固化条件对环氧树脂/丙烯酸酯橡胶共混体系结构与性能的影响

利用丙烯酸酯橡胶(ACM)提高热固性环氧树脂(EP)的韧性,系统研究共混体系固化条件对材料结构和性能的影响.研究表明,固化前环氧树脂与丙烯酸酯橡胶在整个组成范围内为均相体系,固化过程中两组份分子量不断增大,部分组成环氧树脂/丙烯酸酯橡胶共混体系(80/20及50/50)发生反应诱导相分离现象(RIPS).在发生反应诱导相分离的体系中,分相后的环氧树脂和丙烯酸酯橡胶两相彼此包含对方的组分,是一种不彻底的相分离.同时,固化后材料的结构与性能强烈依赖于所用固化条件(包括固化时间、固化温度及固化剂含量等).因此,可以通过调节体系固化条件实现对环氧树脂/丙烯酸酯橡胶共混体系结构和性能的调控.     

环氧树脂共混物相结构的调控方法研究

研究了环氧树脂(E51)/聚砜(PSF)共混物相结构的控制方法.通过抑制相分离、控制预固化的反应程度控制环氧树脂的分子量,固化后可获得不同的共混物相结构.依据红外测定的固化反应程度设定固化程序,可有效控制共混物的相结构.加入促进剂三氟化硼-乙基胺(BTF-EA)可提高固化反应速度,使相分离结构在早期被抑制,以获得小微区的相结构.     

橡胶改性环氧树脂的固化诱导相分离

研究了一种新型的液体橡胶ZR与环氧树脂的固化反应诱导相分离过程,分别通过时间分辨的激光光散射、光学显微镜研究了两相结构的发展,并用DSC跟踪该体系的固化动力学。结果表明,该固化反应经历了不稳相分离过程(spindodal decomposition),固化动力学过程与相分离过程有强烈的依赖性,固化速度越快,橡胶相尺寸越大;并且当环氧固化反应转化率达80％时,橡胶相结构基本得以固定,最终得到双连续结构。     

多壁碳纳米管对环氧树脂/聚醚酰亚胺体系相分离的影响

通过溶液混合的方法制备了环氧树脂/聚醚酰亚胺(PEI)/多壁碳纳米管(MWCNTs)三元复合物,并使用扫描电镜(SEM)、原位红外分析(FTIR)、流变测试和非等温DSC等手段研究了MWCNTs的存在对体系相分离形貌和固化反应的影响.扫描电镜的结果显示,在固化后的样品中MWCNTs较均匀地分散在两相中.150℃下固化,不含MWCNTs和MWCNTs含量为0.75 pbw的体系相分离形貌呈海岛状结构,而进一步增大MWCNTs含量后相分离形貌呈双连续结构,且相区尺寸随MWCNTs含量的增加而减小.120℃下固化,不含MWCNTs和MWCNTs含量为0.75 pbw的体系相分离形貌呈双连续结构,而进一步增大MWCNTs含量后,体系相分离形貌呈相反转结构.FTIR和DSC的测试结果表明,MWCNTs表面的羟基对环氧树脂的固化反应起到催化作用,使得固化反应速度加快,反应活化能降低.而流变测试的结果表明,随着MWCNTs含量增加,一方面交叉跨越多个相区的碳纳米管使得体系黏度增大,对相分离起到了一定的抑制作用;另一方面使得体系凝胶化时间提前,导致体系相分离形貌被固定在相分离的较早阶段,起到有效调控相分离形貌的作用.     

高分子相分离的分子动力学模拟

用粗粒化分子动力学(MD)模拟方法从分子层次研究两组分聚合物共混体系相分离过程中的动力学. 在相分离初期, 相区尺寸不随时间增加而变化; 在相分离中期, 相区尺寸与时间有很好的标度关系, 标度指数(α=1/3)符合Lifshiz-Slyozov提出的以扩散为主导的蒸发-凝聚机理的标度预测; 在相分离后期, 体系实现宏观相分离, 相区尺寸不再随时间改变而变化. 体积分数小的高分子链尺寸在相分离过程中先收缩再扩张, 在实现宏观相分离后, 高分子链尺寸又回到本体状态尺寸.     

反应诱导相分离过程的超声波在线跟踪

利用高频超声波对多相体系的界面Rayleigh散射作用实现了反应诱导相分离过程的在线跟踪.新技术用来跟踪环氧树脂在聚乙二醇介质中的固化反应,研究体系在不同浓度、不同反应介质、不同固化剂用量以及不同反应温度下的相分离过程.在对旋节线相分离模式深入分析的基础上,提出了双函数模型来描述相分离过程.将超声波散射强度与相分离速率函数以及相离散速率函数相结合,所得到的数学模型合理解释了超声波跟踪数据.跟踪技术发现,反应体系的浓度对相分离的速率和相结构的离散程度有很大影响,高浓度下的固化反应抑制了相分离,使相结构保持高的连续性;在高浓度和PEG2000介质中发现了l(t)滞后现象,证明了旋节线相分离的分离机理;环氧树脂与固化剂重量比为4/1时,相分离达到最佳状态;升高反应温度,固化反应速率提高快于相分离速率的提高,相分离被固化反应所抑制.新的技术将散射强度与微相结构中的离散程度对应起来,从而能实时分析相分离过程中微相结构的变化过程,为相分离的控制提供实验依据.     

两种不同化学组成的超支化聚氨酯改性环氧树脂

利用芳香族二元异氰酸酯和脂肪族二元异氰酸酯分别与二乙醇胺反应,设计合成了不同化学组成的超支化聚氨酯,考察了其对环氧树脂的改性作用.运用核磁共振、傅里叶红外光谱(FTIR)、扫描电子显微镜(SEM)、弯曲、拉伸、冲击强度、储能模量、示差扫描量热法(DSC)以及热失重(TGA)等对超支化聚氨酯的结构及其性能进行了证实和表征,并发现基于芳香族超支化聚氨酯改性的环氧树脂共混体系表现出均相结构,而脂肪族超支化聚氨酯和环氧树脂共混后却形成了非均相体系.均相的共混体系证明超支化聚合物自身能够有效地改善环氧树脂的力学性能和热学性能.     

聚合物交联反应诱导相分离过程的光散射二维相关分析研究

采用二维相关分析技术对聚醚砜(PES)/环氧树脂/二(2,6-二甲基苯胺基)甲烷体系的相分离过程的光散射数据进行了分析研究. 分析结果表明二维光散射分析可以提供一维光散射较难得到的信息: 在该体系相分离的演化过程早期, 即扩散控制期内, 体系中较小尺寸相区的粗大化早于较大的相区. 在相分离的中后期, 较小尺寸的富集相因碰撞融合产生更大尺寸相区的变化优先于较大尺寸相区的粗大化过程. 其原因可能是: 一方面这种增长方式比较有利于体系的能量较快地降低, 另一方面是在相分离的中后期界面运动导致的流动作用影响不容忽视.     

聚醚酰亚胺改性TGDDM环氧树脂的相分离研究

合成了不同化学结构的聚醚酰亚胺(PEI)并用于4,4′-二氨基二苯甲烷四缩水甘油醚(TGDDM)环氧树脂的增韧改性,以DSC,TRLS和SEM等方法研究了体系相分离过程中相容性和熔融粘度对相分离过程和结构的影响,对固化反应诱导相分离中相结构的控制提出初步的看法.     

热塑性聚醚酰亚胺改性四官能度环氧树脂的相分离研究──固化剂用量的影响

以DSC、TRLS和SEM等方法研究了固化剂DDS用量对苯端基聚醚酰亚胺(P-PEI)改性4,4'-二氨基二苯甲烷四缩水甘油环氧树脂(TGDDM)体系的固化速率及相结构的影响.结果表明,20phrP-PEI改性环氧体系在150℃固化时,随DDS量增加,固化反应速率增大,相分离时间提前,形成了不同的相结构,解释了DDS量对粘接剪切强度的影响.     

The compatibilizing effect of epoxy resin (EP) on polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr) blends

A new method was used to prepare thermoplastic elastomers based on polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr) with improved mechanical properties. An epoxy resin (EP) was used as a compatibilizing agent. The effect of EP on mechanical properties, swelling percentage and morphological characteristics of the blends was investigated with different blend compositions. The results showed that the incorporation of EP has improved the tensile strength, Young's modulus and elongation at break of PP/NBRr-EP blends compared with PP/NBRr blends. The enhancement of tensile properties of PP/NBRr-EP blends is due to the better adhesion between the two phases with the incorporation of EP. This is quite evident by scanning electron microscopy of tensile fractured surfaces. PP/NBRr-EP blend exhibits lower stabilization torque and swelling percentage than PP/NBRr blends. The lower stabilization torque is an indication of better processing characteristics.     

Free volume hole size of Cyanate ester resin/Epoxy resin interpenetrating networks and its correlations with physical properties

Cyanate ester (CE) resin was blended with epoxy resin (EP) at different mass ratios (CE/EP: 100/0, 90/10, 70/30, 50/50, 30/70, 10/90, and 0/100). The curing process of the blend system was characterized by Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry (DSC). Examination of the mechanical properties, thermal stability, and morphology of the blend systems showed that addition of epoxy resin resulted in improved toughness but a little sacrifice in thermal stability when compared with neat CE. The free volume size of the blend system determined by positron annihilation lifetime spectroscopy (PALS) decreased with the epoxy resin content, which is consistent with the chemical structure changes for the copolymerization between CE and EP. The crosslinking units of curing products (oxazoline, oxazolidinone, and polyether network) of the blends are all smaller in size than those of triazine ring structure from neat CE. Therefore, the free volume size of the blends decreases with increase of EP content. The correlations between the free volume properties and other physical properties (thermal stability and mechanical properties) have also been discussed.     

Property correlations for dynamically cured rice husk ash filled epoxidized natural rubber/thermoplastic polyurethane blends: Influences of RHA loading

Novel thermoplastic vulcanizates based on thermoplastic polyurethane (TPU) and epoxidized natural rubber (ENR) were prepared with rice husk ash (RHA) filler. Therefore, two major renewable resource materials (i.e., ENR and RHA) were exploited. Influences of RHA loading on mechanical, morphological, thermal and dynamic properties of dynamically cured ENR/TPU blends were investigated. It was found that the RHA showed good dispersion and was mainly localized in the ENR phase. Increasing the RHA loading led to the formation of larger ENR domains dispersed in the TPU matrix. Also, migration of the RHA particles from ENR to TPU phases was observed, resulting in reduced strength properties. It was found that the RHA acted as a nucleating agent in the TPU matrix and could accelerate the crystallization of TPU. Additionally, stress relaxation of the blends was evaluated by temperature stress scanning relaxation (TSSR). Higher relaxation stresses or raised relaxation curves were observed with increased RHA loadings in the dynamically vulcanized ENR/TPU blends.     

Enhanced dielectric performance of TPU composites filled with Graphene@poly(dopamine)-Ag core-shell nanoplatelets as fillers

A new type of graphene@poly(dopamine)-Ag (Gns@PDA-Ag) core-shell nanoplatelets was designed to improve the dielectric properties of thermoplastic polyurethane (TPU) composites. The microstructure, dielectric performances and the effects of Ag nanoparticles’ content on the dielectric properties of composites were investigated. Results showed that the addition of Gns@PDA-Ag nanoplatelets could effectively improve the dielectric constant of the composite. When tested at low frequency (below 100 Hz), the highest dielectric constant of the TPU/Gns@PDA-0.78Ag (3 wt%) composite was 118.82, which was 14 times higher than that of pure TPU (8.39). This increase in dielectric constant should be attributed to the strong polarization effect of conductive graphene nanoflakes (Gns) and Ag nanoparticles to TPU molecules. The PDA shell could prevent direct contact between Gns and Ag nanoparticles, limit the formation of conductive pathways, which kept the dielectric loss of the composites at a low level and maintained the breakdown strength in a stable state. Compared with pure TPU (0.29), the minimum dielectric loss of composites was only 0.36. Moreover, after Gns@PDA-Ag nanoplatelets with higher Ag content were doped into TPU, the composite showed a higher dielectric constant, and due to the existence of the Coulomb blocking effect, the dielectric loss did not increase significantly. The scalability and simplicity of the described method will provide a promising route to polymer composites for highspeed integrated circuits and energy storage applications.     

Direct diazotization of graphite nanoplatelets with melamine and their favorable application in epoxy resins

The ease of undesirable agglomeration and a low efficiency are two problems that restrict the application of graphite nanoplatelets (GNPs) in epoxy resins (EP). Herein, a new strategy with melamine (MEL) as the precursor to functionalize GNPs chemically, which form a bonding layer that is compatible with epoxy matrix, is reported. The MEL fragments with secondary amine groups were grafted uniformly on the GNPs surface by covalent junctions to exploit the diazonium chemistry. This behavior led to a better dispersion and a stronger interaction with the epoxy matrix and resulted in an enhanced glass transition temperature and bending strength, compared with the pure EP. When only 1 wt% functionalized GNPs (f‐GNPs) was used, the Tg of the modified EP raised of about 15°C compared with pure EP, and the bending strength increased by approximately 39%. The dielectric constant of the EP with f‐GNPs was impacted slightly, and the dielectric loss decreased. At 10⁵ Hz, the dielectric loss of the EP with 1 wt% f‐GNPs decreased by approximately 11% compared with pure EP. Therefore, diazotization modification of the GNPs is a useful approach to improve the compatibility in nanoparticle networks.     

Miscibility and cure kinetics studies on blends of bisphenol-A polycarbonate and tetraglycidyl-4,4′-diaminodiphenylmethane epoxy cured with an amine

Differential scanning calorimetry (DSC) has been applied to characterize the glass transition behavior of the blends formed by bisphenol-A polycarbonate (PC) with a tetrafunctional epoxy (tetraglycidyl-4,4′-diaminodiphenyl methane, TGDDM) cured with 4,4′-diaminodiphenylsulphone (DDS). A rare miscibility in the complete composition range has been demonstrated in these blends. Additionally, the blend morphology was examined using scanning electron microscopy (SEM) and a homogeneous single-phase PC/epoxy network has been observed in the blends of all compositions. Moreover, polycarbonate incorporation has been found to exert a distinct effect on the cure behavior of the epoxy blends. The cure reaction rates for the epoxy-PC blends were significantly higher due to the presence of PC. In addition, the cure mechanism of the epoxy blends was no longer autocatalytic. An n-th order reaction mechanism with n = 1.2 to 1.5 has been observed for the blends of DDS-cured epoxy with PC of various compositions studied using DSC. The proposed n-th order kinetic model has been found to describe well the cure behavior of the epoxy/PC blends up to the vitrification point. © 1995 John Wiley & Sons, Inc.     

Investigation of cure kinetics of epoxy resin/organic montmorillonite system by differential scanning calorimetry

The cure kinetics of the epoxy resin (EP)/organic montmorillonite, with 4-diamino diphenyl methane (DDM) as curing agent, was studied by non-isothermal differential scanning calorimetry (DSC) at four linearly programmed heating rates of 5, 10, 15, and 20 deg/min, and the effects of original montmorillonite (OMMT) on cure kinetics of epoxy resin were investigated. A two parameter (m, n) autocatalytic model was used to describe the cure kinetics of the epoxy resins. The kinetic parameters were calculated with the Malek method and the curves obtained by the Málek method showed a good agreement with experimental data for EP/DDM and EP/DDM/OMMT systems. The results, based on the isoconversional method showed that the activation energy was obvious difference with the addition of OMMT in the early stages of the cure, which indicated that the OMMT have catalytic effect on the epoxy ring-opening.     

Thermal conductivity epoxy resin composites filled with boron nitride

Boron nitride (BN) micro particles modified by silane coupling agent, γ‐aminopropyl triethoxy silane (KH550), are employed to prepare BN/epoxy resin (EP) thermal conductivity composites. The thermal conductivity coefficient of the composites with 60% mass fraction of modified BN is 1.052 W/mK, five times higher than that of native EP (0.202 W/mK). The mechanical properties of the composites are optimal with 10 wt% BN. The thermal decomposition temperature, dielectric constant, and dielectric loss increase with the addition of BN. For a given BN loading, the surface modification of BN by KH550 exhibits a positive effect on the thermal conductivity and mechanical properties of the BN/EP composites. Copyright © 2011 John Wiley & Sons, Ltd.     

酸酐固化环氧树脂/蒙脱土复合材料的等温固化动力学

用等温差示扫描量热法(DSC)研究了酸酐固化环氧树脂/蒙脱土复合材料的等温固化过程，考察了未处理的蒙脱土(MMT)和有机蒙脱土(OMMT)对环氧树脂固化动力学的影响. 实验表明， 环氧树脂的固化过程包含自催化机理，加入蒙脱土没有改变固化反应机理. 用Kamal方程对该体系的固化过程进行拟合，得到反应级数m、n，反应速率常数k1、k2，总反应级数(m + n)在2.4～3.0之间. MMT的加入使环氧树脂体系的k1、k2有所降低，而OMMT的加入对体系的k1、k2影响较为复杂，加入蒙脱土对环氧树脂固化体系的活化能影响较小.     

Compatibilized blends of thermoplastic polyurethane (TPU) and polypropylene

Compatibilized blends of thermoplastic polyurethane (TPU) and polypropylene (PP) were developed using amine (primary or secondary) functionalized PP's (PP-g-NH₂ or PP-g-NHR). The strategy of reactive compatibilization is based on fast reactions between amine functional groups and urethane linkages or traces of free isocyanates released by thermal degradation of TPU. Excellent compatibilization between TPU and PP was confirmed by rheological, morphological, and mechanical properties. Much finer domain size, higher interfacial adhesion, and more stable morphologies were clearly observed by scanning electron microscopy. Significant improvements in the overall mechanical properties (tensile, tear, abrasion) imply significantly more reaction between TPU and PP phases in the two TPU/PP blends containing PP-g-NH₂ or PP-g-NHR than a TPU/PP blend using PP-g-MA as a compatibilizing agent.