POLYMER DEGRADATION AND STABILITY
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2022
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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
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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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
CHEMICAL ENGINEERING JOURNAL
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2022
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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
CHEMICAL ENGINEERING JOURNAL
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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
Polymer Chemistry
·
2022
·Vol. 13
·期 15
·2178-2186
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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 ENGINEERING AND SCIENCE
·
2022
·Vol. 62
·期 4
·1269-1280
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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
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2022
·Vol. 60
·期 9
·1492-1500
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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
ACS Applied Polymer Materials
·
2023
·
IF 5
Zhongxi Miao,Chaohua Peng,Long Xia,Hui Xu,Siyuan He,Cheng Chi,Jiahui Zhong,Shuchuan Wang,Weiang Luo,Guorong Chen,Birong Zeng,Lizong Dai
Currently, because of the depletion of petroleum resources and pollution problems associated with the use of petrochemicals, bio-based epoxy thermosets have received wide attention. However, epoxy thermosets derived entirely from bio-based raw materials combining high performances in mechanical properties, fire resistance, and degradation are less reported. In this work, a fully bio-based Schiff base epoxy resin named VA-FA-EP is prepared from vanillin (VA) and 2-furfurylamine (FA). The curing kinetics and behavior of the imine exchange reaction are explored systematically. After being cured by 4,4′-diaminodiphenylmethane (DDM), VA-FA-EP/DDM exhibits excellent mechanical properties with a glass transition temperature of 200.1 °C. VA-FA-EP/DDM has also been proven to have good fire resistance. There are significant reductions of 66.73% and 81.72% in total heat release (THR) and total smoke production (TSP), respectively. The intrinsic flame-retardant mechanism is systematically illustrated. In addition, the VA-FA-EP/DDM has also shown a good degradation property. In summary, this study offers a viable approach for producing eco-friendly fire-safe Schiff base epoxy thermosets utilizing entirely sustainable raw materials.
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高影响因子
MOLECULES
·
2023
·Vol. 28
·期 9
·3944
·
IF 4.6
Yin Lu,Yaliang Peng,Yi Yang,Jiahao Liu,Kan Zhang
There is an urgency to produce novel high-performance resins to support the rapid development of the aerospace field and the electronic industry. In the present work, we designed and consequently synthesized a benzoxazine monomer (oHPNI-fa) bearing both norbornene and furan groups through the flexible benzoxazine structural design capability. The molecular structure ofoHPNI-fawas verified by the combination characterization of nuclear magnetic resonance spectrum, FT-IR technology, and high-resolution mass spectrum. The thermally activated terpolymerization was monitored by in situ FT-IR as well as differential scanning calorimetry (DSC). Moreover, the low-temperature-curing characteristics ofoHPNI-fahave also been revealed and discussed in the current study. Furthermore, the curing kinetics of theoHPNI-fawere investigated by the Kissinger and Ozawa methods. The resulting highly cross-linked thermoset based onoHPNI-fashowed excellent thermal stability as well as flame retardancy (Td10of 425 °C, THR of 4.9 KJg−1). The strategy for molecular design utilized in the current work gives a guide to the development of high-performance resins which can potentially be applied in the aerospace and electronics industries.Keywords:benzoxazine;norbornene;furan;thermosets;thermal stability
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PubMed
高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2021
·
IF 6.953
Hongliang Wei,Songmao Li,Zijun Liu,Hongli Chen,Yuhua Liu,Weikun Li,Gang Wang
Herein, starch-cellulose interpenetrating network (IPN) hydrogels were fabricated by sequential Diels-Alder click reaction and photopolymerization in water. Moreover, β-cyclodextrin, a commonly used host molecule in supramolecular chemistry, was also introduced to improve the performance of the IPN hydrogel. Firstly, the starch-based dienes were synthesized by modifying starch with N-maleoyl-β-alanine, and the cellulose-based dienophiles were obtained by the reaction of cellulose and furfurylamide succinate; Secondly, the as-synthesized starch-based dienes, cellulose-based dienophiles, polymerizable β-cyclodextrin, crosslinker, and acrylamide were dissolved in water and obtained a transparent solution. The solution was maintained in a water bath of 50 °C for 3 h, forming the first network via catalyst-free click Diels-Alder reaction, subsequently, the second network was formed by photopolymerization. Their preparation conditions were optimized via one-factor experiments and their properties and structures were characterized. Finally, 5- fluorouracil (5-Fu) was used as a model drug to study the sustained release behavior of the drug-loaded hydrogels. Release profile was found to fit in Ritger-Peppas kinetic model and polymer relaxation and drug diffusion made a valuable contribution to drug release. Taking into account the virtues of easily controllable photopolymerization and catalyst-free Diels-Alder reaction, the strategy described here has a potential application in the preparation of IPN hydrogels.
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PubMed
高影响因子
JOURNAL OF POLYMER SCIENCE
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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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REACTIVE & FUNCTIONAL POLYMERS
·
2023
·
IF 5.1
Zhicheng Wang,Liang Qi,Zhigang Yuan,Athar Ali Khan Gorar,Abdul Qadeer Dayo,Wen Bin Liu,Jun Wang,Jun-yi Wang
Biobased diamine, difuran diamine (B-DFDA) synthesized from benzaldehyde and furfurylamine, was innovatively used to synthesize novel bio-based benzoxazine (V-bfa and Gu-bfa) by reacting with vanillin and guaiacol , respectively. The curing behavior was studied by differential scanning calorimetry (DSC) and fourier transform infrared spectroscopy (FT-IR), revealing that V-bfa has a low curing temperature, and the aldehyde group was not only consumed but also engaged in the formation of hydrogen bonds . Meanwhile, the V-bfa monomer required lower activation energy ( E k = 119.2 kJ/mol and E o = 120.9 kJ/mol), suggesting that the aldehyde group has a more unique effect, which may promote the ring opening of oxazine rings. Compared with poly(Gu-bfa), poly(V-bfa) has better mechanical properties , higher glass transition temperature (248 °C) and char yield (59.8%). At the same time, its lower dielectric constant ( k ) makes it promising for application in the field of electronic packaging and communications.
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高影响因子
危险品化学品经营许可证（带存储）