CTBN与ATBN改性环氧胶粘剂的研究

将端羧基丁腈橡胶(CTBN)接枝上环氧官能团进行改性,将改性后的CTBN添加到环氧胶粘剂的A组分中;将端氨基丁腈橡胶(ATBN)以不同的比例加入到环氧胶粘剂的固化剂即B组分中。考查胶粘剂的剪切、剥离强度和玻璃化转变温度以及2组分的配比对胶粘剂性能的影响。结果表明,将改性后的CTBN橡胶与ATBN配合使用比单独使用其中一种的综合性能更好,2者在A、B组分中分别占12质量份数左右时其增韧效果最显著。     

Mechanical behavior and structure of rubber modified vinyl ester resins

Vinyl esters are used widely as thermoset matrix materials for reinforced composites; however, they suffer from low‐impact resistance. Substantial enhancement of the toughness of brittle polymers may be achieved by dispersing elastomeric inclusions or rubber particles in the polymer matrix, inducing multiple crazing and shear yielding of the matrix. The main objectives of this work are morphological characterization of vinyl ester/reactive rubber systems and investigation of the mechanical and fracture behavior of these systems. Additional studies focused on rubber endcapped vinyl ester in the absence and presence of added reactive rubber. The initial compatibility of the liquid rubber with the liquid resin was studied. This is a key factor, along with cure conditions, in determination of the possible morphologies, namely, the degree of phase separation and particle size. The initial rubber/resin compatibility was found poor and all attempts to improve it by means of surfactants or ultrasonic treatment have not been successful. The flexure mechanical and fracture behavior of the cured resin/rubber systems was investigated. Three basic types of crack propagation behavior, stable, unstable, and stick‐slip, were observed. Fracture toughness of various resin/rubber systems was evaluated and was found to increase with increased content of rubbery second‐phase material. However, there is some payoff in stiffness and flexural strength of the cured resins. The addition of rubber does not affect the resin toughness at impact conditions. Analysis and interpretation of fractures morphology show that both multiple crazing and external cavitation play an important role in the fracture mechanism of the rubber modified specimens. No shear yielding is evident. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 647–657, 1999     

Structure and properties of epoxy resins modified with acrylic particles

The morphology and material properties of dicyandiamide (DICY)‐cured epoxy resins modified with acrylic particles consisting of a PBA (polybutyl acrylate) core and a PMMA (polymethyl methacrylate) shell and epoxy resins modified with acrylic rubber (PBA) particles alone were studied. It was found that the epoxy system modified with core/shell acrylic particles showed higher fracture toughness, indicating that the modification had a larger effect on improving the material properties of the epoxy resin. A characteristic shown by the core/shell acrylic particles is that they swell along with the epoxy resin under exposure to heat and gel before the latter cures. In this process, the epoxy resin penetrates the surface of the shell layer and a bond is formed between the epoxy matrix and the core/shell acrylic particles. This suggests that the epoxy matrix around the core/shell acrylic particles has the effect of increasing the level of energy absorption due to plastic deformation of the matrix. This is thought to explain why the epoxy resin modified with core/shell acrylic particles showed higher fracture toughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2955–2962, 1999     

纳米丁腈橡胶改性环氧树脂的性能及其应用

简述了纳米硫化丁腈橡胶改性环氧树脂的性能特点;介绍了一种耐低温环氧电子灌封胶和一种常温固化耐高温胶的配方、性能及其应用.     

Blends of epoxy resin with amine‐terminated polyoxypropylene elastomer: Morphology and properties

A liquid diglycidyl ether of bisphenol A (DGEBA) epoxy resin is blended in various proportions with amine‐terminated polyoxypropylene (POPTA) and cured using an aliphatic diamine hardener. The degree of crosslinking is varied by altering the ratio of diamine to epoxy molecules in the blend. The mixture undergoes almost complete phase separation during cure, forming spherical elastomer particles at POPTA concentrations up to 20 wt %, and a more co‐continuous morphology at 25 wt %. In particulate blends, the highest toughness is achieved with nonstoichiometric amine‐to‐epoxy ratios, which produce low degrees of crosslinking in the resin phase. In these blends, the correlation between G_IC and plateau modulus (above the resin T_g), over a wide range of amine‐to‐epoxy ratios, confirms the importance of resin ductility in determining the fracture resistance of rubber‐modified thermosets. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 427–434, 1999     

Study on relationship between mechanical properties and particle size distribution for polyhexamethylene carbonate diol toughened epoxy resin

The relationship between the mechanical properties and morphology of polyhexamethylene carbonate diol (PHMCD) toughened epoxy resin was investigated. The parameters describing the morphology (e.g., average diameter of particles and volume fraction of dispersed phase, etc.) were determined through SEM observation. It was observed that the particle size distribution changes from a unimodal distribution to a bimodal one and then tounimodal again with an increase in curing temperature. When it was cured at 120°C, an epoxy resin with a bimodal distribution of rubber particle size was obtained. The mechanical properties, especially the impacting strength, of the resin are the best because of the synergistic effect of the PHMCD particles. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 569–575, 1998     

Studying the pulverization mechanism of rubber with a modified design of the solid‐state shear extrusion process

Waste rubber cannot be reprocessed by melting because of its three‐dimensionally crosslinked molecular structure. Mechanical size reduction is the most common method for recycling and reusing waste rubber. The modified solid‐state shear extrusion (SSSE) process developed at the Illinois Institute of Technology was used for mechanical size reduction of rubber in a continuous process. In this work, an extended screw was used in conjunction with the original design of the SSSE apparatus to achieve greater rubber pulverization with a higher throughput rate and lower power consumption. The operating conditions of the modified SSSE apparatus were optimized to produce finer rubber particles that could be further used in a wide variety of applications. Controlling the residence time of rubber particles inside the pulverization section was crucial for producing a fine powder without agglomeration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of the addition of aramid-CTBN block copolymer on adhesive properties of cured epoxy resins modified with CTBN

To improve the bond strength of carboxy-terminated butadiene acrylonitrile (CTBN)-modified epoxy resin, aramid-CTBN block copolymer was used as an additive to a bisphenol-A-type epoxy resin modified with CTBN. With the addition of aramid-CTBN block copolymer, the fracture energy values of the adhesive joints were more than twice that of the CTBN-modified system and about twelve times that of the unmodified system. Observations of the adhesive layers using an optical microscope revealed that the width of the damage zone near the crack-tip in the double cantilever specimen increased with the addition of the aramid-CTBN block copolymer. TEM micrographs showed that the diameter of the CTBN-dispersed phases decreased and a number of fine CTBN phases were dispersed in the epoxy matrix with the addition of the block copolymer. It is concluded that addition of the block copolymer leads to an increase in the dispersibility of the CTBN elastomer into the epoxy matrix and thus the bond strength of the block copolymer-added system is increased due to the increase in the area of the damage zone and the occurrence of shear deformation of the epoxy matrix.     

Novel amine terminated elastomeric oligomers and their effects on properties of epoxy resins as a toughener

The objective of this study was to investigate the effects of amine terminated elastomeric epoxy tougheners on the mechanical and thermal properties of diglycidyl ether of bisphenol A based epoxy resin. The amine terminated polycaprolactone (PCL) (1) and PCL‐PDMS‐PCL (2) based oligomers were synthesized and characterized by FTIR spectroscopy. The stoichiometrical amount of the reactive oligomers as toughener, reactive epoxy resin and the curing agent, 4,4′‐diaminodiphenyl sulfone (DDS) were mixed and degassed. The homogenous mixtures were cured at 120°C into the preheated molds. The mechanical and thermal characterizations of toughened epoxy resin system were evaluated. It has been shown that the mechanical and thermal properties of toughened epoxy system vary as a function of the chemical structure and the concentration of rective oligomers. Higher mechanical properties were obtained for epoxy resin toughened by PCL‐PDMS‐PCL (2) based oligomer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermoplastic‐modified epoxy resins cured with different functionalities amine mixtures: Morphology,thermal behavior,and mechanical properties

Epoxy matrices inherent brittleness and poor crack resistance make necessary some form of toughening. In this work, to improve their fracture toughness and ductility epoxy matrices were modified by changing its architecture and by the addition of a third component. The matrices architecture were modified by stoichiometrically reacting a bifunctional epoxy resin with different functionalities amine mixtures, one of which being a monoamine that plays the role of chain extender. In the modification by the addition of a third component, poly(methyl methacrylate) (PMMA) was selected as modifier. PMMA is initially miscible with epoxy/amine systems but can phase separate during curing. The kinetics and miscibility of these systems were studied previously. At constant curing conditions, materials from completely opaque (phase separated) to transparent (miscible) can be obtained with the increase in monoamine content. In this work, the effects of the modifier content and of the monoamine : diamine ratio in stoichiometric epoxy/amine mixtures on the resultant morphologies as well as on their thermal and mechanical properties was studied.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of organoclay‐rubber nanocomposites via a new route with skim natural rubber latex

Skim natural rubber latex (SNRL) is a protein rich by‐product obtained during the centrifugal concentration of natural rubber (NR) latex. A new method to recover rubber hydrocarbon and to obtain nanocomposites with organoclay (OC) was investigated. The approach involved treatment of SNRL with alkali and surfactant, leading to creaming of skim latex and removal of clear aqueous phase before addition of OC dispersion. Clay mixed latex was then coagulated to a consolidated mass by formic acid, followed by drying and vulcanization like a conventional rubber vulcanizate. X‐ray diffraction (XRD) studies revealed that NR nanocomposites exhibited a highly intercalated structure up to a loading of 15 phr (parts per hundred rubber) of OC. Transmission electron microscopy studies showed a highly exfoliated and intercalated structure for the NR nanocomposites at loadings of 3–5 phr organically modified montmorillonite (OMMT). The presence of clay resulted in a faster onset of cure and higher rheometric torque. The rubber recovered from skim latex had a high gum strength, and a low amount of OC (5 phr) improved the modulus and tensile strength of NR. The high tensile strength was supported by the tensile fractography from scanning electron microscopy. Thermal ageing at 70°C for 6 days resulted in an improvement in the modulus of the samples; the effect was greater for unfilled NR vulcanizate. The maximum degradation temperature was found to be independent of the presence and concentration of OC. The increased restriction to swelling with the loading of OC suggested a higher level of crosslinking and reinforcement in its presence. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3277–3285, 2006     

Mechanical and tribological properties of epoxy modified by liquid carboxyl terminated poly(butadiene-co-acrylonitrile) rubber

Diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin was modified using liquid carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) rubber. The liquid CTBN contents used ranged from 2.5 to 20 parts per hundred parts of resin (phr). Mechanical properties of the modified resins were evaluated and the microstructures of the fracture surfaces were examined using SEM technique. The changes in storage modulus and the glass transition temperature were also evaluated using dynamic mechanical analysis (DMA). The tribological tests were performed using a ball-on-disc tribometer. The worn surfaces and the ball counter-mates after tribological tests were investigated using optical microscope technique. The results revealed the influence of liquid CTBN content on mechanical and tribological properties, and also microstructure of the modified epoxy resins. Impact resistance increased whereas the storage modulus and the hardness decreased when the CTBN rubber was introduced to the epoxy network. The coefficient of friction of the CTBN-modified epoxy was lower than that of the neat epoxy. The CTBN content of lower than 10 phr was recommended for improving the wear resistance of epoxy resin. Changes in tribological properties of the CTBN-modified epoxy correspond well to those in mechanical changes, especially the toughness properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Pulverization of rubber using modified solid state shear extrusion process (SSSE)

The challenge of reusing scrap rubber material is mainly due to its crosslinked/vulcanized structure, which prevents the material from melting and from being melt processed into new items. The most feasible recycling approach is believed to be a process in which the vulcanized rubber is first pulverized into a fine powder and then incorporated into new products. Solid state shear extrusion (SSSE), developed at Illinois Institute of Technology, is a process for continuous pulverization of rubber materials into a fine powder (Aratoopour, H. U.S. Pat. 5,704,555 15 ; Arastoopour, H.; Schocke, D. A.; Bernstein, B.; Bilgili, E. U.S. Pat. 5,904,885 11 ; Ivanov, G. Polym Eng Sci 18 ). In this work, the design of the SSSE apparatus was modified to overcome heat generation due to pulverization and the limitation from the torque/feeding rate relation and, thus, to increase the efficiency of the process in the production of finer particles at higher throughput. The modification was achieved by separating the original process into the extrusion section and the pulverization section. The extrusion section is dedicated to convey material to the pulverization section, which consists of a cylindrical housing and a rotatable cylindrical element that rotates independent of the extruder's screw. The rotatable cylindrical element can be treaded or flightless. Both sections are connected with an adapter. This new approach to the design allowed us to apply a more efficient cooling system, capable of removing the heat of pulverization and, in turn, results in the production of finer rubber particles. Furthermore, separation of the conveying process from the pulverization process resulted in a reduction in extruder's torque and a significant increase in the throughput. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 119–127, 2006     

Synthesis and characterization of epoxy/amine terminated amide‐imide‐imide blends

A new amine terminated amide‐imide (ATAI) was synthesized by the polycondensation reaction of tetrimide dicarboxylic acid containing bulky m‐chloro phenyl pendant with p‐phenylene diamine. The structure of all the prepared compounds were confirmed by FTIR,¹H‐NMR and ¹³C‐NMR techniques. This new diamine was then used to cure epoxy resin namely diglycidyl ester of bisphenol‐A and the cure reaction was studied by Differential scanning calorimetry. The cured blends show better thermal properties. The T_g of the epoxy resin was increased from 134°C to 156°C on addition of 6% of ATAI. The DMA results indicate that the polymer blend with 8% ATAI composition has higher storage modulus compared to 3% and 6% ATAI composition. The polymer blends with 3% and 6% ATAI composition have higher crosslinking density and lower intersegmental and intrasegmental friction coefficients than 8% ATAI composition. In the DMA curves an increase in the peak half‐width was observed with increasing ATAI composition, indicating the possibility of the existence of more than one phase with increasing ATAI concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and molecular weight characterization of rubber seed oil‐modified alkyd resins

Alkyd resins of 40% (I), 50% (II), and 60% (III) oil length (OL) were prepared with rubber seed oil (RSO), phthalic anhydride (PA), and glycerol (GLY), employing the two‐stage alcoholysis method. Changes in the physical characteristics of the reaction medium were monitored by determination of the acid value and the number‐average molecular weight, M_n , of in‐process samples withdrawn at different stages of the reaction. The mode of variation of these properties denotes that the preparation of RSO alkyds is complex. Molecular weight averages and the molecular weight distribution (MWD) of the finished alkyds were determined by GPC, cryoscopy, and end‐group analysis. Molecular weight averages and the MWD vary with differences in the formulation, with sample II exhibiting the narrowest size distribution. Values of M_n with the corresponding polydispersities in brackets are 3234 (1.91), 1379 (1.56), and 3304 (2.56) for samples I, II, and III respectively. M_n values obtained by cryoscopy are comparable to those obtained by gel permeation chromatography (GPC), while end‐group analysis seems to grossly overestimate their molecular weights. Correlation of M_n and the MWD with the quality of the finished alkyds shows that the narrower the size distribution the better the quality of the alkyd. Properties such as the rate of drying and resistance of the alkyds are optimum at 50% OL. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2431–2438, 2001     

常温酮肼自交联纳米环氧树脂乳液的制备与表征

以环氧树脂E-20合成了环氧月桂酸酯, 以丙烯酸单体与双丙酮丙烯酰胺(DAAM)对其进行接枝改性, 添加己二酸二酰肼(ADH)制备了常温酮肼自交联纳米环氧树脂乳液。以红外光谱仪表征了合成过程中各步产物及乳液固化后的结构, 结果表明得到了设计结构的树脂, 干燥后涂膜的FTIR谱图表明酮羰基与酰肼基发生交联反应生成了腙;DSC分析表明合成的树脂具有两个玻璃化温度(T_g), 分别为丙烯酸接枝环氧树脂和纯丙烯酸树脂的T_g, 前者低于常温, 表明可以实现常温自交联。在改性环氧树脂乳液的合成过程中, 以粒径分析和综合性能分析对功能性单体配比进行了研究, 结果发现当MAA与E-20质量比为11.0%~14.7%、DAAM的用量为2%~3%、m(ADH)/m(DAAM)为0.8~1.0时, 制得的乳液具有良好的储存稳定性和涂膜性能。透射电镜及粒径测试表明乳液粒径为纳米级, 约88 nm, 且粒径分布均匀, 基本呈稳定的球形结构。将所制备的纳米乳液配制成防腐涂料, 性能测试表明该涂料具有良好的综合性能。     

Thermal stability and kinetics analysis of rubber‐modified epoxy resin by high‐resolution thermogravimetric analysis

A dynamic heating rate mode of high‐resolution thermogravimetric analysis was used to study the thermal and thermal‐oxidative stability, as well as kinetics analyses, of a model liquid rubber‐modified epoxy resin, Ep/CTBN, made up of bisphenol A diglycidyl ether‐based epoxy and carboxyl‐terminated butadiene acrylonitrile rubber (CTBN). Results show that the thermal degradation of Ep/CTBN resin in nitrogen and air consists of two and three independent steps, respectively. Moreover, Ep/CTBN has a higher initial degradation temperature and higher activation energy than those of pure epoxy resin in both gases, indicating that the addition of CTBN to epoxy can improve the thermal and thermal‐oxidative stability of pristine epoxy resin. Kinetic parameters such as activation energy, reaction order, and preexponential factor of each degradation step of both Ep/CTBN and pure epoxy resins in air and nitrogen were calculated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3594–3600, 2003     

Morphology,thermal and mechanical behavior of polypropylene nanocomposites toughened with poly(ethylene‐co‐octene)

Rubber‐toughened polypropylene (PP) nanocomposites containing organophilic layered silicates were prepared by means of melt extrusion at 230 °C using a co‐rotating twin‐screw extruder in order to examine the influence of the organoclay and the addition of PP grafted with maleic anhydride (PPgMAH) as a compatibilizer on the morphological, mechanical and thermal properties. The mechanical properties of rubber‐toughened polypropylene nanocomposites (RTPPNCs) were studied through tensile, flexural and impact tests. Scanning electron microscopy (SEM) was used for investigation of the phase morphology and rubber particles size. X‐ray diffraction (XRD) was employed to characterize the formation of nanocomposites. The thermal properties were investigated by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The dynamic mechanical properties were examined by using dynamic mechanical analysis (DMA). From the tensile and flexural tests, the optimum loading of organoclay in RTPP was found to be 6 wt%. The optimum loading of PPgMAH, based on the tensile and flexural properties, was also 6 wt%. The increase in the organoclay and PPgMAH content resulted in a severe embrittlement, manifested by a drop in the impact strength and tensile elongation at break. XRD studies revealed that intercalated RTPPNCs had been successfully prepared where the macromolecular PP segments were intercalated into the interlayer space of the organoclay. In addition, the organoclay was dispersed more evenly in the RTPPNC as the PPgMAH content increased. TGA results revealed that the thermal stability of the RTPPNC improved significantly with the addition of a small amount of organoclay. Copyright © 2006 Society of Chemical Industry     

Fracture toughness of epoxy resins modified with polyethersulfone: Influence of stoichiometry on the morphology of the mixtures

Toughened mixtures containing 15 wt % polyethersulfone were made with diglycicdyl ether of bisphenol-A resin and 4,4′-diaminodiphenylmethane curing agent, with amine/epoxy group stoichiometric ratios varying from 0.6 to 1.5. Fracture behavior of the modified mixtures has been investigated as a function of the stoichiometry in the matrix. Morphology has been analyzed by transmission and scanning electron microscopy. The increase of amine content in the matrix results in a further increased fracture toughness. This behavior has been related to the changes on the ductility of the matrix upon stoichiometric ratio, but also to the changes on microstructural features of the modified mixtures as stoichiometric amine/epoxy group ratio increased. These morphological changes have been interpreted in terms of spinodal decomposition during curing of the epoxy matrix. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 183–191, 1998     

干磨与湿磨对粒配及粒形的影响

本文着重从流变学角度探讨干法及湿法球磨对粒子形貌和粒子级配的影响,并得出湿磨效率优于干磨,干磨粒形更为圆整的结论。