动态固化聚丙烯／马来酸酐接枝聚丙烯／滑石粉／环氧树脂复合材料研究

将动态硫化技术应用于热塑性树脂／填料／热固性树脂复合体系，制备了动态固化聚丙烯(PP)／马来酸酐接枝PP(PP-g-MAH)/滑石粉(Talc)／环氧树脂(EP)复合材料。研究了动态固化PP／PP-g-MAH/Talc／EP复合材料的界面作用、形态结构、力学性能以及热稳定性。实验结果表明：PP／PP-g—MAH的加入，可明显增加PP/Talc复合材料的界面作用。在动态固化PP／PP-g-MAH/Talc／EP复合材料中，PP和Talc两相界面更加模糊，动态固化EP进一步增加了PP和Talc间的界面作用。当EP的用量超过5份时，部分EP呈颗粒状分布在PP基体中。与PP／PP-g-MAH/Talc／EP和PP／PP-MAH-Talc／EP复合材料相比，动态固化PP／PP-g-MAH/Talc／EP复合材料的冲击强度、拉伸强度和弯曲模量均有明显提高。当EP用量超过5份时，复合材料的冲击强度和断裂伸长率明显降低，但拉伸强度和弯曲模量继续增加。热分析表明动态固化PP／PP-g-MAH/Talc／EP复合材料具有较高的热稳定性。     

New polythiourethane hardeners for epoxy resins

New mercaptan‐terminated polythiourethanes were synthesized from low‐molecular‐weight dimercaptan oligomers and diisocyanates. The characteristic bands in the FT‐IR spectra, and the specific peaks in the ¹H‐NMR spectra correlate rather well with the proposed structures of these polymers. Chemical analysis of the epoxy group conversion and swelling measurements were conducted in order to determine the crosslink densities of the cured epoxy resins. The curing characteristics and thermal behaviour of the formulated curing mixtures indicate that the epoxy/polythiourethane stoichiometry and thermal history during cure may greatly affect the curing mechanism and final properties of the epoxy networks. Mechanical studies indicated that the application of polythiourethane hardeners improves the flexibility with increasing tensile strength and impact toughness. The prepared polythiourethane hardeners have an acceptable odour and give a perfectly homogeneous system with the epoxy resins and have good storage stability with other coreactants such as diamines. Copyright © 2005 Society of Chemical Industry     

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.     

Preparation and Application of a New Curing Agent for Epoxy Resin

A new curing agent based on palmitoleic acid methyl ester modified amine (PAMEA) for epoxy resin was synthesized and characterized. Diglycidyl ether of bisphenol A (DGEBA) epoxy resins cured with different content of PAMEA along with diethylenetriamine (DETA) were prepared. The mechanical properties, dynamic mechanical properties, thermal properties, and morphology were investigated. The results indicated that the PAMEA curing agent can improve the impact strength of the cured epoxy resins considerably in comparison with the DETA curing agent, while the modulus and strength of the cured resin can also be improved slightly. When the PAMEA/epoxy resin weight ratio is 30/100, the comprehensive mechanical properties of the cured epoxy resin are optimal; at the same time, the crosslinking density and glass transition temperature of the cured epoxy resin are maximal.     

环氧树脂对过氧化物硫化丁腈橡胶性能的影响

研究了环氧树脂用量对过氧化物硫化丁腈橡胶的硫化特性及其物理机械性能的影响。结果表明,环氧树脂对正硫化时间及其拉伸性能影响较大,随着环氧树脂用量增加,正硫化时间明显缩短,拉伸强度与拉断伸长率逐渐下降,而100%定伸强度逐渐提高。差示扫描量热仪(DSC)分析发现,环氧树脂的加入能够影响硫化反应的热效应。     

棉油酸甲酯改性胺固化剂的合成及性能研究

利用棉油酸甲酯制备了一种环氧树脂固化剂棉油酸甲酯改性胺,研究了棉油酸甲酯改性胺用量对环氧树脂体系的力学性能和热性能的影响,利用红外光谱、热分析、动态力学分析讨论了棉油酸甲酯改性胺的结构、环氧树脂固化物的性能。结果表明,环氧树脂固化物的拉伸性能、弯曲性能和冲击强度随着棉油酸甲酯改性胺用量的增加而增加。     

呋喃改性胺固化环氧树脂的耐强碱性研究

制备了一种新型的环氧树脂室温固化剂-呋喃改性胺,并用该固化剂固化E-51环氧树脂,研究了其浇铸体经108℃、25%的NaOH水溶液处理后,力学性能和电性能随碱煮时间的变化关系,并且采用扫描电镜表征了碱煮前后其复合材料拉伸断面形貌。结果表明,改性胺用量为24phr时,浇铸体的力学性能最优。碱煮150min以后,树脂固化物的力学性能变化比较小,拉伸强度、拉伸弹性模量和冲击强度的保留率分别为93.6%、87.1%和86.5%,绝缘性能有所下降,介电常数和介质损耗出现起伏性变化。     

Chain length effect of alkenyl succinic anhydride on thermal and mechanical properties of the cured epoxy resins

As epoxy curing agents three alkenyl succinic anhydrides (ASA) with varying side chain length (2-octenyl, 2-dodecenyl and 2-hexadecenyl succinic anhydride) were prepared by the ene synthesis and thermal and mechanical properties of a bisphenol A epoxy resin cured with the ASA's were measured. With increase in the side chain length of the ASA the Tg, the tensile strength and the impact strength decreased. All the cured samples exhibited excellent transparency and flexibility.     

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     

聚氨酯嵌段改性环氧树脂的合成及性能

通过两步法在环氧树脂主链中成功引入了聚氨酯链段,合成了新型环氧树脂。采用傅立叶变换红外光谱仪、热失重分析仪、差示扫描量热仪等对其进行了结构、热学和力学性能表征。通过合成条件优化及固化过程的研究,得到了最佳反应条件:第一步反应为50℃下反应1 h,第二步反应为70℃下反应1 h,固化条件为110℃反应1 h,升高至140℃后反应2 h,继续升高至160℃后再反应1 h。通过对固化后环氧树脂的热性能及拉伸性能的研究发现,聚氨酯链段的引入可将环氧树脂的断裂伸长率提高至36.7%~130.1%,但是却在一定程度上降低了其热稳定性和拉伸强度。     

Effect of the structure of curing agents modified by epoxidized oleic esters on the toughness of cured epoxy resins

The aim of this study was to determine the effect of the ester carbon chain length of curing agents modified by epoxidized oleic esters on the toughness of cured epoxy resins. An amine‐terminated prepolymer (i.e., curing agent G) was synthesized from a bisphenol A type liquid epoxy resin and triethylene tetramine. The toughening curing agents (G1 and G2) were prepared by reactions of epoxidized oleic methyl ester and epoxidized oleic capryl ester, respectively, with curing agent G. Fourier transform infrared spectrometry was used to characterize the chemical structure of the curing agents. The effects of the carbon chain length of the oleic ester group in the curing agents on the toughness and other performances of the curing epoxy resins were investigated by analysis of the Izod impact strength, tensile strength, elongation at break, thermal properties, and morphology of the fracture surfaces of the samples. The results denote that the toughness of the cured epoxy resins increased with the introduction of oleic esters into the curing agents without a loss of mechanical properties and that the toughness and thermal stability of the materials increased with increasing ester carbon chain length. The toughness enhancement was attributed to the flexibility of the end carbon chains and ester carbon chains of the oleic esters in the toughening curing agents. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

风力发电机叶片用环氧树脂复配体系的研究

采用CYD-128(E1)、双酚F环氧树脂(E2)、己二醇二缩水甘油醚(E3)为主要原材料配制可用于真空灌注的环氧树脂体系,通过粘度和拉伸、弯曲性能测试及示差扫描量热分析研究了树脂体系的流变特性,固化物力学性能和耐热性。结果表明,E1,E2,E3的质量比为65∶15∶20,固化剂为CYDHD-501,固化条件为70℃/6 h时,体系初始粘度较低,工艺性好,固化后力学性能、热性能优异,能够满足1.5 MW风电叶片用环氧树脂指标要求。     

Epoxidized pine oil‐siloxane: Crosslinking kinetic study and thermomechanical properties

In this study, a novel approach to toughen biobased epoxy polymer with different types of siloxanes was explored. Three different modified siloxanes, e.g., amine‐terminated polydimethyl siloxane (PDMS‐amine), glycidyl‐terminated polydimethyl siloxane (PDMS‐glycidyl), and glycidyl‐terminated polyhedral oligomeric silsesquioxane (POSS‐glycidyl) were used as toughening agents. The curing and kinetics of bioepoxy was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy. The mechanical, thermal, and morphological properties of the cured materials were investigated. Rheological characterization revealed that the inclusion of POSS‐glycidyl slightly increased the complex viscosity compared to the neat resin. The morphology of the cured bioresin was characterized by transmission electron microscopy and scanning electron microscopy. The inclusion of POSS‐glycidyl to bioepoxy resin resulted in a good homogeneity within the blends. The inclusion of PDMS‐amine or PDMS‐glycidyl was shown to have no effect on tensile and flexural properties of the bioresins, but led to a deterioration in the impact strength. However, the inclusion of POSS‐glycidyl enhanced the impact strength and elongation at break of the bioresins. Dynamic mechanical analysis showed that the siloxane modified epoxy decreased the storage modulus of the bioresins. The thermal properties, such as decomposition temperature, coefficient of linear thermal expansion, and heat deflection temperature were improved by inclusion of POSS‐glycidyl. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42451.     

Laboratory investigation of the properties of asphalt modified with epoxy resin

Epoxy asphalts were prepared by mixing styrene–butadiene–styrene (SBS) modified asphalt with epoxy resin. The curing process and morphology of epoxy asphalts were characterized by infrared spectroscopy and fluorescent microscope, respectively. The effects of epoxy resin contents, ratio of curing agent to epoxy resin and curing temperature on properties of epoxy asphalt were investigated. Results indicated that epoxy resin and epoxy asphalt showed similar curing efficiency. Epoxy asphalts can be cured at 120 or 60°C and its viscosity at 120°C can meet the demands of asphalt mixture mixing and paving. The chemical reaction of epoxy resin in epoxy asphalt is slow and reaction occurs not only with the curing agent but also carboxylic acid in epoxy asphalt. The microstructure of epoxy asphalt transforms from the dispersed structure to networks structure with epoxy resin content increasing and phase transition starts when 30 wt % epoxy resin present in asphalt. The softening point and tensile strength of epoxy asphalt increased with epoxy resin contents increasing. The softening point and tensile strength of epoxy asphalt were markedly improved when epoxy resin content was more than 30 wt %, which is attributed to formation of continuous structure of epoxy resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Mechanical and Morphological Behavior of Bismaleimide-Modified Soy-Based Epoxy Matrices

This study is concerned with the preparation and mechanical characterization of bio-based polymers from renewable resources. Epoxidized soybean oil at various concentrations is cured with an amine curing agent. The prepared matrices have been chemically modified with three types of bismaleimides, namely N, N′-bismaleimido-4, 4′-diphenyl methane (BMI-1), 1,3-bis(maleimido)benzene(BMI-2) and 3,3′-bis(maleimido phenyl)phenyl phosphineoxide (BMI-3). The crosslinked matrices thus developed were characterized for their mechanical properties such as tensile strength, tensile modulus, flexural strength, flexural modulus, and impact strength. The incorporation of bismaleimides in the soy-based matrices significantly enhances the mechanical properties. The morphological behavior of matrices is also studied using a scanning electron microscope. The results indicate that the bismaleimide-modified soy-based epoxy resin at appropriate concentration holds great potential as a replacement for petroleum-based materials in engineering applications.     

Synthesis and characterization of chlorinated soy oil based epoxy resin/glass fiber composites

Composites with good toughness properties were prepared from chemically modified soy epoxy resin and glass fiber without additional petroleum based toughening agent. Chlorinated soy epoxy (CSE) resin was prepared from soybean oil. The CSE was characterised by spectral, and titration method. The prepared CSE was blended with commercial epoxy resin in different ratios and cured at 85°C for 3 h, and post cured at 225°C for 2 h using m‐phenylene diamine (MPDA) as curing agent. The cure temperatures of epoxy/CSE/MPDA with different compositions were found to be in the range of (151.2–187.5°C). The composite laminates were fabricated using epoxy /CSE/MPDA‐glass fiber at different compositions. The mechanical properties such as tensile strength (248–299 MPa), tensile modulus (2.4–3.4 GPa), flexural strength (346–379 MPa), flexural modulus (6.3–7.8 GPa) and impact strength (29.7–34.2) were determined. The impact strength increased with the increase in the CSE content. The interlaminor fracture toughness (G_IC) values also increased from 0.6953 KJ/m² for neat epoxy resin to 0.9514 KJ/m² for 15%CSE epoxy‐modified system. Thermogravimetric studies reveal that the thermal stability of the neat epoxy resin was decreased by incorporation of CSE. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

含巯基聚硅氧烷改性环氧树脂的制备及性能

以双酚A环氧树脂（E51）为基料、聚醚胺（D?230）为固化剂、含巯基聚硅氧烷（PMMS）为改性剂,分别经过简单物理混合和化学改性的方法,制备了一系列聚硅氧烷改性环氧树脂（E51⁃D⁃PMMS）固化物。通过衰减全反射红外（ATR?FTIR）和X射线衍射仪（XRD）表征了固化物的结构特征;通过拉伸测试和冲击实验、扫描电子显微镜（SEM）、接触角测量（CA）、动态热力学分析（DMA）及中性盐雾实验探究了改性固化物的力学性能、热稳定性、防腐性能等。结果表明,化学改性的E51?D?PMMS固化物的综合物理化学性能优于简单物理改性的,当PMMS含量为1 %（质量分数,下同）时,改性固化物的拉伸强度为74.63 MPa,较改性前提高了13.5 %,断裂伸长率提高了40.2 %,冲击强度提高了43.7 %;水接触角从改性前的72.8 °增至100.3 °,表面能从39.4 J/m²降至17.4 J/m²,吸水率下降了44 %,耐水性能大大增强;其防腐性能和玻璃化转变温度（T_g）也有一定的提升。     

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.     

超支化聚酯增韧改性环氧树脂

采用端羧基的超支化聚酯(HBP-SA)和甲基四氢苯酐(MeTHPA)作为混合固化剂固化普通环氧树脂。考察了HBP-SA加入量对环氧固化物性能的影响,发现HBP-SA的加入降低了树脂固化的体积收缩率,提高了环氧固化物的拉伸强度和冲击强度。加入10%的HBP-SA,拉伸强度从22 5MPa提高到64 66MPa,而冲击强度从4 99kJ/m2提高到30 63kJ/m2,分别提高150%和500%,增韧增强效果也明显,但固化物的弯曲强度和耐热性能有所下降。