with a maximum weight loss rate in temperatures above 450°C and good chemical resistance with a weight change of about 1% in both acidic and alkaline media highlight the promising potential of these materials for use in harsh environments. The simple yet efficient approach of TOS, NB-TBE, and NA-enhanced layered CF shows great promise as advanced composite materials for industrial applications. Highlights Norbornene derivatives such as TOS, NB-TBE, and NA are suitable modifiers for CF. ROMP of DCPD and norbornene group onto CFs, fabrication of PDCPD/CF composite materials. The composite exhibited remarkable interfacial adhesion and mechanical properties.
研究领域:
材料科学
·
复合材料
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER TESTING
·
2026
·
IF 6.4
Xiong Xiao,Hongying Duan,Qipu Feng,Yushang Lai,Fenglin Xiong,Liping Yang,Ziwei Huang,Chenxi Li,Yuchu Yang,Dan Long,Li Feng
A new strategy to synthesize norbornene-modified gelatin (GelNB) was introduced by utilizing norbornene-2-carboxylic anhydride. The synthesized GelNB showed great compatibility with positively charged thiolate ε- Polylysine (PLSH). • Compared with the GelMA or GelNB/DTT, the developed GelNB/PLSH exhibited superior photo-crosslinking reactivity, bioactivity, and printability. • Both GelNB/PLSH solution and hydrogel exhibited broad-spectrum antibacterial ability without the addition of any antibacterial additives. • The rat adipose-derived stem cells (ADSCs)-laden GelNB/PLSH scaffolds enhanced the wound healing outcomes of full-thickness skin defects. Photo-crosslinking-based 3D bioprinting is a promising approach to fabricate bioactive cell-laden scaffolds for wound healing. While thiol-ene-based bioink has been developed to fabricate 3D devices with improved gelation and bioactivity, the bacterial contamination remains a threat to further application. To address this problem, we have introduced a strategy to modify ε-Polylysine (ε-PL) with thiol groups (PLSH) and combine it with norbornene-modified gelatin (GelNB). The GelNB/PLSH bioink not only holds robust photo-crosslinking reactivity but also exhibits superior antibacterial capacity. The GelNB/PLSH hydrogel showed rapid photo-crosslinking rate, tunable physicochemical properties, improved bioactivity, favorable biocompatibility, and good printability. The GelNB/PLSH antibacterial bioink, along with rat adipose-derived stem cells (rADSCs), can be used to construct 3D scaffolds that promote full-thickness skin defects healing in rats. Overall, this study preliminarily prove the potential of GelNB/PLSH as an antibacterial bioink for wound healing and tissue engineering.
✓ 已验证
DOI
高影响因子
MOLECULES
·
2026
·Vol. 31
·期 16
·2800
·
IF 5.1
Peng Zhao,Jianming Zhang,Li Li,Long Zhao
In this work, to meet the requirements of high-performance electronic devices for high-frequency/speed telecommunication and semiconductor packaging, we developed a norbornene (NB)-backboned epoxy/cyanate ester compound system to modify the commercial bisphenol-A (BPA) diglycidyl ether (DGEBA) epoxy resin. A norbornene-based epoxy monomer (ENBDE) and cyanate ester (ENBCY) were synthesized using 5-ethylidene-2-norbornene (ENB) as the key starting material. The ENBDE was blended with DGEBA as the epoxy resin compound, which was cured using ENBCY as the curing agent to form a cross-linked thermoset. The effect of ENBDE content on thermal stability, mechanical properties, dielectric performance, and bonding strength of the thermosets was investigated. The optimized formula showed a significantly improved thermal stability of the cured resin with a glass-transition temperature of 249.2 °C and a 5% weight-loss temperature (T 5% ) of 351.5 °C; the dielectric constant and dissipation factor at a high frequency of 10 GHz were measured to be as small as 2.57 and 0.0068, respectively, showcasing great potential as a high-performance dielectric epoxy material for high-frequency/speed electronic applications.
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产品关联
DOI
PubMed
高影响因子
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