Thermal and mechanical properties of aminopropoxylate-cured epoxy matrices

Bisphenol A diglycidyl ether–aminopropoxylate mixtures have been characterized with respect to their viscosities in the presence and absence of butanediol diglycidyl ether (reactive diluent), and their curing patterns have been studied at room temperature with or without 2,4,6-tris(dimethylaminomethyl)phenol (initiator/accelerator). A priori, these mixtures are expected to provide low connectivities to infinite networks at gelation, a prediction supported by the multiple glass-transition-temperature (T_g) behaviour of their cured forms. The effect of the aminopropoxylate curing agent chemistry/functionality, and the presence or absence of accelerator and reactive diluent on the tensile and impact behaviour of cured materials, is reported. An expectation of increased importance of polymerization with increases in the initiator/accelerator levels, alongside epoxy–amine addition reactions, has not been evidenced by the mechanical measurements. For diglycidyl ether bisphenol A–aminopropoxylate epoxy systems, in the glycidyl ether/reactive hydrogen molar ratio range 0·80 (set A) to 1·95 (set B), the tensile failure mode is brittle fracture. For the set A formulations, this mode of failure persists up to reactive diluent loadings of 1·01wt% based on the weight of bisphenol A diglycidyl ether. Beyond 1·01wt% reactive diluent loadings, the set A formulations show ductile failure with yielding; the tensile toughness increases with increases in reactive diluent levels. For the set B formulations, and for all reported loading levels of reactive diluent, the castings failed in brittle fashion with pronounced cavitation and stress whitening. © 1998 Society of Chemical Industry     

聚硫橡胶对环氧树脂固化动力学及力学强度的影响

用红外光谱分析了在环氧树脂中加入聚硫橡胶的固化及增韧过程,通过差示扫描量热法研究了增韧体系的反应动力学,探讨了聚硫橡胶用量对固化产物力学强度的影响,并对试样断口形貌进行了扫描电镜观察。结果表明,聚硫橡胶的加入降低了环氧树脂的表观活化能而没有改变反应级数,使得固化反应的总放热量减少、放热过程更加平均。聚硫橡胶对环氧树脂的增韧效果明显,二者通过化学键结合,韧性撕裂的冲击断面形貌验证了这种活性增韧。当聚硫橡胶用量为30份(质量)时,环氧树脂固化物的冲击强度可达到未增韧者的896%。     

Morphology,mechanical and viscoelastic properties of nitrile rubber/epoxidized natural rubber blends

A new class of blend membranes from blends of nitrile rubber (NBR) and epoxidized natural rubber (ENR) has been prepared and their morphology, miscibility, mechanical, and viscoelastic properties have been studied. The ebonite method was used to study the blend morphology of the membranes. The morphology of the blends indicated a two‐phase structure in which the minor phase is dispersed as domains in the major continuous phase. The performance of NBR/ENR blend membranes has been studied from the mechanical measurements. The viscoelastic behavior of the blends has been analyzed from the dynamic mechanical data. An attempt was made to relate the viscoelastic behavior with the morphology of the blends. Various composite models have been used to predict the experimental viscoelastic data. The area under the linear loss modulus curve was larger than that obtained by theoretical group contribution analysis. The homogeneity of the system was further evaluated by Cole–Cole analysis. Finally, a master curve for the modulus of the blend was generated by applying the time–temperature superposition principle. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1561–1573, 2005     

Processability characteristics and physico‐mechanical properties of natural rubber modified with rubber seed oil and epoxidized rubber seed oil

The processability characteristics and physico‐mechanical properties of natural rubber (NR) modified with raw rubber seed oil and epoxidized rubber seed oil have been studied. The modified mixes showed higher scorch time and lower cure rate, crosslink density, and ultimate state of cure compared to an unmodified mix. The thermal stability of the vulcanizates was practically unaffected by the modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1413–1418, 2000     

环氧化天然橡胶贮存性能的变异

对环氧化天然橡胶 (ENR)及其胶乳 (ENRL)进行了为期 2年的贮存试验 ,考察其外观和主要物理性能的变异状况 ,探讨了这些性状变异的机理 ,了解到ENR和ENRL原材料长期贮存 ,其外观无明显变化。     

Physical properties of natural rubber/organoclay nanocomposites compatibilized with epoxidized natural rubber

Onium ion‐modified montmorillonite (organoclay) was melt compounded with natural rubber (NR) in an internal mixer and cured by using a conventional sulfuric system. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) was used in 10 parts per hundred rubber (phr) as a compatibilizer. The effect of organoclay with different filler loading up to 10 phr was studied. Cure characteristics were determined by a Monsanto MDR2000 rheometer, whereas the tensile, compression, and tear properties of the nanocomposites were measured according to the related ASTM standards. While the torque maximum and torque minimum increased slightly, both scorch time and cure time reduced with the incorporation of organoclay. The tensile strength, elongation at break, and tear properties went through a maximum (at about 2 phr) as a function of the organoclay content. As expected, the hardness, moduli at 100% (M100) and 300% elongations (M300) increased continuously with increasing organoclay loading. The compression set decreased with incorporation of organoclay. The dispersion of the organoclay in the NR stocks was investigated by X‐ray diffraction and transmission electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1083–1092, 2006     

Moisture cure and in-situ silica reinforcement of epoxidized natural rubber

Epoxidized natural rubber (ENR) was first precured with 3-aminopropyltriethoxysilane (APS) by the normal compression molding technique. The resultant sheet was further subjected to moisture cure, via hydrolysis and condensation reactions, by soaking it in water. The moisture-cured sample, when prepared under appropriate reaction conditions, demonstrated partial strain-induced crystallization behavior and moderate tensile strength, as opposed to typical peroxide-cured and sulfur-cured vulcanizates. The suitability of the ENR–APS precured sample for in-situ silica reinforcement by the sol–gel process, using tetraethyl orthosilicate (TEOS) as the silica precursor, was also demonstrated. Silica content as high as 36% by weight could be incorporated into the rubber, and TEOS-to-silica conversion of over 60% was observed. Comparative analysis with a typical peroxide-cured sample that was subjected to the same sol–gel process indicates that the silica in the final ENR–APS sol–gel vulcanizate is chemically bound to the rubber network.     

Study on the thermal degradation of epoxidized natural rubber

The thermal degradation and thermooxidative degradation of epoxidized natural rubber (ENR) were studied by thermogravimetry (TG). In the thermal degradation of ENR, the initial temperature of weight loss T₀ = 1.20B + 348, the temperature of maximum weight loss rate T_p = 1.07B + 392, and the final temperature of weight loss T_f = 0.77B + 445. The C_p, which corresponds to the degradation rate at temperature T_p, increases along with the heating rate B and its mean value is 43%, but C_f, which corresponds to the degradation rate at temperature T_f, is not affected by the heating rate, and its average value is close to 100%. As in the thermooxidative degradation, T₀ = 1.84B + 246, T_p = 0.30B + 378, and T_f = 2.27B + 584. The value of C_p increases along with the heating rate B and its mean value is 36%, but C_f is not affected by the heating rate and the average value approximately equals 100%. The thermal degradation in nitrogen could be a one-step reaction, whereas the thermooxidative degradation has a multiple-step reaction. The reactive environment has a great effect on the thermal degradation of ENR and the difference of the mechanisms of the two reaction systems is obvious. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2207–2211, 1998     

环氧化天然橡胶的研究与应用

环氧化天然橡胶（ENR）是由NR化学改性而成,笔者阐述了环氧化天然橡胶制备原理和方法、环氧化天然橡胶性能及应用研究、环氧化天然橡胶共混改性研究,其中包括ENR与PVC共混体系的研究、ENR其它共混体系的研究和ENR改性的研究.     

Hysteresis and strain-dependent dynamic mechanical properties of epoxidized natural rubber filled with surface-oxidized carbon black

High-temperature molding of a mixture of epoxidized natural rubber (ENR) and intermediate super abrasion furnace (ISAF) carbon black results in strong rubber–filler interaction, the extent of which is greater in the case of the oxidized grade of the carbon black. It has been observed that ENR is bonded to the filler surface through the formation of primary bonds, such as ester and phenolic ether. An extensive filler–filler network formation takes place through the hydrogen bonding between the active groups of the rubber and filler surface. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 723–730, 1998     

Dynamic mechanical properties and hysteresis loss of epoxidized natural rubber chemically bonded to the silica surface

High‐temperature (180°C) molding of epoxidized natural rubber (ENR) filled with precipitated silica leads to chemical bond formation between epoxy groups of ENR and silanol groups of silica. The extent of chemical bond formation is further enhanced in the presence of the silane coupling agent N‐3‐N‐(vinyl benzyl amino)ethyl‐γ‐amino‐propyl trimethoxy silane mono hydrogen chloride (trade name Z‐6032). The results of hysteresis loss measurements show that hysteresis loss increases with increase in coupling agent loading as a result of the higher modulus of the compounds compared to that of the ENR–silica mix. The dynamic mechanical property measurements show that the addition of coupling agent increases the glass‐transition temperature. Whereas strain‐dependent dynamic mechanical properties show that filler structure breakdown increases with increasing loading of coupling agent. Sulfur‐cured systems show higher filler structure breakdown compared to that of nonsulfur systems. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2171–2177, 2002     

Mechanical properties and morphology of epoxidized soyabean‐oil‐modified epoxy resin

Epoxidized soyabean oil (ESO) has been used to toughen epoxy resin cured with an ambient temperature hardener. The ESO was prepolymerized before blending with epoxy resin to obtain modified networks having various concentrations of ESO. The modified networks were also made by blending the ESO with epoxy resin by a one‐stage process. All the modified networks were characterized for their thermal, flexural and impact properties, and compared to the parent epoxy network. The optimum properties were obtained at 20 parts per hundred grams of resin (phr) of ESO. The impact behaviour is explained in terms of morphology observed by scanning electron microscopy. © 2001 Society of Chemical Industry     

环氧化天然橡胶的研究及应用进展

环氧化天然橡胶(ENR)具有良好的耐油性、气密性和粘着性,同时还具备一些特殊性能,是一种具有广阔应用前景的橡胶材料。本文介绍了近年环氧化天然橡胶的制备、结构、性能、改性和应用的研究工作,并对其研究趋势进行了展望。     

High-toughness,environment-friendly solid epoxy resins: Preparation,mechanical performance,curing behavior,and thermal properties

The development of a facile and efficient approach to prepare high-toughness epoxy resin is vital but has remained an enormous challenge. Herein, we have developed a high-performance environment-friendly solid epoxy resin modified with epoxidized hydroxyl-terminated polybutadiene (EHTPB) via one-step melt blending. The characterization, mechanical performance, curing behavior, and thermal properties of EHTPB-modified epoxy resin were investigated. EHTPB-modified epoxy resin exhibited excellent toughness with a 100% increase in elongation at break of tensile than that of neat epoxy resin. The transfer stress and dissipated energy in the rubber phase were predominant mechanisms of toughening. The toughening effect of EHTPB on solid epoxy resin was better than that of some of the previously reported liquid epoxy resins. Meanwhile, at 10 wt % of EHTPB loading, the EHTPB-modified epoxy resin displayed high strength and 22 and 101% improvement of flexural strength and impact strength, respectively. Moreover, at 10 wt % of EHTPB loading, the activation energy of EHTPB-modified epoxy resin for curing reaction decreased from 73.89 to 65.12 kJ·mol⁻¹, which is beneficial for the curing reaction. Furthermore, EHTPB-modified epoxy resin had a good thermal stability and the initial degradation temperature increased from 249 to 313 °C at 10 wt % of EHTPB loading. This work provides a simple-preparation and highly efficient and large-scale approach for the production of high-toughness environment-friendly solid epoxy resins. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48596.     

Synthesis and properties of epoxy resin modified with epoxy-terminated liquid polybutadiene

Epoxy resin networks have been modified with block copolymer of polybutadiene and bisphenol A diglycidyl ether (DGEBA)-based epoxy resin. Block copolymers prepared from isocyanate-terminated polybutadiene (NCOPBER) resulted in cured transparent epoxy networks with no discernible phase-separated morphology, as indicated by scanning electron microscopy. Epoxy resin modified with block copolymer derived from carboxyl-terminated polybutadiene (CPBER) presented an opaque aspect with dispersed rubber particle diameters in the range of 0.5-3μm. This value is substantially smaller than that found in epoxy matrix modified with hydroxyl-terminated polybutadiene. The different morphological characteristics observed in these modified systems were attributed to the different times to achieve the gelation (gel time) and also to the different structures of the block copolymers. The visual homogeneity of the NCOPBER block copolymer-modified network cannot be attributed to the presence of dissolved rubber, since the glass transition temperature of the epoxy matrix (determined from dynamic mechanical analysis) has not been substantially influenced by the presence of this block copolymer. The epoxy resin modified with the different block copolymers presented an improved impact resistance. The best mechanical performance in terms of flexural and tensile properties was achieved with the block copolymer derived from carboxyl-terminated polybutadiene, whereas a more flexible material has been obtained with NCOPBER block copolymer-modified network.     

Effect of surface modification of silicon carbide nanoparticles on the properties of nanocomposites based on epoxidized natural rubber/natural rubber blends

Improvement of the properties of rubber nanocomposites is a challenge for the rubber industry because of the need for higher performance materials. Addition of a nanometer‐sized filler such as silicon carbide (SiC) to enhance the mechanical properties of rubber nanocomposites has rarely been attempted. The main problem associated with using SiC nanoparticles as a reinforcing natural rubber (NR) filler compound is poor dispersion of SiC in the NR matrix because of their incompatibility. To solve this problem, rubber nanocomposites were prepared with SiC that had undergone surface modification with azobisisobutyronitrile (AIBN) and used as a filler in blends of epoxidized natural rubber (ENR) and natural rubber. The effect of surface modification and ENR content on the curing characteristics, dynamic mechanical properties, morphology and heat buildup of the blends were investigated. The results showed that modification of SiC with AIBN resulted in successful bonding to the surface of SiC. It was found that modified SiC nanoparticles were well dispersed in the ENR/NR matrix, leading to good filler‐rubber interaction and improved compatibility between the rubber and filler in comparison with unmodified SiC. The mechanical properties and heat buildup when modified SiC was used as filled in ENR/NR blends were improved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45289.     

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     

Rheological behavior of reactive blending of epoxidized natural rubber with cassava starch and epoxidized natural rubber with natural rubber and cassava starch

Epoxidized natural rubbers (ENR‐25 and ENR‐45) were prepared using the performic epoxidation method. Two‐component (ENR–cassava starch) and three‐component (ENR–NR–cassava starch) blends were prepared. ENR‐25 and ENR‐45 were blended with various quantities of gelatinized cassava starch in the latex state. The pure ENR exhibited lower shear stress and shear viscosity than those of the blends with cassava starch. Furthermore, the shear stress and shear viscosity were increased with an increase in the cassava starch concentration. The chemical interaction between the epoxide groups in the ENR and the hydroxyl groups in the cassava starch molecules might be the reason for the increasing trends of the shear stress and shear viscosity. The blends are classified as compatible blends because of the strong chemical bonding between different phases. SEM micrographs were used to clarify the compatibility. Power law behavior with pluglike flow profiles was observed for all sets of ENR–NR–cassava starch blends. Very low power law index values (<0.34) and highly pseudoplastic fluid behavior were also observed. The log additive rule was applied to plots of zero shear viscosity (consistency index) and the shear viscosity versus the concentration of ENR‐25. Positive deviation blending was observed, which indicates compatible blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1752–1762, 2004     

端羟基液体丁腈橡胶改性环氧树脂的结构与性能

用端羟基液体丁腈橡胶(HTLN)与2,4-甲苯二异氰酸酯进行反应得到HTLN预聚体,用其对环氧树脂进行化学改性,得到HTLN改性环氧树脂;考察了HTLN用量对改性环氧树脂微观形貌、拉伸强度和剪切强度的影响及改性环氧树脂的抗磨蚀性能。结果表明,随着HTLN预聚体用量的增加,改性环氧树脂的拉伸强度、剪切强度先升高后降低,在其质量分数为30%时,拉伸强度和剪切强度达到最高;在施加的负荷和HTLN用量一定的情况下,改性环氧树脂的磨蚀随滑动速率的增加而明显增加。     

Influence of aminosilane‐functionalized carbon nanotubes on the rheometric,mechanical, electrical and thermal degradation properties of epoxidized natural rubber nanocomposites

We describe the preparation, characterization and physical properties of multiwalled carbon nanotube (MWCNT)‐filled epoxidized natural rubber (ENR) composites. To ensure better dispersion in the elastomer matrix, the MWCNTs were initially subjected to aminopropyltriethoxysilane (APS) treatment to bind amine functional groups (?NH₂) on the nanotube surface. Successful grafting of APS on the MWCNT surface through Si–O–C linkages was confirmed using Fourier transform infrared spectroscopy. Grafting of APS on the MWCNT surface was further corroborated using elemental analysis. ENR nanocomposites with various filler loadings were prepared by melt compounding to generate pristine and APS‐modified MWCNT‐filled elastomeric systems. Furthermore, we determined the effects of various filler loadings on the rheometric, mechanical, electrical and thermal degradation properties of the resultant composite materials. Rheometric cure characterization revealed that the torque difference increased with pristine MWCNT loading compared to the gum system, and this effect was more pronounced when silane‐functionalized MWCNTs were loaded, indicating that this effect was due to an increase in polymer–carbon nanotube interactions in the MWCNT‐loaded materials. Loading of silane‐functionalized MWCNTs in the ENR matrix resulted in a significant improvement in the mechanical, electrical and thermal degradation properties of the composite materials, when compared to gum or pristine MWCNT‐loaded materials.© 2013 Society of Chemical Industry