Cage–ladder-structure,phosphorus-containing polyhedral oligomeric silsesquinoxanes as promising reactive-type flame retardants for epoxy resin

We synthesized a novel cage–ladder-structure, phosphorus-containing polyhedral oligomeric silsesquinoxane (CLEP–DOPO–POSS) via the hydrolytic condensation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)–vinyl trimethoxysilane (VTMS) with 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane and then incorporated it into epoxy resins (EPs) in different ratios with thermal curing technology. The structure of CLEP–DOPO–POSS was confirmed by Fourier transform infrared spectroscopy, NMR spectroscopy (¹H-NMR and ²⁹Si-NMR), matrix-assisted laser desorption ionization time-of-flight, and X-ray diffraction. The thermal stability, mechanical properties and flame retardancy effect of CLEP–DOPO–POSS on EP were comprehensively evaluated via thermogravimetric analysis (TGA), dynamic mechanical analysis, universal tensile testing, limiting oxygen index (LOI) measurement, UL-94 testing, and cone calorimetry. The flame-retardant mechanism of the EP modified with CLEP–DOPO–POSS was investigated by TGA–IR, TGA–mass spectrometry, and scanning electron microscopy. The experimental results show that CLEP–DOPO–POSS was homogeneously dispersed in the EP matrix. The LOI value reached 31.9, and the UL-94 grade passed V-0 with the presence of only 0.28% P (2.91 phr CLEP–DOPO–POSS). In addition, the EP composite containing CLEP–DOPO–POSS exhibited a better thermal stability and mechanical properties. The flame-retardant mechanism was attributed to the quenching effect of the phosphorus-containing free radicals and the formation of phosphorus- and silicon-containing char layers in the condensed phase. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47607.     

无卤阻燃PF/EP/GF布复合材料的固化性能和阻燃性能

采用环氧树脂(EP)作固化剂,2,4,6-三(二甲胺基甲基)-苯酚(DMP30)作固化促进剂改善酚醛树脂(PF)的固化性能,以氢氧化铝和有机磷阻燃剂协同改性其阻燃性能,将其涂覆于玻璃纤维(GF)布上,压制成无卤阻燃PF/EP/GF布复合材料.用傅立叶变换红外光谱(FTIR)仪和差示扫描量热(DSC)仪对无卤阻燃PF/EP/GF布复合材料的固化反应机理、固化反应动力学进行了分析研究,并测试了该复合材料的阻燃性能.结果表明,无卤阻燃PF/EP/GF布复合材料的固化反应表观活化能Ea=75.7 kJ/mol、反应级数n=0.91,起始固化温度、固化峰顶温度、固化终止温度分别为108.6、133.2、152.9℃;当氢氧化铝质量分数为14%、DMP30质量分数为1%、有机磷阻燃剂质量分数为4.8%时,无卤阻燃PF/EP/GF布复合材料的固化性能、阻燃性能均达到较佳状态.     

Medium dielectric constant and low-loss PTFE composites filled with MgO-LiF co-doped Li2TiO3 particles

In this work, we presented a simple strategy to fabricate medium dielectric constant and low-loss composites for microwave substrate applications. MgO-LiF co-doped Li₂TiO₃ (LT) powders were fabricated by the solid-state reaction route and modified by perfluorooctyltriethoxysilane (F8261). The LT/polytetrafluoroethylene (PTFE) composites were fabricated by cold pressing and hot treatment. The XPS and contact angle analysis indicated that the fluorinated group was introduced to LT particle successfully. The effects of modified LT powders content on the dielectric, thermal, and mechanical properties of composites were investigated. As the modified LT content increases, the dielectric constant, dielectric loss, and temperature coefficient of dielectric constant (τ_ε) increase while the bending strength and coefficient of thermal expansion (CTE) decrease, which is attributed to the higher dielectric constant of LT ceramic, more pores, stable τ_ε of LT ceramic, interface defects and low CTE of LT ceramic, respectively. The composites with 60 wt % LT exhibit the best microwave dielectric properties: ε_r = 6.8, tanδ = 0.001, τ_ε = −29.6 ppm °C⁻¹ at 8 GHz and acceptable coefficient of thermal expansion (28.3 ppm °C⁻¹). Therefore, modified LT powders filled PTFE composites are potential materials for high-frequency microwave substrate applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47980.     

摩尔质量对软质PVC/EP树脂复合材料性能的影响

以环氧树脂(EP)为改性剂,研究了三种不同摩尔质量软质聚氯乙烯(S-PVC)的力学性能,考察了EP含量,后热处理等条件对S-PVC/EP复合材料性能的影响。实验结果表明:EP能有效降低S-PVC的压缩永久变形;后热处理使得EP进一步固化,有利于压缩永久变形的降低;随着PVC摩尔质量的增加,S-PVC/EP复合材料的力学性能提高。     

晶须改性二苯甲烷型双马来酰亚胺树脂体系的研究

以硼酸铝晶须、钛酸钾晶须为增强剂，以N，N′-二胺基二苯甲烷型双马来酰亚胺(BMI)／O，O′-二烯丙基双酚A(BA)体系作为基体，采用浇注成型工艺制备了晶须增强二苯甲烷型双马来酰亚胺树脂基复合材料。研究了晶须对树脂体系凝胶特性的影响，晶须对体系固化反应性的影响；晶须的种类、表面处理方法、含量对树脂体系力学性能和热性能的影响；树脂体系的固化工艺材料对性能的影响。结果表明，晶须对树脂体系固化工艺影响不大；硼酸铝晶须增强效果优于钛酸钾晶须；偶联剂以丙酮作溶剂处理的效果优于乙醇水溶液，酸化溶剂的效果更好；晶须可明显改善体系的力学性能和耐热性，在晶须添加量为15％左右时，所得体系的综合性能较好；改进的固化工艺有助于树脂体系性能的改善。在本研究中，弯曲强度最大提高了约18％，热变形温度最大提高了12％。     

Molecular design and properties of intrinsic flame-retardant P-N synergistic epoxy resin

In recent years, the poor weather resistance and aging resistance of additive flame retardants have caused researchers to pay attention to reactive flame retardants. A novel P-N coacting epoxy curing agent with intrinsic flame retardancy was designed and synthesized. The mechanical properties, crosslinking curing properties and flame-retardant properties of intrinsic flame-retardant epoxy resin were characterized. The results show that the cross-linking curing performance of hexa (3,5-diamino-1,2,4 triazolyl)-cyclotriphosphonitrile) (VCP) is lower than that of DDM. This is due to the decrease in cross-linking density caused by the VCP ring molecular structure. Therefore, the mechanical properties of the epoxy resin cured with VCP decreased, but the flame-retardant properties of the material significantly improved. The limiting oxygen index of the VCP/EP flame retardant epoxy thermosets was 27.3%, reaching the UL 94 V-1 level. The peak heat release rate and total heat release rate of the VCP/EP flame retardant epoxy thermosets were significantly reduced. The flame retardancy mechanism was studied by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, and x-ray photoelectron spectroscopy. The results show that the intrinsic flame-retardant P-N coacting epoxy resin has excellent curing and flame-retardant properties.     

端羧基修饰单宁酸/没食子酸环氧树脂复合材料的制备与性能研究

通过A₂+B₃一步法及缩聚反应分别制备生物质超支化聚合物 （CTMTA）和没食子酸环氧树脂（GAER）,采用熔融共混法制备了没食子酸环氧树脂（GAER）/甲基四氢苯酐（MTHPA）/2?甲基咪唑（2?MI）/ 超支化聚合物 （CTMTA）复合材料。利用傅里叶变换红外光谱仪（FTIR）、核磁共振仪（¹H?NMR）、差示扫描量热仪（DSC）、扫描电子显微镜（SEM）、力学性能和吸水率等试验,研究了CTMTA 含量对GAER/MTHPA/2?MI复合体系性能的影响。结果表明,CTMTA的加入能提高复合体系的力学性能和吸水率,降低复合体系的固化温度。当CTMTA含量为1.5 %（质量分数,下同）时,GAER/MTHPA/2?MI/CTMTA复合体系的力学性能和吸水率最佳,拉伸强度、断裂伸长率、冲击强度和吸水率分别比GAER/MTHPA/2?MI体系提高了33 %、37 %、47.6 %和45.5 %。GAER/MTHPA/2?MI/CTMTA复合体系的最佳固化工艺参数为110 ℃/20 min。     

Influence of modified fiber–MHSH hybrids on fire hazards,combustion dynamics,and mechanical properties of flame-retarded poly(butylene succinate) composites

Environmental problems caused by polymers and polymers have historically dominated both academic and industrial attention. Sustainable biodegradable wood-plastic composites (WPCs) as an optimum can solve the environmentally critical problems caused by petroleum-based polymers. However, they are flammable, prone to fire accidents, and often have a contradiction between mechanical performance and flame-retardant properties, which limits their range of applications. Here, we reported a flame-retarded poly(butylene succinate) (PBS) WPC prepared with modified natural fiber-magnesium hydroxide sulfate whisker (MHSH) hybrids and intumescent flame retardant s (IFRs). The mechanical performance, flame-retardant properties , thermal stability, and actual fire simulation parameters of composites were investigated. Owing to the unique composition characteristics of modified cassava dregs-MHSH hybrids, the mechanical properties (70P/23I/5C/2M, flexural strength was 39.2 ± 1.960/MPa, impact strength was 7.95 ± 0.3975/ [KJ/m²]), flame retardant properties (70P/23I/5C/2M, the limiting oxygen index value was 39.6%, UL-94 was V0) and thermal stability of WPC have been improved. Thereby, the balance between mechanical performance and flame retardant properties of biocomposites has been achieved in the practical engineering requirements. Furthermore, cone calorimeter data indicated that modified cassava dregs–MHSH hybrids played a role in improving the fire safety of composites. The total heat release, total smoke produce, toxic gas release, and total oxygen consumed of 70P/23I/5C/2M were lowered compared with those of 70P/25I/5C. Dynamics analysis indicated that the addition of modified cassava dregs–MHSH hybrids increased the activation energy of composites. Based on the experimental and analyses data, especially the morphological characterization of char residue analysis, it illustrated that modified cassava dregs–MHSH hybrids have a reinforcement and flame-retardant effect. The combusted residue of the incorporated modified cassava dregs–MHSH hybrids could support the three-dimensional charred layer formed by the combustion products of the IFR and the PBS. Thus, the more stable three-dimensional charred layer could not only effectively reduce thermal conductivity of composites but also hinder the propagation of heat into the interior substrate, thereby improving the flame-retardant properties of the WPC. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48490.     

The production of carbon nanotube/epoxy composites with a very high dielectric constant and low dielectric loss by microwave curing

Multiwalled carbon nanotube (MWCNT)/epoxy (EP) composites were developed using microwave curing (m-MWCNT/EP). They have a very high dielectric constant and low dielectric loss. For comparison, composites based on the same components were also prepared by thermal curing (t-MWCNT/EP). Results show that the two types of composites have greatly different dielectric properties. With the same content of MWCNTs, m-MWCNT/EP composites show a much higher dielectric constant and lower dielectric loss than t-MWCNT/EP composites. Specifically, the dielectric constant and loss at 100 Hz of m-MWCNT/EP composite with 0.04 vol% MWCNTs are about 2.5 and 0.05 times the corresponding value of t-MWCNT/EP composites, respectively, because of their different structures. Compared with t-MWCNT/EP composites, the nanotubes in m-MWCNT/EP composites not only have a better dispersion in the matrix, but also align in a direction. An equivalent circuit model was set up to evaluate the influence of dispersion and spatial distribution of MWCNTs on the dielectric properties. It shows that it is possible to control the dispersion and spatial distribution of carbon nanotubes using a different curing technique to obtain high performance composites with unexpected dielectric properties, especially those with very high dielectric constant and low dielectric loss.     

耐水阻燃透明型环氧树脂的制备及其应用研究

以二苯基次磷酰氯和哌嗪为原料,成功合成了疏水性阻燃剂哌嗪-1,4-二烷基双(二苯基氧化膦)(PPDO),并将其添加到环氧树脂(EP)中,制备了阻燃EP复合材料.通过垂直燃烧、氧指数、热失重分析、锥形量热分析和力学性能测试对EP复合材料的阻燃性能、热分解行为、燃烧行为和力学性能进行了详细研究.结果表明,阻燃剂含量为17％...     

A high-efficiency DOPO-based reactive flame retardant with bi-hydroxyl for low-flammability epoxy resin

A high-efficiency DOPO-based reactive flame retardant (DPE) with bi-hydroxyl was successfully synthesized via reacting DOPO with imine obtained from the condensation of ethanolamine and 1,4-phthalaldehyde, and used as co-curing agent to improve the fire safety of epoxy resin (EP). Its chemical structure was characterized by Fourier transform infrared (FTIR) spectra, ¹H, ³¹P nuclear magnetic resonance (NMR) spectra and elemental analysis. The curing behavior, thermal properties, flame-retardant properties of EP/DPE systems were investigated. The results revealed that DPE slightly decreased the glass transition temperature (T_g), but accelerated the curing cross-linking reaction of EP. Furthermore, DPE decreased thermal degradation rate of epoxy matrix and promoted the formation of residual char at high temperature. After adding DPE, the flame retardant of epoxy thermosets was greatly improved. Especially, the thermoset modified with 5 wt% DPE achieved limiting oxygen index (LOI) value of 33.6% and V-0 rating in UL-94 test, demonstrating the highly efficient flame retardancy. While its peak heat release rate (PHRR), total heat release (THR) and total smoke production (TSP) were respectively decreased by 32.6%, 17.8%, and 13.9% compared with neat EP. Moreover, the research on flame retardant mechanism disclosed that DPE played dual flame-retardant effect in the gaseous and condensed phases.     

Novel multi-element DOPO derivative toward low-flammability epoxy resin

In order to obtain cured epoxy resin (EP) with satisfactory thermal stability and flame retardancy, a multi-element P/N/Si-containing flame retardant (DPAK) was synthesized by a facile way and was used as a reactive flame retardant to prepare flame-retardant EP. The flame-retardant efficiency of DPAK was subsequently evaluated by limiting oxygen index (LOI), UL-94, and cone calorimeter (CC) test. With a low incorporation amount of DPAK (4 wt%), the resultant EP achieve to UL-94 V-0 rating, and the corresponding LOI value reached to 30%, which was higher than that of EP containing DOPO (2.9 wt%). More importantly, the thermogravimetric analysis (TGA) revealed their higher thermal stability than those of EP containing DOPO. Furthermore, dynamic mechanical analysis (DMA) shown the maintained glass transition temperature of DPAK-EP. The increase of CO/CO₂ ratio in the CC test for the DPAK-EP samples proved the gas-phase activity of DPAK. Additionally, DPAK showed evidence of condensed phase activity by increasing char residue in TGA and CC test. The scanning electronic microscope together with the energy dispersive X-ray spectrometer (SEM–EDX) and X-ray photoelectron spectroscopy (XPS) exhibited that DPAK promoted the formation of compacted phosphorus-silicon char layer. Subsequently, TG-FTIR results indicated that DPAK-EP produced lesser combustible gases than neat sample did, improving flame-retardant properties of epoxy resin.     

含亚甲基链段柔性固化剂的制备与性能研究

以双官能度EP(环氧树脂)对脂肪族二胺进行改性,制备了含多段长亚甲基链段的柔性固化剂。采用FT-IR(红外光谱)法、TGA(热失重分析)法、非等温DSC(差示扫描量热)法和β-T(升温速率-温度)外推法等对改性固化剂的结构、改性固化剂/EP胶粘剂的性能(包括热稳定性、动态力学参数和最佳固化温度等)进行了分析和验证。结果表明:改性固化剂/EP胶粘剂固化体系的表观活化能为86.73 kJ/mol、反应级数为1.24和最佳固化温度为66℃;当n(EP):n(改性固化剂)=1:0.50时,相应胶接件的-196℃、室温、60℃剪切强度分别为16.84、14.73、13.52 MPa,说明其强度和韧性俱佳,并且完全满足实际使用要求。     

Application of the thermal energy storage concept to novel epoxy–short carbon fiber composites

For the first time, multifunctional epoxy–short carbon fiber reinforced composites suitable for thermal energy storage technology were developed. Paraffin microcapsules (MC) and short carbon fibers (CFs) were added at different relative amounts to an epoxy matrix, and the microstructural and thermomechanical properties of the resulting materials were investigated. Scanning electron microscopy images of the composites showed a uniform distribution of the capsules within the matrix, with a rather good interfacial adhesion, while the increase in the polymer viscosity at elevated CF and MC amounts caused an increase in the void content. Differential scanning calorimetry tests revealed that melting enthalpy values (up to 60 J/g) can be obtained at high MC concentrations. The mixing and thermal curing of the composites did not lead to breakage of the capsules and to the consequent leakage of the paraffin out of the epoxy matrix. The thermal stability of the prepared composites is not negatively affected by the MC addition, and the temperatures at which the thermal degradation process begins were far above the curing or service temperature of the composites. Flexural and impact tests highlighted that the presence of MC reduces the mechanical properties of the samples, while CF positively contributes to retaining the original stiffness and mechanical resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47434.     

Morphology and thermal/mechanical properties of alkyl‐imidazolium‐treated rectorite/epoxy nanocomposites

A novel organic rectorite (OREC) was prepared by treating the natural sodium‐rectorite (Na‐REC) with ionic liquid 1‐hexadecyl‐3‐methylimidazolium bromide ([C₁₆mim]Br). X‐ray diffraction (XRD) analysis showed that the interlayer spacing of the OREC was expanded from 2.23nm to 3.14nm. Furthermore, two types of OREC/epoxy nanocomposites were prepared by using epoxy resin (EP) as matrix, 2‐ethyl‐4‐methylimidazole (2‐E‐4‐MI) and tung oil anhydride (TOA) as curing agents, respectively. XRD and transmission electron microscope (TEM) analysis showed that the intercalated nanocomposite was obtained with addition of the curing agent 2‐E‐4‐MI, and the exfoliated nanocomposite was obtained with addition of the curing agent TOA when the OREC content was less than 2 wt %. For the exfoliated nanocomposite, the mechanical and thermal property tests indicated that it had the highest improvement when OREC content was 2 wt% in EP. Compared to pure EP, 60.3% improvement in tensile strength, 26.7% improvement in bending strength, 34% improvement in bending modulus, 14°C improvement in thermal decomposition temperature (T_d) and 5.7°C improvement in glass transition temperature (T_g) were achieved. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

三乙烯四胺固化有机蒙脱土/环氧树脂复合体系的研究

以三乙烯四胺作为EP(环氧树脂)的常温固化剂制备EP/OMMT(有机蒙脱土)/三乙烯四胺纳米复合材料。采用X射线衍射(XRD)法,差示扫描量热(DSC)法等手段研究了不同配方对EP/OMMT/三乙烯四胺固化体系的凝胶时间、力学性能、热性能及OMMT的插层剥离行为等影响。结果表明:对EP/OMMT/三乙烯四胺复合材料而言,90~120℃固化体系的OMMT剥离与插层效果优于室温固化体系;当固化温度为120℃时,EP/OMMT/三乙烯四胺复合材料的耐湿热性能和弯曲强度均优于常温固化体系;EP/OMMT/三乙烯四胺复合材料经常温固化24 h后,其冲击强度比纯EP体系提高了7%~12%。     

反应型含磷阻燃环氧树脂体系的研究进展

含磷单体是新一代无卤、环保型阻燃环氧树脂(EP)的改性单体,可以合成具有优异热稳定性和阻燃性能的新型含磷EP。详细阐述了通过合成含磷EP单体和含磷固化剂来合成新型含磷EP的合成方法及性能等,最后指明了它的发展方向。     

Thermo-mechanical behaviors of epoxy resins reinforced with nano-Al2O3 particles

This study examined the thermo-mechanical behavior of epoxy resins/nano-Al₂O₃ composites including the curing behavior, thermal stability, dynamic mechanical properties and thermal mechanical properties. The DSC curve peak temperature of the composites was decreased by the addition of nano-Al₂O₃. The thermal stability of the composites was similar to that of the neat epoxy resins. Dynamic mechanical analysis (DMA) indicated the glass transition temperature of the composites to be approximately 11 °C higher than that of the neat epoxy resins. The coefficient of thermal expansion (CTE) of the composites decreased with increasing nano-Al₂O₃ content.     

The Preparation and Cure Kinetics Researches of Thermal Conductivity Epoxy/AlN Composites

The aluminum nitride (AlN) was employed to prepare epoxy/AlN composites by blending-casting moulding method, two different coupling agents were used to functionalize the surface of AlN. The thermal conductivity and mechanical properties of the composites were investigated. And the cure kinetics of the EP/AlN composites was studied by means of isothermal DSC. Results revealed that the thermal conductivity of EP improved remarkably with the addition of AlN, a higher thermal conductivity of 1.05 W/mK can be achieved with 42 vol% AlN, about 5 times higher than that of native epoxy resin. And the flexural and impact strength of the EP/AlN composites were optimal with 3.3 vol% AlN. The curing process of the EP/AlN composites contained autocatalytic mechanism, the whole process was according with the Kamal model. The presence of AlN did not change the cure reaction mechanism, and had little effecting on the activation energy, but decreased the rate constants k_l and k₂.     

Studies on the curing behavior,thermal, and mechanical properties of epoxy resin-co-amine-functionalized lead phthalocyanine

A high performance copolymer was prepared by using epoxy (EP) resin as matrix and 3,10,17,24-tetra-aminoethoxy lead phthalocyanine (APbPc) as additive with dicyandiamide as curing agent. Fourier-transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetric analysis (DSC), and thermogravimetric analysis (TGA) were used to study the curing behavior, curing kinetics, dynamic mechanical properties, impact and tensile strength, and thermal stability of EP/APbPc blends. The experimental results show that APbPc, as a synergistic curing agent, can effectively reduce the curing temperature of epoxy resin. The curing kinetics of the copolymer was investigated by non-isothermal DSC to determine kinetic data and measurement of the activation energy. DMA, impact, and tensile strength tests proved that phthalocyanine can significantly improve the toughness and stiffness of epoxy resin. Highest values were seen on the 20 wt% loading of APbPc in the copolymers, energy storage modulus, and impact strength increased respectively 388.46 MPa and 3.6 kJ/m², T_g decreased 19.46°C. TGA curves indicated that the cured copolymers also exhibit excellent thermal properties.