A random acrylate copolymer with epoxy‐amphiphilic structure as an efficient toughener for an epoxy/anhydride system

Toughening of epoxy resin by block copolymers containing an epoxy‐philic block and an epoxy‐phobic block is usually costly because of their complex preparation procedure. In this work, a novel, random epoxy‐amphiphilic copolymer (PHGEL), which combines an “epoxy‐philic” component and an “epoxy‐phobic” component, has been synthesized and evaluated as a potential toughening agent for a diglycidyl ether of bisphenol A–based epoxy thermoset (EP). The curing behavior of the EP/PHGEL system has been investigated, and the results show that the hydroxyl group on the PHGEL chain can slightly activate the curing reaction. The mechanical testing shows that the toughness of the epoxy resin is improved by 294% when 4 wt % of PHGEL is added. Simultaneously, the tensile strength, elongation at break, and glass‐transition temperature are also improved. In addition, the thermogravimetric analysis shows that PHGEL has no obvious effect on the thermal stability of the epoxy thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44863.     

水中固化环氧树脂胶黏剂制备与性能研究

以固化剂、偶联剂及水泥用量,填料种类及其用量、促进剂及其用量等因素为考察对象,进行正交实验设计,考察了环氧胶黏剂中各组分用量对其剪切粘接强度的影响,并测试了其粘接性能及动态黏弹力学性能,同时进行了傅立叶红外光谱(FTIR)结构表征和热重(TGA)分析。通过粘接性能测试,得到了自制固化剂复配环氧树脂及不同助剂的最优配方:环氧树脂100份、固化剂30份、偶联剂5份、水泥120份、填料10份、促进剂2.8份,该环氧胶黏剂的剪切粘接强度为22.0MPa左右,拉伸强度为12.50MPa左右,冲击强度为9.41kJ/m2。TGA表明:环氧胶黏剂在低于335℃时,热稳定性比较好,保留率为90%以上。DMA测试得到:该胶玻璃化温度Tg为50℃左右。通过探索,混凝土哑铃型试件水中固化环氧胶黏剂的拉伸粘接强度达2.5MPa以上。     

Structural Carbon/Epoxy Prepregs Properties Comparison by Thermal and Rheological Analyses

Two different carbon/epoxy prepreg materials were characterized and compared using thermal (DSC, TGA, and DMA) and rheological analyses. A prepreg system (carbon fiber preimpregnated with epoxy resin F584) that is currently used in the commercial airplane industry was compared with a prepreg system that is a prospective candidate for the same applications (carbon fiber prepreg/epoxy resin 8552). The differences in the curing kinetics mechanisms of both prepreg systems were identified through the DSC, TGA, DMA, and rheological analyses. Based on these thermal analysis techniques, it was verified that the curing of both epoxy resin systems follow a cure kinetic of n order. Even though their reaction heats were found to be slightly different, the kinetics of these systems were nevertheless very similar. The activation energies for both prepreg systems were determined by DSC analysis, using Arrhenius's method, and were found to be quite similar. DMA measurements of the cured prepregs demonstrated that they exhibited similar degrees of cure and different glass transition temperatures. Furthermore, the use of the rheological analysis revealed small differences in the gel temperatures of the two prepreg systems that were examined.     

环氧树脂对PA6/EPDM-g-MAH共混体系性能的影响

将两种不同型号的环氧树脂（EP(903)、EP(619D)）分别与PA6/EPDM-MA体系进行共混,制备了PA6/EPDM-MA/EP三元共混物。通过力学测试、动态流变(DMA)、差示扫描量热法（DSC）研究了不同EP添加量和环氧当量对PA6/EPDM-MA/EP共混体系性能的影响。实验结果表明：添加EP可以提高PA6/EPDM-MA共混物的拉伸强度,缺口冲击强度,并随着EP含量的增加而增加;而PA6/EPDM-MA/EP三元共混体系的动态储能模量（G′）,复合黏度（η*）随着EP含量的增加而增大,损耗因子（tanδ）减小;结晶度比未加环氧的共混物的结晶度稍高,并且随着环氧含量增加先增加后降低。此外,添加EP(903)的共混物各种性能变化比EP(619D)快。     

环氧树脂对PVC/ABS共混物性能的影响

研究了固体环氧树脂(EP)对聚氯乙烯(PVC)/丙烯腈-丁二烯-苯乙烯共聚物(ABS)/EP共混物力学性能和热稳定性的影响,重点考察了EP环氧值和固化剂DDM对共混物性能的影响。结果表明:PVC/ABS/EP共混物表现为脆性断裂;加入DDM后,共混物的拉伸强度明显提高,但冲击性能影响不大;对于PVC/ABS/EP/DDM共混物,随着EP含量的增加,共混物的拉伸强度上升,且环氧值高的EP704对共混物拉伸强度的提高更大;加入2%的低环氧值EP903后,共混物的冲击强度达到最大值,而EP704的加入则对共混物的冲击性能影响不大;环氧树脂的加入在一定程度上削弱了PVC/ABS共混物的热稳定性。     

Synthesis of a novel lignin-based epoxy resin curing agent and study of cure kinetics,thermal, and mechanical properties

In this contribution, first of all, the methoxy groups of organic solvent lignin (OSL) was converted to phenolic hydroxyl groups through demethylation reaction for the purpose of fabricating demethylated organic solvent lignin (DOSL). In addition, the resulting DOSL was utilized as a renewable material to synthesize a novel esterified lignin (EDOSL) by reacting with isobutyryl chloride for curing of epoxy resin. Finally, commercial liquid diglycidyl ether of bisphenol A was cured by EDOSL in the presence of 4-dimethylaminopyridine (DMAP) used as a catalyst based on dual-curing mechanism. Dual curing is a processing methodology based upon the alliance of two diverse and compatible polymerization reactions occurring sequentially or simultaneously. According to the FTIR spectra and ¹H-NMR analyses, the demethylation of OSL, esterification of DOSL, and the curing reaction of epoxy resin with EDOSL were successfully conducted. The value of the phenolic hydrogen in the DOSL was approximately 4.89 mmol/g, which increased by 12.64% after demethylation. The thermal and mechanical performances of these cured epoxy samples were measured by DSC, DMA, TGA, and tensile testing. The epoxy system cured by 10%wt esterified lignin with 1%wt DMAP possessed the tensile strength of 71.54 ± 7.50 MPa and the initial degradation temperature (T_5%) of 370°C, which can compete fairly with commercial aromatic curing agents or other lignin-based agents studied currently for the curing of epoxy systems.     

氯甲基笼型倍半硅氧烷改性双酚A环氧树脂性能

引言双酚A环氧树脂是目前应用最广、用量最大的环氧树脂,具有良好的化学稳定性、电气绝缘性被广泛应用于涂料和电子电器等领域;然而,双酚A环氧树脂存在耐热性较差和固化后脆性大等缺点,因此如何提高环氧树脂的耐热性及力学性能等是目前改性研究的热点之一[1-5]。而笼型多面体倍半硅氧烷(POSS)是一类具有(RSiO1.5)n通式的纳米材料,因其特殊的分子组成结构使得POSS具     

DDS固化EP/MMT纳米复合材料性能研究

以4,4′-二氨基二苯砜(DDS)为固化剂,制备出一种剥离型MMT/EP(蒙脱土/环氧树脂)纳米复合材料。采用红外光谱(FT-IR)法、X射线衍射(XRD)法和动态力学分析(DMA)法等对复合材料的微观结构、插层剥离行为、热性能和力学性能等进行了研究。结果表明:MMT对EP分子结构无影响,有利于EP结构和性能的设计,也便于确定其固化工艺。在无促进剂的情况下,当体系中引入5%MMT(相对于EP质量而言)时,复合材料的干态热变形温度、玻璃化转变温度(Tg)、冲击强度和拉伸强度分别提高了39℃、21℃、27.30%和10.50%;适量的MMT能有效提高纳米复合材料的耐湿热性能。     

Simultaneously Improving the Thermal,Flame‐Retardant and Mechanical Properties of Epoxy Resins Modified by a Novel Multi‐Element Synergistic Flame Retardant

To obtain epoxy resins with satisfactory thermal, flame retardant, and mechanical properties, a novel multi‐element synergistic flame retardant (PPVSZ) is synthesized through the reaction between P? H of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and C?C of polysilazane (PVSZ) and utilized as a multi‐element synergistic flame retardant for epoxy resins. The flame retardant mechanism is explored by XPS and SEM, confirming that the excellent flame‐retardance efficiency owes itself to an optimal flame retardant way which jointly exerts the flame‐retardant effects in the gaseous and condensed phase. The thermal properties deduced from DSC, TGA, and DMA, indicate the glass transition temperature, maximum weight loss rate, and char yields at 700 °C for EP‐2 increase by about 5.0 °C, 8.4 °C and 8.8%, respectively. Furthermore, mechanical properties such as impact strength, tensile strength, and flexural strength are also increased by 45.38%, 14.16%, and 17.43%, respectively, which show that the incorporation of PPVSZ does not deteriorate the mechanical properties of modified resin. All the results demonstrate that epoxy resins modified by PPVSZ not only have good effect on the flame retardance, but also have good improvement on thermal and mechanical properties, indicating the potential for applications in many fields requiring fire safety.     

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。     

Effect of polythiourethane hardener modification on the behaviour of epoxy resin

Polythiourethanes based on oligomeric polymercaptans were employed as curing agent of epoxy resin. The epoxy matrices, in the form of castings, were characterized for their mechanical properties such as tensile strength, elongation at break and unnotched Charpy impact strength as per ISO methods. Mechanical studies indicated that the incorporation of polythiourethane into epoxy resin improves the toughness and flexibility with reduction in tensile strength for samples cured at ambient conditions and influences the mechanical and thermal properties according to its percentage content for samples cured at 130°C. The high increase of impact strength was explained by the development of two-phase morphology during the cure process. The results of this study indicate that both the stoichiometry of the curing mixture and the initial thermal condition are of critical importance in governing the curing mechanism, structure of the network, morphology and the final properties of epoxy/polythiourethane compositions.     

改性己二胺柔性固化剂的合成与性能研究

采用二官能度环氧树脂对己二胺进行改性,得到了一种含多段长亚甲基链段的柔性固化剂。利用红外光谱表征其基本结构,通过60℃下的在线红外检测以及不同温度下固化时间对力学强度影响的分析,初步确定了其最佳固化工艺条件为80℃×6h。通过热重分析法（TG）测试了不同固化剂用量的固化产物热稳定性,并采用差示扫描量热法（DSC）研究了该固化剂固化时放热状况,进一步得到并验证了前面工作的正确性。以环氧树脂E-44为主体树脂,分别对其固化物在-196℃、室温、60℃下的剪切强度、90°剥离强度进行探讨。当主体树脂与固化剂按1∶0.5质量比混合时,其在各温度下的拉伸剪切强度分别为16.84MPa、14.73MPa和13.52MPa,可满足实际应用的要求。     

Thermo mechanical behaviour of unsaturated polyester toughened epoxy–clay hybrid nanocomposites

The intercrosslinked networks of unsaturated polyester (UP) toughened epoxy–clay hybrid nanocomposites have been developed. Epoxy resin (DGEBA) was toughened with 5, 10 and 15% (by wt) of unsaturated polyester using benzoyl peroxide as radical initiator and 4,4′-diaminodiphenylmethane as a curing agent at appropriate conditions. The chemical reaction of unsaturated polyester with the epoxy resin was carried out thermally in presence of benzoyl peroxide-radical initiator and the resulting product was analyzed by FT-IR spectra. Epoxy and unsaturated polyester toughened epoxy systems were further modified with 1, 3 and 5% (by wt) of organophilic montmorillonite (MMT) clay. Clay filled hybrid UP-epoxy matrices, developed in the form of castings were characterized for their thermal and mechanical properties. Thermal behaviour of the matrices was characterized by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Mechanical properties were studied as per ASTM standards. Data resulted from mechanical and thermal studies indicated that the introduction of unsaturated polyester into epoxy resin improved the thermal stability and impact strength to an appreciable extent. The impact strength of 3% clay filled epoxy system was increased by 19.2% compared to that of unmodified epoxy resin system. However, the introduction of both UP and organophilic MMT clay into epoxy resin enhanced the values of mechanical properties and thermal stability according to their percentage content. The impact strength of 3% clay filled 10% UP toughened epoxy system was increased by 26.3% compared to that of unmodified epoxy system. The intercalated nanocomposites exhibited higher dynamic modulus (from 3,072 to 3,820 MPa) than unmodified epoxy resin. From the X-ray diffraction (XRD) analysis, it was observed that the presence of d ₀₀₁ reflections of the organophilic MMT clay in the cured product indicated the development of intercalated clay structure which in turn confirmed the formation of intercalated nanocomposites. The homogeneous morphologies of the UP toughened epoxy and UP toughened epoxy–clay hybrid systems were ascertained from scanning electron microscope (SEM).     

Polydimethylsiloxane-Epoxy Copolymer for Industrial Applications

The copolymers of functionalized polydimethylsiloxane (PDMS) and epoxy resin were prepared by varying the concentration of PDMS with an objective to produce products with high-performance properties. These copolymers were cured using polyamide as a curing agent and characterized by FT-IR. The thermal properties and completion of curing were checked by DSC. The copolymers were evaluated for electrical and mechanical properties. The dielectric strength of the material increases with decrease in dissipation loss and dielectric constant. The mechanical properties were improved by 30–40 percent. The main objective was to reduce the brittleness and improve impact strength of epoxy systems.     

Interpenetrating polymer networks of bismaleimide and polyether polyurethane–crosslinked epoxy

In this work, we prepared the interpenetrating polymer networks of bismaleimide and polyether-type polyurethane(polyoxypropylene)–crosslinked epoxy (BMI/PU(PPG)–EP IPNs) by employing the simultaneous bulk polymerization technique. The polyurethane (PU)–crosslinked epoxy was identified via infrared (IR) spectra analysis. Also investigated herein were the mechanical properties, including tensile strength, Izod impact strength, and fracture energy (G_IC) of the IPNs with various BMI contents in PU–crosslinked epoxy matrix. In addition, differential scanning calorimetry (DSC) analysis and the thermogravimetric analysis (TGA) were performed to examine the thermal properties of the BMI/PU(PPG)–EP IPNs. In addition, morphology and dynamic mechanical analysis (DMA) of the BMI/PU(PPG)–EP IPNs were also studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2635–2645, 1998     

Preparation and characterization of 3,3′‐bis (maleimidophenyl)phenylphosphine oxide (BMI)/polysulfone modified epoxy intercrosslinked matrices

An intercrosslinked network of polysulfone (PSF)—bismaleimide (BMI) modified epoxy matrix system was made by using diglycidyl ether of bisphenol A (DGEBA) epoxy resin, hydroxyl terminated polysulfone and bismaleimide (3,3′‐bis(maleimidophenyl) phenylphosphine oxide) with diaminodiphenylmethane (DDM) as curing agent. BMI–PSF–epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterized for their mechanical properties such as tensile strength, flexural strength, and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of polysulfone into epoxy resin improves the toughness to an appreciable extent with insignificant increase in stress–strain properties. DSC studies indicated that the introduction of polysulfone decreases the glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of polysulfone as well as BMI modified epoxy resin show a unimodal reaction exotherm. The thermal stability and flame retardant properties of cured epoxy resins were improved with the introduction of bismaleimide and polysulfone. Water absorption characteristics were studied as per ASTM method and the morphology of the BMI modified epoxy and PSF‐epoxy systems were studied by scanning electron microscope. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Design,preparation and properties of novel renewable UV-curable copolymers based on cardanol and dimer fatty acids

A cardanol-based UV-curable vinyl ester (VE) monomer was prepared via simple esterification, and its successful synthesis was demonstrated by FTIR and ¹H-NMR. In order to improve its rigidity, it was mixed with certain proportions of another reactive bio-based VE monomer, maleic anhydride modified dimer fatty acids polymerized glycidyl methacrylate (MA-m-DA-p-GMA) which had rigid and strong polar groups, and then a series of UV-cured copolymers were prepared from the two VE monomers. The UV curing process was monitored by FTIR analysis. The tensile and thermal properties of the cured copolymer films were also investigated. UV curing analysis demonstrated that the double bonds in the mixed VE could be converted to ultimate curing level within 40 s. Tensile tests showed the prepared copolymers had a tensile strength of 8.86 MPa. Dynamic mechanical analysis (DMA) revealed the copolymers had relatively high glass transition temperature (T_g) from 40 to 60 °C. Thermogravimetric analysis (TGA) showed the copolymers containing higher content of CDMA had higher thermal stability, and all copolymers’ main thermal initial decomposition temperatures were above 410 °C, indicating the copolymers had certain thermal stability. These copolymer films can be used as eco-friendly materials in coatings and other applications to replace the currently used petroleum-based polymers.     

Preparation and properties of halogen‐free flame‐retarded phthalonitrile–epoxy blends

Halogen‐free flame‐retarded blends composed of 2,2‐bis[4‐(3,4‐dicyanophenoxy) phenyl] propane (BAPh) and epoxy resin E‐44 (EP) were successfully prepared with 4,4′‐diaminodiphenyl sulfone as a curing additive. The structure of the copolymers was characterized by Fourier transform infrared spectroscopy, which showed that epoxy groups, a phthalocyanine ring, and a triazine ring existed. The limiting oxygen index values were over 30, and the UL‐94 rating reached V‐0 for the 20 : 80 (w/w) BAPh/EP copolymers. Differential scanning calorimetry and dynamic rheological analysis were employed to study the curing reaction behaviors of the phthalonitrile/epoxy blends. Also, the gelation time was shortened to 3 min when the prepolymerization temperature was 190°C. Thermogravimetric analysis showed that the thermal decomposition of the phthalonitrile/epoxy copolymers significantly improved with increasing BAPh content. The flexible strength of the 20:80 copolymers reached 149.5 MPa, which enhanced by 40 MPa compared to pure EP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of high performance phthalide‐containing bismaleimide modified epoxy matrices

A series of intercrosslinked networks formed by diglycidyl ether of bisphenol A epoxy resin (DGEBA) and novel bismaleimide containing phthalide cardo structure (BMIPP), with 4,4′‐diamino diphenyl sulfone (DDS) as hardener, have been investigated in detail. The curing behavior, thermal, mechanical and physical properties and compatibility of the blends were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), notched Izod impact test, scanning electron microscopy (SEM) and water absorption test. DSC investigations showed that the exothermic transition temperature (T_p) of the blend systems shifted slightly to the higher temperature with increasing BMIPP content and there appeared a shoulder on the high‐temperature side of the exothermic peak when BMIPP content was above 15 wt %. TGA and DMA results indicated that the introduction of BMIPP into epoxy resin improved the thermal stability and the storage modulus (G′) in the glassy region while glass transition temperature (T_g) decreased. Compared with the unmodified epoxy resin, there was a moderate increase in the fracture toughness for modified resins and the blend containing 5 wt % of BMIPP had the maximum of impact strength. SEM suggested the formation of homogeneous networks and rougher fracture surface with an increase in BMIPP content. In addition, the equilibrium water uptake of the modified resins was reduced as BMIPP content increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

热致性液晶固化剂增韧环氧树脂的研究

合成了一种环氧树脂的热致性液晶固化剂,利用红外光谱、偏光显微镜（POM）、差热分析仪（DSC）、元素分析等手段确认其结构。将此液晶固化剂加入环氧树脂／二氨基二苯砜（DDS）固化体系中,测试了固化物的力学性能,并用热重量分析仪（TG）、DSC测试了固化物的玻璃化转变（Tg)和热失重温度（Td),用偏光显微镜（POM）以不同配比的环氧树脂／液晶固化剂体系的固化样品形貌进行观察。结果表明：加入不到3％的液晶固化剂,可以使环氧固化物的拉伸强度提高50％,冲击强度提高一倍,Tg和Td明显提高,偏光显微镜照片表明液晶固化剂的加入使固体体系出现了相分离。