PROGRESS IN PHASE INVERSION EMULSIFICATION FOR EPOXY RESIN WATERBORNE DISPERSIONS

In this review, our recent work in phase inversion emulsification （PIE） for polymer （especially epoxy resin） waterborne dispersions is summarized. Based on experimental results about PIE process, the physical model is proposed which can guide the synthesis of the waterborne dispersions such as polymer/nanoparticle composite dispersion. In the presence of a latent curing catalyst, PIE can give a crosslinkable epoxy resin waterborne dispersion. The dispersions can form cured transparent coatings with some unique properties such as UV shielding. They are promising in functional coatings, waterborne resin matrices for composites, and sizing for high performance fibers.

Waterborne Epoxy Resin Modified by AMPS

A stable epoxy emulsion was prepared with epoxy resin （EP） as raw material, 2-acrylamido-2- methyl-l-propanesulfonic acid （AMPS） as modifier and benzoyl peroxide as initiator. By criterion of yield of the copolymer AMPS-EP, water-solubility, change of the acid value and intrinsic viscosity [η] along with reaction time, the copolymerization course was deduced. It is found that during the process, AMPS takes part in both the grafting copolymerization with epoxy principal chain and the ring-opening polyaddition with epoxy group. It is also discovered that the yield of AMPS-EP and water dispersing varies with reaction time. When it reaches 1.5 h, AMPS-EP can obtain good water-solubility; but the water-solubility will go bad gradually if it exceeds 3.5 h.. R spectrum analysis indicates that partial epoxy group partially remains and the others create sulfonic ester.

PREPARATION OF WATERBORNE ULTRAFINE PARTICLES OF EPOXY RESIN BY PHASE INVERSION TECHNIQUE

Waterborne ultrafine particles of epoxy resin were prepared by phase inversion technique. The results of SEM revealed that the particles diameter was in the range of 50 to 100 nm and the effects on amount of water required at phase inversion point were also discussed.

PREPARATION OF BISPHENOL A EPOXY RESIN WATERBORNE DISPERSIONS BY THE PHASE INVERSION EMULSIFICATION TECHNIQUE

The phase inversion emulsification technique (PIET) is an effective physical method for preparing waterborne dispersions of polymer resins. Some results concerning the preparation of bisphenol A epoxy resin waterborne dispersions by PIET in our laboratory were summarized. Electrical properties, rheological behavior and morphological evolution during phase inversion progress were systematically characterized. The effects of the emulsifier concentration and emulsification temperature on phase inversion progress and the structural features of the waterborne particles were studied as well. The deformation and break up of water drops in a shear field were analyzed in terms of micro-theology, while the interaction and coalescence dynamics of water drops were discussed in terms of DLVO theory and Smoluchowski effective collision theory, respectively. Based on the experimental results and theoretical analysis, a physical model of phase inversion progress was suggested, by which the effects of the parameters on phase inversion progress and the structural features of the waterborne particles were interpreted and predicted.

Cure Behaviors and Water Up-take Evaluation of a New Waterborne Epoxy Resin

Cure behaviors and water up-take evaluation of a low cost, ecofriendly and water soluble epoxy resin prepared by reaction between epichlorohydrin and PEG400, PEG600 and PEG1000, respectively, were investigated using non-isothermal differential scanning calorimetry （DSC） and gravimetrical method, respectively. Factors affecting the cure behaviors as well as water up-take of waterborne epoxy resins, such as amount of triethylenetetramine （TETA） and triethylene diamine （TEDA）, PEG molecular weight, curing temperature, were systematically investigated. The prepared water soluble epoxy resins can be cured under room temperature with the shape of the curing curves similar to that expected for an autocatalytic reaction.

Mechanism Analysis of Stiffness Improvement by Waterborne Epoxy Resin Surface Sizing Agent

Low-basis-weight paper lacks normal strength and stiffness. Waterborne epoxy resin could be employed with oxidized starch to improve paper stiffness through surface sizing. In this study,the mechanism of enhancing stiffness by adding waterborne epoxy resin was fully investigated. The results indicated that through surface sizing with epoxy resin,the paper thickness was preserved,whereas the elastic modulus increased significantly and the epoxy resin had positive impact on single fiber strength. A rigid resin layer and interpenetrating polymer network formed on the surface and in the inner layer of the paper,respectively. The formed resin layer and interpenetrating polymer network strongly supported the paper,leading to the improvement of the elastic modulus and stiffness. The stiffness improvement through surface sizing was mainly due to the formation of a fibrous composite layer and penetration of the sizing agent into the inner layers of the paper. The better the combination between fiber and sizing agent,the higher were the elastic modulus and the stiffness of the whole paper.

MICRO-PHASE SAEPARATION IN EPOXY RESIN WATERBORNE PARTICLES DURING CURING PROCESS

Sub-micron sized phenolic epoxy resin waterborne particles were prepared by phase inversion emulsification. Micro-phase separation occurred during the curing process at high temperature. The as-prepared samples possessed one glass transition temperature （Tg） and two exothermal processes during DSC heating scannings. After being thermally treated above the exothermal peak temperature, they possessed two glass transition temperatures with the disappearance of exothermal peaks, whilst a core/shell structure was formed. This was likely related with the outward diffusion of reactive oligomers to the outer layer of particles.

RHEOLOGICAL BEHAVIOR OF EPOXY RESIN WATERBORNE DISPERSIONS

The waterborne dispersions of epoxy resin were prepared by the phase inversion emulsification technique. Rheological behavior and its relationship with the structural change of the systems were studied. It was shown that the concentrated dispersions were highly viscoelastic and pseudoplastic, which was attributed to the formation of a physical network among the waterborne particles via hydrogen bond. The dilute dispersions were Newtonian fluids. The discrete clusters composed of small waterborne particles were found in diluted dispersions. With increasing solid content, there existed a structural transition via percolation through a cluster-cluster aggregation mode to form the physical network, which was qualitatively evidenced by the TEM morphologies.

Compatibility evaluation between waterborne epoxy resin and SBR latex modified asphalt emulsion

Good compatibility between waterborne epoxy resin(WER)modifier and styrene-butadiene rubber(SBR)latex modified asphalt emulsion(SBRE)is an essential premise for good pavement performance of WER and SBR latex compositely modified asphalt emulsion(WSAE).This study aims to explore the compatibility between WER modifier and SBRE.To achieve the goal,several WER modifiers produced by two methods were first selected to modify SBRE,thus the WSAEs were prepared.Next,storage stability and workability of the WSAEs themselves,and high-temperature performance,rheological behavior and temperature sensitivity of their evaporated residues were compared and evaluated via performing a series of experiments,respectively,thus the WER modifier possessing an optimal modification effect was recommended.Results show that the storage stability of WSAEs is sensitive to the amount of WERs.The incorporation of 1%WERs by the mass of SBRE improves the storage stability of SBRE,while WERs that exceed 1%weaken its storage stability.When the WERs reach 3%and 4%,the 5 d storage stability of prepared WSAEs will be beyond the limitation of specification.Incorporating WERs into SBRE negatively affects the workability of SBRE,and the workability of WSAEs is adversely influenced by the WERs content and the storage time.To ensure the construction,the WSAEs with 3%and 4%WERs should not be stored for more than 36 h and 48 h,respectively.The WERs effectively improve the high-temperature performance of SBRE residue,especially the 3%WERs.Besides,the WERs notably enhance the rheological property and thermal stability of SBRE residue.In contrast,the WER modifier produced by chemically modified method has a smaller adverse impact on the storage stability and workability of WSAE,and a larger enhancement on the high-temperature performance,rheological property and thermal stability of SBRE residue,which is thus recommended to modify SBRE.

HYDRODYNAMIC AND THERMODYNAMIC EFFECTS IN PHASE INVERSION EMULSIFICATION PROCESS OF EPOXY RESIN IN WATER

The mechanism of phase inversion emulsification process （PIE） was studied for waterborne dispersion of highly viscous epoxy resin using non-ionic polymeric surfactants. Drop deformation and breakup, rheological properties, conductivity, and particle size measurements reveal the micro-structural transition amid emulsification. It is revealed that strong flow causes water drop to burst with the formation of droplets and huge interface. Phase inversion corresponds to an abrupt rheological transition from a type of viscous melt with weak elasticity to a highly elastic type of aqueous gel. This implies that the phase inversion equivalent to a curvature inversion. Based on this, a geometric model is postulated to correlate process variables to the particle size. The coverage and conformation of the surfactant plays key role for the particle size of the final emulsion. The interactions of thermodynamic and hydrodynamic effects are also discussed. It is concluded that the thermodynamics control the PIE while the hydrodynamics drives the creation of interface and involves every step of PIE.

Rheological Behavior of Epoxy Resin Concentrated Dispersions

For the concentrated dispersions of epoxy resin prepared by phase inversion emulsification technique, the effects of solid content and temperature on the rheological behavior are studied. It is found that there exists reversible structural transition in concentrated dispersions subjected to shearing. The viscosity oscillation correlated with high viscoelasticity at lower stress is remarkable in highly concentrated dispersions. There exists storage modules overshot at higher stress during the dynamic stress time ramp test. This could provide some information on dynamics of structure changes during shear action. Besides, the effects of solid content and temperature on the relationship between tangent delta and frequency are essentially different.

水性环氧树脂-聚丙烯纤维改性水泥基快速修补砂浆性能研究

为改善机场道面修补砂浆脆性大和粘结性能差等问题,本文利用水性环氧树脂(WER)、聚丙烯(PP)纤维和硫铝酸盐水泥(SAC)制备出一种快速修补砂浆,并对其工作性能、力学性能、阻尼性能和耐硫酸盐腐蚀性能进行研究。结果表明,PP纤维和WER可显著提高快速修补砂浆韧性和粘结性能,使得快速修补砂浆2 h抗压、抗折强度和粘结强度分别达到22.3,5.1和3.7MPa,满足民用机场规范要求,同时可改善快速修补砂浆的阻尼性能和抗硫酸盐侵蚀性能。

水性环氧乳液/海泡石复合改性苯丙乳液涂层粘结性能研究

采用物理共混法制备水性环氧乳液/海泡石复合改性苯丙乳液涂层,探讨了苯丙-水性环氧乳液配比,三乙醇胺、填料及乳化沥青掺量对涂层粘结强度的影响,同时考察了复合涂层的抗渗性和耐高低温性。结果表明,当苯丙乳液与水性环氧乳液的有效质量比为1∶2,三乙醇胺、海泡石和乳化沥青掺量分别为2%、3%、5%时,复合涂层粘结强度为3.54MPa,与钢板间具有较好的相容性,且不透水性和耐高低温性优良。

基于响应曲面法的WER-SBR复合改性乳化沥青性能研究

为了定量分析水性环氧树脂(WER)和丁苯橡胶乳液(SBR)对乳化沥青性能的影响,并优化其配合比设计。基于响应曲面法设计了三因素三水平正交试验并以WER掺量、SBR掺量及固化温度为试验变量,以三大指标、车辙因子以及S/m值作为响应指标,利用Box-Behnken模型进行WER-SBR复合改性乳化沥青试验设计,并对试验结果进行回归分析。结果表明:WER能显著提高乳化沥青的高温性能,而低温性能的改善主要得益于SBR的低温柔韧性,固化温度对各响应指标的影响均呈现先增加后减小的变化趋势;当WER掺量为16%,SBR掺量为4%,固化温度为70℃时综合性能最优,其三大指标均满足规范值,高低温性能均优于单一改性乳化沥青和基质乳化沥青;实际试验值与预测值误差均不超过1%,表明改性剂掺量及固化条件可以利用响应曲面法进行设计、优化、预测,且结果具有一定的可靠度。

热塑性复合材料玻璃纤维环氧成膜剂的制备与性能研究

本文采用化学改性法,以环氧氯丙烷、共聚物P105、环氧树脂E-51和双酚A为原料,制备了一种水性环氧树脂乳液作为玻璃纤维成膜剂,研究了原料摩尔比、E-P105用量和乳化温度对乳液粒径和稳定性的影响。结果表明,当P105、ECH、NaOH摩尔比为1∶1.5∶1.2,环氧树脂与双酚A摩尔比为2.25∶1,E-P105质量份数为环氧树脂和双酚A质量的20%,乳化温度为60℃时,乳液粒径为0.387μm,粒径分布均匀,具有良好的稳定性,经上浆处理后的玻璃纤维复合材料力学性能优异。

咪唑啉季铵盐缓蚀剂改性蒙脱土/水性环氧纳米复合涂料

以油酸、二乙烯三胺和氯化苄为原料,合成了油酸基咪唑啉季铵盐缓蚀剂。通过FTIR、^(1)HNMR对其结构进行了表征,并离子交换至钠基蒙脱土(DK0)层间,制备了缓蚀剂改性蒙脱土(QACDK0)。通过XRD、TGA和UV-Vis对其结构、组成及层间缓蚀剂释放性能进行了表征。结果表明,咪唑啉季铵盐缓蚀剂约占QACDK0质量的38.96%,并将蒙脱土层间距由1.28 nm(DK0)扩大至3.98 nm(QACDK0)。利用DLS及Zeta电位对添加有QACDK0的水性环氧树脂进行了稳定性测试,其Zeta电位为–27.8 mV,具有较高的稳定性。电化学阻抗谱(EIS)测试表明,在腐蚀介质中浸泡30 d后,基于QACDK0制备的清漆漆膜仍具有2.29×10^(8)Ω·cm^(2)的高阻抗,表明涂层具有较好的耐腐蚀性。并且在耐中性盐雾测试中,QACDK0对应的防腐色漆耐盐雾时间最长,验证了该涂层具有良好的耐盐雾性能。

水性环氧树脂改性的建筑结构密封胶缓凝性能研究

为研究水性环氧树脂建筑结构密封胶缓凝性能,选用水性环氧树脂、水性环氧树脂固化剂、MS聚合物、硅烷偶联剂、纳米碳酸钙以及不同填料等试剂,以MS聚合物质量为标准设定试剂比例,分别制备A组分与B组分,将2组分依照1∶1质量比混合配比,由此获取不同配比条件下的改性密封胶样本。结果显示,在偶联剂用量达到2%以上时,密封胶样本的适用期符合建筑结构密封胶应用的适用期标准;水性环氧树脂用量为25%,密封胶样本硬度最优;当密封胶样本内不同填料质量比达到3.4∶20∶66∶16时,密封胶样本不会发生流淌现象;不同MS聚合物具有不同特征。

水性有机硅改性环氧树脂的制备与性能

利用二甲基二氯硅烷(DMDCS)与环氧树脂E51中-OH缩合反应合成有机硅改性环氧树脂,并采用相反转法制备水性有机硅改性环氧树脂,以疏水性优选有机硅改性环氧树脂合成条件,分析了乳化工艺对乳液平均粒径的影响,并考察了固化膜性能。结果表明,在环氧树脂40 g、DMDCS 1.6 g、溶剂用量20 mL、50℃反应8 h的条件下,有机硅改性环氧树脂与水的接触角为106.8°;当乳化剂用量为25%、乳化温度为65℃、剪切机转速为3000 r/min时,乳液平均粒径为1.011μm,储存稳定性(30 d)和离心稳定性(3000 r/min,30 min)良好;水性有机硅改性环氧固化膜固化时间短,具有优良的疏水性、力学性能、耐腐蚀性能。

水性环氧-SBR乳化沥青微表处混合料路用性能研究

以水性环氧树脂(WER)和丁苯(SBR)胶乳为乳化沥青改性剂,制备水性环氧-SBR乳化沥青(WESEA),采用蒸发残留物三大指标、旋转黏度、水煮法、湿轮磨耗试验、冻融循环试验、轮辙变形试验,探究水性环氧掺量对WESEA胶结料及其微表处混合料路用性能的影响。结果表明:WESEA胶结料高温性能、黏度与黏附性均随着水性环氧掺量增加而提升;当水性环氧掺量为10%时,WESEA微表处混合料1h湿轮磨耗值、6d湿轮磨耗值分别较SBR改性乳化沥青微表处混合料降低50.2%、44.0%,宽度变形率降低了41.8%;WESEA微表处混合料的耐磨性、抗水损能力以及抗车辙性能均优于SBR改性乳化沥青微表处混合料。

不同高分子防腐材料表面涂层粘附性能变化规律研究

为提高高性能混凝土的耐久性,通过分别在混凝土表面涂一层约3 mm的水性环氧树脂类防腐涂料、聚氨酯类防腐涂料和丙烯酸树脂类防腐涂料,来对比分析有防腐涂料和无防腐涂料的混凝土的抗氯离子性能、抗硫酸根离子性能和抗碳化性能等3种耐久性。试验结果表明,相比较于无涂料混凝土,含有防腐涂料的混凝土抗氯离子侵蚀性能、抗硫酸根离子侵蚀性能和抗碳化性能要好;聚氨酯防腐涂料对混凝土抗氯离子侵蚀性能、抗硫酸根离子侵蚀性能和抗碳化性能等耐久性最强,水性环氧树脂防腐涂料次之,丙烯酸树脂防腐涂料最弱。