环氧树脂/聚氨酯共混体系相行为研究

利用小角光散射 (SALS)技术实时记录了环氧树脂 聚氨酯共混体系在固化过程中的相行为发展情况 ,得到了表征共混体系相区结构尺寸大小的相关距离ac 和表征体系均匀程度的均方介电常数涨落 η2 ,讨论了等温固化条件下 ,环氧树脂 聚氨酯共混体系的相区大小随时间的变化规律 .实验结果表明 ,环氧树脂 聚氨酯共混体系的固化过程是典型的反应诱导相分离的过程 .相分离初期 ,符合Cahn的线性理论 ;随着固化时间的延长 ,相区由小变大 ,约至反应开始后 3 2 1 0s,相分离趋于平衡态 ,相区尺寸趋于稳定     

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.     

制备方法对聚合物共混物相分离与黏弹弛豫的影响

采用小角激光光散射(SALLS)和动态流变方法研究了通过不同制备方法得到的等规聚丙烯/乙丙橡胶共混物(iPP/EPR)的相分离行为与黏弹行为.依据Cahn-Hilliard-Cook理论分析了熔融共混和溶液共混法制备的质量比为60/40和40/60的iPP/EPR共混物在恒温相分离早期的动力学,发现熔融共混iPP/EPR具有更大的表观扩散系数(Dapp).相分离中后期的实验结果表明,当相区尺寸增长程度相同时,熔融共混试样所用时间更短.表明熔融共混iPP/EPR试样具有更快的相分离速率.动态流变测试结果表明,与溶液共混相比,熔融共混试样具有更快的松弛速率.考虑到相分离过程实质是由高分子链的运动与扩散所控制,两种方法制备的iPP/EPR共混物相分离速率的差异应归于其分子链运动能力的不同.     

聚醚砜改性环氧树脂体系粘弹性相分离的研究

采用光学显微镜、光散射和扫描电镜等技术对聚醚砜(PES)/环氧树脂/二(2,6-二甲基苯胺基)甲烷体系的相分离过程进行了研究. 实验结果表明在该体系的相分离的演化过程中存在着明显的慢动态相的粘弹性效应, 同时对于PES含量较低的体系(PES-13.2 wt%和15.9 wt%), 在120和140 ℃固化时均观察到二次相分离现象, 而PES含量较高的体系(PES-18.5 wt%), 在同样温度下固化时仅观察到一次相分离过程.     

温度效应对氟链封端聚醚酰亚胺改性环氧树脂相分离的影响

用差示扫描量热仪(DSC)、扫描电镜(SEM)和时间分辨光散射(TRLS)比较了全氟碳链封端和苯环封端聚醚酰亚胺改性环氧树脂在不同温度下的相分离.结果表明,与P-blend相比,F-blend的固化速度和相分离速度较慢,诱导期和相结构固定时间推迟,相间距较小.升高温度,相间距因相分离速度加快而增大,同时由于全氟碳链端基引起的差异减小.因此,通过改变固化温度和聚醚酰亚胺的端基来降低聚醚酰亚胺的表面能,可以在一定程度上调控反应诱导相分离体系的相结构,并获得相间距较小的双连续结构.     

环氧化聚丁二烯-聚苯乙烯嵌段共聚物对聚苯醚/环氧体系反应诱导 相分离行为的影响

采用扫描电镜、光学显微镜和光散射仪研究了环氧化聚丁二烯-聚苯乙烯嵌段共聚物(EBS)对聚苯醚(PPO)/双酚A型环氧树脂(DGEBA)/4,4’-二(2,6-二甲基苯胺基)甲烷(DIM-DDM)体系反应诱导相分离行为的影响. 实验结果表明, EBS的加入对PPO/DGEBA/DIM-DDM体系反应诱导相分离的演化过程有阻滞作用. 随着EBS加入量的增加, 体系形成双连续相结构所需的PPO含量范围变宽, 而对于相同PPO含量、形成双连续相的体系则相结构尺寸减小.     

环氧化聚丁二烯-聚苯乙烯嵌段共聚物对聚苯醚/环氧体系反应诱导相分离行为的影响

采用扫描电镜、光学显微镜和光散射仪研究了环氧化聚丁二烯一聚苯乙烯嵌段共聚物(EBs)对聚苯醚(PPO)/双酚A 型环氧树脂(DGEBA)/4,4二(2,6-二甲基苯胺基)甲烷(DIM-DDM)体系反应诱导相分离行为的影响.实验结果表明,EBS的加入对PPo/DGEBA/DIM-DDM体系反应诱导相分离的演化过程有阻滞作用.随着EBS加入量的增加,体系形成双连续相结构所需的PPO含量范围变宽,而对于相同PPO含量、形成双连续相的体系则相结构尺寸减小.     

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.     

聚醚砜改性环氧体系的聚合诱导相分离行为: 固化机理的影响

对聚醚砜(PES)改性环氧体系在两种不同固化机理(逐步聚合和链增长聚合)的情况下的聚合诱导相分离行为进行了对比研究. 采用光学显微镜、时间分辨激光光散射、流变仪等手段对相分离的全过程进行了跟踪. 结果表明, 小分子的扩散行为是控制相分离的主要因素, 对于逐步聚合体系扩散主体为环氧低聚物, 而链增长聚合体系扩散主体为环氧单体. 在高含量PES(SPES-20%)体系中, 光散射结果显示了黏弹相分离的过程且相分离的特征松弛时间可以用WLF方程描述; 而在低含量PES(SPES-14%)体系中可以通过光学显微镜观测到二次相分离的现象, 并由流变学研究进一步证明.     

环氧树脂/聚砜共混体系相结构的调控研究——环氧预聚物分子量的影响

研究了不同分子量的环氧预聚物对双酚A型双官能团环氧树脂 /聚砜 (PSF) /固化剂 (二氨基二苯基砜 ,DDS)体系相分离结构的影响 .通过红外光谱 (FTIR)和动态热机械分析 (TMA)对反应转化率、玻璃化温度以及固化温度的关系的研究 ,表明环氧预聚物分子量较小时 ,凝胶点和玻璃化是影响相结构的关键因素 ;环氧分子量较大时 ,环氧扩链后粘度的变化则成为抑制相分离的重要因素 .电子显微镜 (SEM)结果表明改变环氧预聚物分子量可以达到调控相结构的目的 ,随着预聚物分子量的增大 ,体系的微区尺寸减小 .     

Using two-dimensional time resolved light scattering to study the cure reaction induced phase separation process of epoxy-amine-polyethersulfone blend with secondary phase separation

<正>The generalized two-dimensional correlation analysis based on time-resolved light scattering patterns(2D TRLS) has been employed to study the phase separation process of an epoxy-amine-polyethersulfone blend in which the secondary phase separation takes place.The results of the 2D TRLS provided more detailed information that was not readily observed in the 1D TRLS patterns.(i) During the first process of phase separation,the sequential order of coarsening in size of the domains among the larger and smaller ones has been reversed between the diffusion regime and the hydrodynamic regime. (ii) The change of the larger domains in size,due to the hydrodynamic flow in the late stage of the first phase separation process,keeps on taking place earlier than that of the new domains appeared in the secondary phase separation process. (iii) During the secondary phase separation process the size growth of the smaller domains takes place earlier than that of the larger ones,probably due to the assumption that the coarsening mode could decrease the interface tension more quickly.     

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.     

Effect of molecular weight on reaction-induced phase separation of epoxy resin modified with fluorocarbon chain terminated polyetherimide

Epoxy resins are currently used for many important applications such as adhesives, encapsulates and ad-vanced composite matrixes. However, the further use of epoxies is limited because of their inherent brittle-ness. Thus, the modifications of epoxy resin…     

Viscoelastic phase separation in polyethersulfone modified bismaleimide resin

The polymerization-induced phase separation process of polyethersulfone (PES) modified bismaleimide resin, 4,4′-bismaleimidodiphenylmethane (BDM), was investigated by time resolved light scattering (TRLS) and scanning electronic microscopes (SEM). At the blends with 10 wt% and 12.5 wt% PES, a phase inversion structure was found by SEM. TRLS results displayed clearly the spinodal decomposition (SD) mechanism and the exponential decay procedure of scattering vector q_m, which followed Maxwell-type relaxation equation. The characteristic relaxation time τ for the blends can be described by the Williams-Landel-Ferry equation. It demonstrated experimentally that the phase separation behaviors in these PES modified bismaleimide blends were affected by viscoelastic effect.     

Polymerization-induced phase separation in polyether-sulfone modified epoxy resin systems: effect of curing reaction mechanism

Polyethersulfone (PES)-modified epoxy systems with stepwise reaction were studied throughout the entire curing process by using optical microscopes, time-resolved light scattering (TRLS), and a rheolometry instrument compared with that of chainwise polymerization. The results suggested that the phase separation process is mainly controlled by the diffusion of epoxy oligomers for stepwise mechanism system and by that of epoxy monomers for chainwise mechanism system. In case of high PES content (SPES-20%) light-scattering results showed a viscoelastic phase separation and the characteristic relaxation time of phase separation can be described well by the WLF equation. However, in the case of low PES content (SPES-14%) secondary phase separation phenomenon was observed by Optical Microscope and further demonstrated by rheological study.     

Phase separation and rheological behavior in thermoplastic modified epoxy systems

The relationship between rheological behavior and phase separation in polyesterimide modified epoxy systems was studied by rheometry, time-resolved light scattering (TRLS), and Differential Scanning Calorimetry (DSC). The rheological behaviors of blends during phase separation showed an exponential grow of complex viscosity, while the phase separation was inhibited by the vitrification of the polyesterimide-rich matrix phase rather than gelation of dispersed epoxy-rich particles. The characteristic relaxation time obtained by the simulation of complex viscosity could be described well by the Williams–Landel–Ferry equation, which corresponded well with the light scattering results. Therefore, this work would further provide the experimental proofs that the exponential relaxation behavior of complex viscosity could be attributed to the viscoelastic flow of epoxy-rich escaping from polyesterimide-rich matrix during phase separation.     

Polymerization-induced viscoelastic phase separation in polyethersulfone-modified epoxy systems

The polymerization-induced phase-separation process of polyethersulfone (PES)-modified epoxy systems was monitored in situ continuously on a single sample throughout the entire curing process by using optical microscopes, time-resolved light scattering (TRLS), scanning electronic microscopes (SEM), and a rheometry instrument. At specific PES content a viscoelastic transformation process of phase inversion morphology to bicontinuous was found with an optical microscope. The rheological behavior during phase separation corresponds well with the morphology development. Light-scattering results monitoring the phase-separation process of systems with final phase inversion morphology show a typical exponential decay procedure of scattering vector qm. The characteristic relaxation time of phase separation can be described well by the WLF equation.     

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.