水性紫外光固化树脂的研究进展

综述了近年来水性紫外光固化树脂及其涂料制备的最新研究进展.详细介绍了各类水性紫外光固化树脂的结构特点、制备方法及其在涂料中的应用情况,尤其对水性紫外光固化环氧树脂、聚氨酯树脂和超支化聚合物树脂等作了重点介绍,并展望了本领域的未来发展趋势.     

接枝环氧树脂/硅溶胶杂化水分散液的制备与表征

利用原位分散法制备了接枝环氧树脂 硅溶胶杂化水分散液 ,并通过红外光谱和 ζ电位测定 ,表征了接枝环氧树脂与硅溶胶之间的杂化作用 .实验结果表明 ,与接枝环氧树脂水分散液相比 ,杂化水分散液的粒径和粘度均减小 .按此探讨了形成杂化水分散液的历程 .初步测定了杂化水分散液成膜后的表面性能 ,发现它们具有更高的硬度和更好的疏水性能 ,与成膜过程中硅溶胶在膜表面的富集效应有关     

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.     

Waterborne Dispersions of a Polymer‐Encapsulated Inorganic Particle Nanocomposite by Phase‐Inversion Emulsification

Inorganic silica nanoparticles were encapsulated with an epoxy resin to give waterborne nanocomposite dispersions, using the phase‐inversion emulsification technique. Sub‐micron‐sized waterborne particles with narrow size distribution were prepared such. Microscopy results indicate that all the silica nanoparticles are encapsulated within the composites and uniformly dispersed therein. Curing of the nanocomposite dispersions proceeded in a controlled manner.     

无皂相反转乳化法制备高分子水基分散体系

高分子树脂水基分散体系是指高分子树脂以微粒形式分散于水中 ,包括高分子乳液、高分子悬浮液等体系 .由于高分子树脂水基分散体系具有低成本 ,高性能 ,无污染等优点 ,一直受到普遍关注 .高分子树脂乳液一般通过乳液聚合制备 .该方法只适用于由含双键的单体制备的加聚产物 .而在制备缩聚产物的乳液时 ,乳液聚合方法局限性很大 ,而最近发展起来的相反转乳化技术 ,适用于制备包括加聚产物和缩聚产物在内的大多数高分子水基分散体系 ,拓宽了高聚物水基分散体系的范围 [1] .杨振忠等 [2～ 5] 利用相反转乳化技术制备了未固化和可固化的环氧树脂…     

Incorporation of Reactive Corrosion Inhibitor in Waterborne Acrylic Polyurethane Coatings and Evaluation of its Corrosion Performance

Hydroxyl-epoxy phosphate (HEP) as a reactive corrosion inhibitor was innovatively synthesized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crosslinked with waterborne isocyanate curing agent, which was used to form waterborne HEP/acrylic polyurethane composite (HEP-APU) coatings on Q235 steel surfaces. Electrochemical impedance spectroscopy and polarization curves were applied to analyze the corrosion behavior of the HEP-APU coatings in 3.5wt% NaCl solutions. The results indicated that the HEP-APU coatings show a superior passivation property and efficient corrosion protection of Q235 steel. The waterborne acrylic polyurethane coating containing 0.5wt% HEP exhibited the best corrosion performance among all the coating specimens. The improved flash-rust resistance can be attributed to the introduction of the phosphate group which could form phosphate film on the steel substrate.     

Direct Synthesis of Fractal Polymer Dispersions by Miniemulsion Polymerization

Fractal colloids, which find applications in the preparation of advanced materials, are currently synthesized by means of a multistep procedure that yields a low solids content dispersion. This is not well suited for certain applications such as superhydrophobic coatings. In this work, a one‐step method for the synthesis of higher solids content waterborne fractal polymer dispersions is presented and it is shown that the surfaces obtained from the fractal dispersions are superhydrophobic (contact angle, θ > 150°) which is beyond the current waterborne coating technology (θ = 130°–137°). This opens the possibility for the large‐scale production of waterborne superhydrophobic coatings.

     

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 theconcentrated dispersions were highly viscoelatic and pseudoplastic, which was attributed to the formation of a physicalnetwor among tbe waterborne particles via hydrogen bond. The dilutc dispersions were Newtonian fluids. The discreteclusters composed of small waterborne particles were found in diluted dispersions. With increasing solid content, thereexisted a structural transition via percolation through a cluster-cluster aggregation mode to form the physical network, whichwas qualitatively evidenced by the TEM morphologies.     

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 waterbornedispersions of polymer resins. Some results concerning the preparation of bisphenol A epoxy resin waterborne dispersions byPIET in our laboratory were summarized. Electrical properties, rheological behavior and morphological evolution duringphase inversion progress were systematically characterized. The effects of the emulsifier concentration and emulsificationtemperature on phase inversion progress and the structural features of the waterborne particles were studied as well. Thedeformation and break up of water drops in a shear field were analyzed in terms of micro-rheology, while the interaction andcoalescence 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 wassuggested, by which the effects of the parameters on phase inversion progress and the structural features of the waterborneparticles were interpreted and predicted.     

环氧树脂在热塑性树脂改性中的应用

本文综述了国内外有关利用环氧树脂改性热塑性树脂共混体系研究的最新进展。着重阐述了环氧树脂在热塑性树脂之间的增容作用,如尼龙6(PA6)合金体系,改性聚苯乙烯塑料(ABS)合金体系,以及聚对苯二甲酸丙二醇酯(PTT)合金体系等。同时,介绍了利用环氧树脂的反应活性提高无机填料在聚合物中分散性研究的情况,如二氧化硅纳米粒子在聚醚砜(PES)中,以及滑石粉在聚丙烯(PP)中分散性的提高。最后,简介了环氧树脂改性热塑性树脂提高热塑性树脂物理机械性能方面的研究方向和成果并展望了环氧树脂在热塑性树脂改性研究中的前景。     

Properties of Aqueous Polyurethane Dispersion Modified by Epoxide Resin and Their Use as Adhesive

The aqueous polyurethane hybrid dispersion modified by the epoxy resin were synthesized using 1,4-butanediol ( BDO ) and dimethylolpropionic(DMPA) as chain extenders. A kind of automobile interior decoration adhesive was made by the modified hybrid dispersions. Effects of the content and the kinds of epoxide resin on the properties of dispersions and dispersion-cast films such as appearance, pot life, viscosity, particle size, molecular mass, hardness, swelling in water, contact angle, strength of stress, elongation at break, and other mechanical properties were studied. At the same time the effect of the E20 content on the peel strength of the adhesive for several automobile interior decoration substrates such as rubber/wood, poly(vinyl chloride)/wood; leather/wood, sponge/wood was investigated. The experimental results show that when the epoxy resin E20 content was 8%, the modified polyurethane hybrid dispersions possess better properties and the adhesive made by the modified dispersions posses better adhesion for automobile interior decoration substrates. The stress-strain curve of the modified aqueous polyurethane hybrid dispersions films shows the modified aqueous cast films possess better rigidity and toughness.     

水性可紫外光固化的硫代聚氨酯分散体的制备

本文利用巯基-点击化学制备了一系列水性可光固化的硫代聚氨酯分散体,即通过连续的巯基-异氰酸酯和巯基-迈克尔加成反应分别合成硫代聚氨酯和聚硫醚：首先,二异氰酸酯与过量的二元硫醇反应生成端基为巯基的硫代聚氨酯低聚物,然后与合成的二丙烯酸酯单甲基丙烯酸酯进行巯基-迈克尔加成反应,得到侧基为甲基丙烯酸酯的硫代聚氨酯树脂,最后,巯基乙酸与端基上的丙烯酸酯反应,提供树脂的亲水基团。将树脂分散在水中后,得到半透明的可光固化硫代聚氨酯分散体。树脂的主链上含有硫醚键,可以有效克服氧阻聚效应,得到较高的转化率;侧基上带有很多可光聚合的甲基丙烯酸酯基团,光聚合后固化膜的交联密度非常高,因而也具有较高的玻璃化转变温度。     

Reinforcement effect of carbon nanofillers in an epoxy resin system: Rheology,molecular dynamics,and mechanical studies

The reinforcing effect of carbon nanoparticles in an epoxy resin has been estimated with different approaches based on rheology, molecular dynamics (evaluated by differential scanning calorimetry, dielectric relaxation spectroscopy, and thermally stimulated depolarization current), and dynamic mechanical analysis. Carbon particles aggregate as the volume increases and form a fractal structure in the matrix polymer. The dispersion microstructure has been characterized by its viscoelastic properties and relaxation time spectrum. The scaling of the storage modulus and yield stress with the volume fraction of carbon shows two distinct exponents and has thus been used to determine the critical carbon volume fraction of the network formation (Φ*) for the carbon/epoxy dispersions. At nanofiller concentrations greater than Φ*, the overall mobility of the polymer chains is restricted in both dispersions and solid nanocomposites. Therefore, (1) the relaxation spectrum of the dispersions is strongly shifted toward longer times, (2) the glass‐transition temperature is increased and (3) the relaxation strength of both the secondary (β) and primary (α) relaxations increases in the nanocomposites, with respect to the pure polymer matrix. The dispersion microstructure, consisting of fractal flocs and formed above Φ*, is proposed to play the main role in the reinforcement of nanocomposites. Moreover, the network structure and the interface polymer layer (bond layer), surrounding nanoparticles, increases the relaxation strength and slows the cooperative α relaxation, and this results in an improvement of the mechanical properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 522–533, 2005     

Effect of carbon nanotubes dispersed in binder on properties of epoxy nanocomposite

Effect of quality parameters of starting raw materials, native carbon nanotubes (degree of defectiveness, thermal stability, morphology) on the properties of carboxylated and amidated nanotubes produced from these raw materials and on the homogeneity of a dispersion of amidated nanotubes in an epoxy oligomer was studied. The physicomechanical properties of epoxy nanocomposites produced from these dispersions were examined. It was found experimentally that an increase in the defectiveness of native nanotubes leads to a rise in the size of numerous aggregates in dispersions composed of an epoxy resin and amidated carbon nanotubes and, as a result, to deterioration of the physicomechanical characteristics of epoxy nanocomposites based on these dispersions.     

不完全相反转乳化过程分散相水滴形态发展研究

相反转乳化技术是制备高分子树脂水基分散体系的新方法[1～4].相反转指多组分体系(如油/水/乳化剂)中的连续相在一定条件下相互转化的过程,如在油/水/乳化剂体系中,其连续相由水相向油相(或从油相变为水相)的转变.在连续相转变区,体系的界面张力最低,因而分散相的尺寸最小.同理,可利用相反转技术直接将高分子树脂乳化为尺寸很小的水基微粒,即制备高分子树脂的水基分散体系.由于高分子树脂的粘弹性及相反转过程的复杂性,对高分子树脂的相反转乳化过程的机理研究较少.杨振忠[5]等通过调节高分子非离子型乳化剂浓度,可以有效地控制相反转完善程…     

化学改性环氧树脂水基涂料的研究——涂膜性能

用对氨基苯甲酸改性环氧树脂 ,使其具有亲水亲油两亲性质 ,测定了改性产物和纯环氧树脂共混物的玻璃化转变温度 ,结果显示两者能够相容 ,并以改性产物及其与纯环氧树脂的混合物制备水基涂料 ,测定了涂膜的物理和化学性能。结果表明 ,涂膜性能优良 ,保持了溶剂型环氧涂料的抗冲击强度、光泽度和硬度等方面的优点 ,而附着力提高 ,同时柔韧性大为改善 ,涂膜耐水性和耐化学药品性能优良。     

自由体积与亲水性对环氧涂层防护性能的影响

报道了涂层聚合物自由体积和亲水性对涂层腐蚀防护性能影响的初步研究结果.实验表明,相对于自由体积,树脂的亲水性是决定树脂吸水率的更主要因素.低亲水性涂层腐蚀防护性能的提高主要源自到达涂层/金属界面的水量的显著降低.但由于采用活性酯固化的环氧树脂涂层中水通道的尺寸相对较大,水合离子扩散较容易,因此该类涂层覆盖下的金属基体被润湿部分的腐蚀趋势反而较一般涂层为大.     

Enhanced corrosion protection performance with MWCNT dispersed epoxy coating prepared under supercritical CO2 assistance

The corrosion protection performance of epoxy coatings could be enhanced by incorporation of nanofillers such as MWCNT. However, a homogeneous dispersion of MWCNT in epoxy polymer is still a teasing challenge. Herein, we report an environmentally benign single‐step supercritical CO₂ processing method to improve the dispersion of MWCNT in epoxy matrix in order to achieve an effective anticorrosive coating. The executed approach provides a cluster‐free uniform distribution of MWCNT in epoxy matrix as characterized with UV‐visible spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffraction, and surface analysis. The anticorrosive characteristics of MWCNT/epoxy coating were studied in NaCl as well as in photodegraded dye medium through electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. We observed the remarkable corrosion of model metal substrate in photodegraded dye medium besides NaCl medium. In both mediums, the protection efficacy of MWCNT/epoxy coating was deduced from the stable impedance arcs in Nyquist plot and increased impedance modulus. The electrochemical impedance spectra were best fitted with equivalent circuits showing the higher values of pore resistance. Also, the MWCNT/epoxy coating exhibited a positive shift of corrosion potential and possessed a lower corrosion rate as compared with neat epoxy coating. More direct evidence of the excellent barrier properties for MWCNT/epoxy coating was visualized in SEM images. The obtained results implied that the superior dispersion of MWCNT into epoxy matrix significantly reduces the porosity of coating and inhibits the permeability of corrosive ions. We expect supercritical CO₂ assisted dispersion method can offer an efficient, cost‐effective, and industrially viable route to develop high performance protective coatings for varied commercialized applications.     

环氧树脂水性化体系研究进展

系统地介绍了目前国内外环氧树脂水性化的研究进展,总结了环氧树脂水性化体系的特点与应用,并提出一种水性环氧树脂乳液制备的新方法。     

Self-emulsifying Hydroxy Acrylic Polymer Dispersions for Two Component Waterborne Polyurethane Coatings

Novel self-emulsifying acrylic polymer aqueous dispersions (NPAD) for two component waterborne polyurethane coatings (2K-WPU) were prepared by the emulsification of self-emulsifying polymer blends in water, which the polymer blends typically consist of two acrylic polymers, one is a salt group containing polymer (P1), the other is a polymer without salt groups (P2). The dynamic light scattering (DLS) analysis showed that the NPAD have a bimodal particle size distribution and the particle diameters can be controlled by the amount of salt group containing polymer and the concentration of salt groups in this polymer. Transmission electron microscopy (TEM) images also testified that the NPADs possess small particles consisted of P1 and core-shell structure large particles which are composed of the P1 in the shell parts and the P2 in the core parts. The property comparisons of the NPAD, conventional polyacrylic dispersion (CPAD) and poylacrylic emulsion (PAE) for 2K-WPU disclosed that the NPADs possess higher solid contents up to 45 wt% and much lower carboxy salt contents than those of the CPAD, and the NPAD-based 2K-WPU films display much better performance including 90% of the gloss, 0.81 of the pendulum hardness, much better solvent- and water-resistance than those of the CPAD and PAE. The TGA curves indicated the NPAD-based 2K-WPU films display good thermal stability.