POLYMER ENGINEERING AND SCIENCE
·
2022
·Vol. 62
·期 4
·1269-1280
·
IF 2.573
Shuo Chen,Yu Feng,Zhi-Yuan Zhang,Xiang-Yuan Li,Jun-Ying Zhang,Jing-Bo Zhao
Diels–Alder (DA) addition is an efficient method to repair damages at mild conditions. It is often used in self-healing polyurethanes and epoxy resins and seldom used in cross-linked polyamides (cPAs). Michael addition becomes a useful method to synthesize cPAs. However, no efficient way has been established to conduct double-addition of primary amines. In this work, organic catalyzed Michael addition and polycondensation were established to prepare polyamide oligomers with furan pendent groups (pFU-PAs), and a DA addition was adopted to prepare self-healing cross-linked polyamides (SH-cPAs). A bulk double Michael addition of furfurylamine and methyl acrylate was performed at 30–70°C in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), or 4-(N,N-dimethylamino) pyridine (DMAP), and a high yield of furfurylamine-N,N-bis(methyl propionate) (FA-BMP) was prepared. The catalytic activity order is MTBD>TBD >>DMAP in Michael addition. Melt polycondensation of FA-BMP with bis(2-aminopropyl) polypropyleneglycol and hexamethylene diamine was catalyzed by MTBD and N,N′-diphenylthiourea. The DA addition of 1,5-bismaleimido-2-methylpentane and pFU-PAs was monitored by FT-IR, 1 H NMR, DSC, polarizing optical microscopy, and gel content. In these catalyzed processes, the structures of FA-BMP, pFU-PAs, and SH-cPAs were controlled easily, and the SH-cPAs showed good mechanical property and excellent self-healing performance of 88%–98%.
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高影响因子
JOURNAL OF POLYMER SCIENCE
·
2022
·Vol. 60
·期 9
·1492-1500
·
IF 3.046
Shitong Ren,Fangjing Tian,Shaoheng Zhang,Weicong Zhou,Yonggang Du
Developing thermosets derived from renewable sources is of great importance. In this work, a fully bio-based benzoxazine monomer, 3,6-bis((3-(furan-2-ylmethyl)-3,4-dihydro-2 H -benzo[ e ][1,3]oxazin-6-yl)methyl)piperazine-2,5-dione (TCDPF), is conveniently synthesized from L-tyrosine cyclic dipeptide (TCDP), furfurylamine and paraformaldehyde. The chemical structure of TCDPF is confirmed by nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy (FT-IR) techniques. The curing behavior of TCDPF is investigated by differential scanning calorimetry and in situ FT-IR techniques. After temperature-programmed curing, the thermomechanical property and thermal stability of the resulting TCDPF polymer (PTCDPF) are evaluated by dynamic mechanical analysis and thermogravimetric analysis techniques, respectively. It is found that PTCDPF have excellent comprehensive performance such as high glass transition temperature ( T g = 322 °C), high thermal degradation temperature ( T 5% = 342 °C, T 10% = 395 °C in N 2 atmosphere), and high char yield (CY = 51.3% at 800 °C in N 2 atmosphere). The results demonstrate that L-tyrosine is a promising bio-based raw material for preparing high performance polybenzoxazines. Graphical
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高影响因子
Polymer Chemistry
·
2022
·Vol. 13
·期 15
·2178-2186
·
IF 5.364
Qi-Sheng Huang,Pei-Chen Zhao,Jian-Cheng Lai,Xiao-Peng Zhang,Cheng-Hui Li
Traditional thermoset polymers such as epoxy resin have strong mechanical strength but are difficult to recycle, reshape and reprocess after being cured. When these materials are damaged, they can only be scrapped, resulting in a waste of resources. Introducing dynamic interactions into thermoset polymers can endow them with recyclable, reshapable and self-healing properties, thus prolonging their lifetime. In this work, we demonstrate that epoxy resin modified by coordination bonds between Ni2+ ions and imidazole/hydroxyl groups can show high mechanical strength (Young's modulus ranges from 210.4 ± 15.7 MPa to 564.7 ± 9.6 MPa) as well as thermoreversible behaviors (can be healed, reshaped and recovered at 80 °C and 0.1 MPa). More interestingly, due to the structural transformation of the Ni2+ coordination complex between the four-coordinated geometry and the six-coordinated geometry upon changing the temperature, this material shows reversible thermochromic behavior. Therefore, it has potential applications in the field of thermochromic smart windows.
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高影响因子
POLYMER DEGRADATION AND STABILITY
·
2022
·
IF 5.204
Dan Xiao,Meng-Ting Zheng,Fang-Juan Wu,Xiao-Xia Cao,Xing-Fang Huang,Li Huang,Xue-Qing Xiao
Aiming to develop the crystallization and anti-flammability additives for creating high performance PLA, in this paper, a novel multifunctional bio-based furan derivative phenyl P-(N-N'-di-(furan-2-ylmethyl))phosphonamidate (PFPA) is synthesized and then is incorporated into PLA to enhance its comprehensive properties. The low loading of multifunctional bio-based PFPA not only as the nucleating agent increases the crystallinity and crystallization rate for PLA matrix, but also significantly improves anti-flammability properties of PLA. The V-0 classification in UL-94 and LOI result of 30.7 % for PLA with only loading 3 wt% PFPA are achieved. Moreover, the heat release values in cone-calorimeter measurement of PLA/3%PFPA composites are obviously decreased. The anti-flammability mechanism displays that PFPA forms highly-efficient fire-retardant radicals, accelerates heat away, suppresses combustible gases, and enhances stable residual carbon during PLA/PFPA combustion. This work provides a facile and efficient strategy for preparing multifunctional bio-based additives crystallization and fire-safety agent for PLA as well as promises broad application in engineering materials.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Dan Xiao,Zi-Bo Wang,Uwe Gohs,Kathrin Harre,De-Yi Wang
In this work, the highly-efficient multifunctional bio-based fire retardant phenylphosphonic difurfurylamine (PPDF) was prepared successfully for poly(lactic acid) using furfurylamine and phenylphosphonic dichloride. Moreover, the structure of PPDF was analyzed by NMR, FTIR and MS. The fire safety, thermal, crystallization, rheological and mechanical properties of PLA/PPDF compounds were systematically tested by LOI, UL94, cone calorimeter test, TGA, DSC, polarizing optical microscope, rheometer, DMA and tensile properties. Surprisingly, only a very small loading of 0.8 wt% loading of bio-fire retardant PPDF could increase the LOI value of PLA from 19.0 % to 30.0 % and achieve V-0 rating in UL-94 vertical burning test. Moreover, PPDF not only reduced the molecular entanglement and viscosity of PLA, but also acted as a nucleating agent to increase crystallinity and crystallization rate of PLA matrix. More importantly, in the gas phase phosphorus, the PLA/PPDF compounds based on highly reactive benzene, phosphorus, phosphooxygen and phosphooxygen benzene radicals from the pyrolysis of PPDF had a highly-efficient fire safety. In the condensed phase, a relative stable residual char layer played a secondary role in the barrier. Thus, the total heat release and ignition time of PLA/PPDF compounds were evidently declined by 8.3 % and 10 s with only 0.8 wt% of PPDF loading.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Yin Lu,Yuan Zhang,Kan Zhang
Developing high-performance thermosets with outstanding anti-flammability from sustainable resources has attracted increasing attention due to both safety and environmental concerns. Herein, a novel bio-based bis-benzoxazine thermosetting resin has been successfully synthesized via Mannich condensation reaction from paraformaldehyde and natural renewable resources, aesculetin and furfurylamine. Detailed information of the chemical structure for this bio-benzoxazine is analyzed by nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopies, elemental analysis and high-resolution mass spectrometry (HR-MS). In addition, the resin polymerization behavior is investigated by differential scanning calorimetry (DSC) and in situ FT-IR analyses. Notably, the fully polymerized bio-thermoset shows high thermal stability with T d10 of 407 °C and T g of 261 °C, and extremely low flammability with heat release capacity (HRC) value of 2.51 J·g −1 ·K −1 and total heat release (THR) value of 0.78 kJ·g −1 . Overall, the current work provides a facile and sustainable synthetic route access to a series of halogen- and phosphorus-free nonflammable bio-thermosets based on smart benzoxazine chemistry.
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高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2022
·
IF 8.025
Dan Xiao,Jin-Xiang Lv,Fang-Juan Wu,Zi-Bo Wang,Kathrin Harre,Jian-Hong Chen,Uwe Gohs,De-Yi Wang
Currently, it is still a huge challenge to prepare high performance eco-friendly poly(lactic acid) (PLA) with high thermal stability , good processability, excellent crystallization behavior, good transparency and highly-efficient fire safety. In this paper, a novel bio-based nucleation agent N-(furan-2-ylmethyl)- P , P -diphenylphosphinic amide (FPPA) was prepared and used for the fabrication of fire safety PLA/FPPA composites. The chemical structure of FPPA was measured by FTIR, NMR and MS. Further, the crystallization behavior, thermal stability, fire safety and mechanical properties of PLA/FPPA composites were performed by TGA , DSC , polarization microscope, LOI, UL94, cone calorimeter, DMA and, SEM, Raman, GC–MS, and TGA-FTIR. The results showed that the multifunctional FPPA not only had a high thermal stability and was a good nucleation agent for PLA. Moreover, only loading of 3 wt% FPPA increased the LOI of PLA from 19.0 to 33.8 % with UL-94 V-0 classification. Furthermore, the heat release rate and total heat release values of PLA/3%FPPA composite reduced by 6.3 % and 15.3 % in cone-calorimeter test. Such high fire safety was mainly attributed to specific fire safety radicals due to thermal degradation of FPPA to interrupt composites burning in gas phase. Besides, transparency and mechanical properties were almost not changed because of low loading of FPPA in PLA. This multifunctional bio-based fire-retardant for PLA with good comprehensive performance promises broad application in engineering electronics, automobiles, 3D printing and construction materials.
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PubMed
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2021
·
IF 3.975
Hafezeh Nabipour,Haoxin Niu,Xin Wang,Sadia Batool,Yuan Hu
There are many applications for epoxy resin as a coating material in the automotive, electronics, and aerospace industries. However, when derived from petrochemical industries, adversely affect the environment, as they are rigid and resistant to recycling due to inherent cross-linked structure. In the present study, we prepared green epoxy resin from renewable resources, able to replace the conventionally produced DGEBA thermoset . Initially, we synthesized an epoxy thermoset from vanillin-derived Schiff base epoxy monomer (VTA-EP) that was thermally cured with bio-based 5, 5′-methylenedifurfurylamine (DFA). Due to the unsaturated double bond in cured VTA-EP/DFA thermoset displayed a relatively high glass transition temperature (T g ~ 170 °C) than the DGEBA/DDM system. Also, tensile strength (60 MPa), storage modulus (3271 MPa), and elongation at break (2.8%) were higher. Additionally, the peak of heat release rate (PHRR) and the total heat release (THR) of the cured VTA-EP/DFA resin decreased, and LOI and UL-94 ratings were improved. The green epoxy thermoset exhibited good dissolution in various acidic conditions due to the degradability of the Schiff base network in contrast to DGEBA/DDM. This work demonstrates that the combination of biomass with Schiff base structure provides a versatile platform for the fabrication of multifunctional vanillin-derived epoxy thermosets.
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高影响因子
RSC Advances
·
2021
·Vol. 11
·期 51
·32369-32375
·
IF 3.361
Min Xia,Yanjie Zhang,Qing Na,Tao Guo,Minghao Zhang,Zhenyu Qi,Ningning Liu,Fanzhi Yang,Yunjun Luo,Wei Yang
Cracks generated in energetic composites will affect their mechanical properties and increase the risk of explosion when they are exposed to external stimuli. Therefore, self-healing properties of energetic composites have always been at the forefront of research in the field of high-performance energetic composites. Hydroxyl-terminated polybutadiene (HTPB) is a kind of binder widely used in propellants. A novel furan-terminated polybutadiene (FTPB) was synthesized by the reaction of NCO-terminated polybutadiene (IPDI-HTPB-IPDI) with furfuryl amine, and then self-healing binder films were obtained based on the DA adduct (FTPB-DA) through the reaction of furan with bismaleimide. The results show that FTPB-DA will transform into FTPB and BMI at 120 °C and recrosslinked at 60 °C to form FTPB-DA again, which gives it self-healing properties and the healing efficiency can reach 92.3%. Then, by adjusting the ratio of –NCO/–OH during the preparation process, we prepared self-healing binders with different DA adduct contents, and further studied the influence of DA adduct content on the mechanical properties and self-healing performance.
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高影响因子
JOURNAL OF POLYMER SCIENCE
·
2021
·Vol. 60
·期 5
·794-802
·
IF 0
Jiarui Yu,Nan Gao,Xiaowen Xie,Xing Xin,Zhanqi Li,Shuai Chen,Jingkun Xu
Thermally healing capability of cracks and defects is important and urgent for the safe operation and life extending of electric materials and devices. Here, by the combination of thermally driven reversible Diels–Alder (DA) interaction and in-situ chemical oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT), a series of intrinsically conductive poly(3,4-ethylenedioxythiophene) (PEDOT)/DA composites possess intrinsically self-healing property under low-temperature (reverse DA reaction at 100°C; DA crosslinking at 60°C) stimulus were achieved. The crosslinking DA bonding reactions are multiple from the co-existence of pre-synthesized macromolecular polyurethane attached DA units (PU-DA) and 2,4-hexadiyne-1,6-diol (DADOL) in the films. PU-DA involved in the polymerization process of EDOT to endow PEDOT with outstanding solution-processability, uniform film making, and structural self-healing capability, while DADOL was added to enhance the cross bonding between polymer chains. This work will accelerate the research and application development of intrinsically self-healing conducting polymers for commercial capacitors, antistatic coatings, implantable, printable electronics, and so on. Graphical
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RSC Advances
·
2021
·Vol. 11
·期 49
·30943-30954
·
IF 3.361
Wei Peng,Yu-xuan Xu,Shi-bin Nie,Wei Yang
Phosphorus-containing flame retardants have received huge interest for improving the flame retardant behavior of epoxy resins (EP) over the past few decades. However, a satisfactory flame retardant effect requires high loading of most phosphorus-containing flame retardants, resulting in the deterioration of the thermo-mechanical properties of the flame retardant epoxy materials. To obtain the flame retardant EP with excellent comprehensive properties, a furfurylamine-derived bis-DOPO derivative (FA-bis-DOPO) was synthesized from bio-mass as a co-curing agent for the flame retardant EP. The incorporation of FA-bis-DOPO improved the mechanical strength, the storage modulus and the glass transition temperature of the flame retardant epoxy materials, owing to its stiffness and reactivity with the epoxy matrix to enhance the crosslinking density. The EP material containing 5.0 wt% of FA-bis-DOPO had an LOI of 31.0% and UL-94 V-0 rating, while the pristine EP had an LOI of 23.5% and failed in the UL-94 test, manifesting the high flame retardant efficiency of FA-bis-DOPO. Besides, the cone calorimeter results demonstrated that the PHRR, THR, and TSP values of the EP/FA-bis-DOPO-5.0 were 28.0%, 27.3%, and 9.9% lower than those of the pristine EP, respectively. The flame retardant mechanism of FA-bis-DOPO could be attributed to the combined vapor and condensed phase mechanisms which involved the interruption of the combustion chain reaction by quenching radicals and the inhibition of the transfer of pyrolytic volatile products by catalytic formation of an intact and compact char layer.
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高影响因子
COMPOSITES PART A-APPLIED SCIENCE AND MANUFACTURING
·
2021
·
IF 7.664
Yuan Cao,Min Zhi Rong,Ming Qiu Zhang
To tackle the challenge of manufacturing highly filled composite materials via melt compounding and injection molding , the authors proposed a novel approach based on Diels-Alder (DA) chemistry. Polycaprolactone oligomers (PCL olig , M w = 2000 g/mol) were firstly crosslinked by DA bonds, and then the resultant network PCL olig -DA was also connected to maleimide functionalized Al 2 O 3 particles (Al 2 O 3 -M) via DA bonds. Upon being heated to the retro-DA reaction temperature, the covalent adaptable composite network exhibited low viscosity due to de-crosslinking, enabling melt processing and well dispersion of high-concentration fillers. During the subsequent cooling, the composite network was regained because of DA reaction, benefiting increase of the composite’s strength . Consequently, the contradictory requirements for molecular weight of matrix polymer under the circumstances, which had better to be as low as possible during the manufacturing but as high as possible in the ultimate composites, were skillfully satisfied.
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高影响因子
危险品化学品经营许可证（带存储）