混合型环氧树脂水分散液的制备与表征

以苯乙烯和甲基丙烯酸的共聚物[P(St-co-MAA)]作为分散剂和高分子量的环氧树脂在120℃下混合,制备了环氧树脂水分散液。测定了环氧树脂与P(St-co-MAA)混合前后的环氧值,证明共聚物中的部分羧基和环氧基团发生反应,形成了接枝共聚物,P(St-co-MAA)与环氧树脂之间的相容性良好,从而制得稳定性良好而且粒径较小的水分散液。同时考察了共聚物组成和环氧树脂分子量时水分散液以及成膜后性能的影响。     

接枝环氧树脂水分散液的合成、分离与表征

控制不同的反应条件,采用甲基丙烯酸、苯乙烯与环氧树脂在丙二醇丁醚/正丁醇溶剂中接枝共聚,合成了粒径在87～104nm范围的环氧树脂水分散液。通过环己烷/乙醇和丙酮两步萃取,对接枝共聚产物进行分离,用FTIR表征,并估算了接枝共聚物的组成。实验结果表明,所制备的粒径为纳米级的环氧树脂水分散液,具有良好的机械稳定性、冻融稳定性及贮存稳定性。ξ电位测定表明,产物在pH>8的条件下更为稳定。     

ZrO2纳米粒子原位杂化PVDF膜的制备及其抗污染性能

针对传统聚合物膜抗污染性差的问题,本文从杂化膜结构设计出发,提出将ZrO2纳米粒子的原位制备和聚偏氟乙烯(PVDF)相转化成膜过程有机结合的制膜新方法.该方法将阴离子交换树脂引入到N,N-二甲基甲酰胺(DMF)中,以氧氯化锆为原料,利用阴离子交换树脂提供的―OH与无机盐的阴离子进行交换,得到ZrO2纳米粒子均匀分散的N,N-二甲基甲酰胺溶胶体系.随后将PVDF聚合物溶解到所得的N,N-二甲基甲酰胺溶胶体系中,获得均一、透明的铸膜液.利用X射线光电子能谱(XPS)和透射电子显微镜(TEM)对杂化膜中锆的存在状态和分散性能进行了表征.结果表明,ZrO2纳米粒子均匀分散在PVDF基体中,并且形成的纳米粒子的粒径约为10-20 nm.通过粘度、分相速度和膜形态的测定,研究了成膜机理.结果表明,ZrO2纳米粒子的引入加速了铸膜液成膜过程的分相速度.杂化膜的亲水性能通过接触角测定仪进行了评价.并选择以牛血清蛋白为代表模拟污染物,考察了杂化超滤膜的抗污染性能.结果表明,原位形成的ZrO2纳米粒子显著提高了膜的亲水性,减少了膜对蛋白质的吸附.这种将ZrO2纳米粒子的原位制备和PVDF相转化成膜过程有机结合的制膜新方法在有机-无机杂化膜的制备领域具有显著意义.     

水性纳米硅溶胶的表面改性及其应用研究

将几种功能性有机硅烷偶联剂与不同pH值的无机纳米硅溶胶水溶液通过表面改性反应和溶胶-凝胶技术制备出水分散纳米杂化改性硅溶胶,并用透射电镜TEM和红外光谱FT-IR对其进行表征和分析,研究了硅烷偶联剂碳链长度及偶联剂用量、溶液pH值对改性硅溶胶稳定性的影响,初步探讨了其在水性涂料、水性纳米罩光防污涂料及砂浆防水中的性能和应用。     

具有明确硬段结构的水性聚氨酯脲的研究

通过逐步反应由4,4′-二苯基甲烷二异氰酸酯、2,2-二羟甲基丙酸和1,4-丁二醇,合成了结构明确的硬段模型化合物.通过13C NMR对其序列结构进行了表征,并通过FTIR、DSC和WAXD对其形态结构进行了研究.进一步制备了具有这类规整结构硬段的水性聚氨酯脲,初步考察了水分散液及其成膜后的性能.实验结果表明,这类聚氨酯脲水分散液的粒径小于110nm,在室温下贮存期大于一年,成膜后具有优异的耐水性能以及表面疏水性能.     

全氟磺酸树脂/二氧化钛杂化薄膜的制备与表征

利用可溶性全氟磺酸树脂和二氧化钛前躯体钛酸丁酯液-液相体系, 结合蒸汽水热结晶方法制备了全氟磺酸树脂/二氧化钛杂化薄膜, 并通过扫描电子显微镜(SEM)、X-射线衍射(XRD)、红外光谱分析仪(FT-IR)及紫外-可见分光光度计(UV-vis)等测试方法对杂化薄膜的形貌、晶型、结构及光学性能进行了表征. 结果表明: 蒸汽水热结晶法能促进全氟磺酸树脂/二氧化钛杂化薄膜的结晶和相变; 水热后该杂化薄膜表面平整光滑, 没有裂纹, 二氧化钛晶型为锐钛矿并以球形微粒均匀分散在全氟磺酸树脂基体中; 随着杂化体系中二氧化钛含量的增多, 其粒径逐渐减小、团聚现象消失且杂化薄膜的紫外吸收性能显著提高.     

有机硅改性UV固化水性环氧树脂的研究

以环氧树脂E-51、甲基三乙氧基硅烷为原料,用接枝共聚的方法合成了有机硅改性水溶性UV固化环氧树脂,该方法有效地改善了环氧树脂的柔韧性、水溶解性,提高了成膜物的机械性能,其拉伸强度达到53.5 MPa,断裂伸长率为46.5%,耐冲击性大于50 kg/cm。通过红外光谱、热重分析表征产物的结构和性能,结果表明,有机硅已经成功接枝到环氧树脂的分子上。有机硅改性后环氧树脂在400℃的分解率由之前的60%降至40%。文章同时讨论了有机硅改性水性UV固化环氧树脂合成中反应温度、有机硅种类以及加入量等对UV固化水性环氧树脂成膜物的附着力、耐水性及耐碱性的影响,以此获得最佳反应条件:质量分数为14.4%的甲基三乙氧基硅烷与羧酸改性的环氧树脂在90℃下反应5～6 h。     

水性环氧树脂的制备和固化机理的探讨

探讨了以环氧树脂、甲基丙烯酸和丙烯酸丁酯为原料,由接枝的路线合成水可分散性环氧树脂的制备、乳化及固化成膜一系列的反应机理,对过程进行了分析,并讨论了有关因素对各步反应的影响。     

由铜-胺氧化还原引发反应一步法简便制备TiO_2表面接枝聚甲基丙烯酸甲酯纳米杂化粒子

提出并验证了一种通过普通自由基聚合在纳米TiO2表面接枝聚甲基丙烯酸甲酯的简单方法.通过在纳米TiO2粒子表面引入伯胺分子层(纳米TiO2-NH2粒子),利用Cu2+-胺氧化还原体系实现了CuSO4催化纳米TiO2-NH2粒子表面引发甲基丙烯酸甲酯(MMA)的自由基接枝聚合,从而一步得到表面固定有聚甲基丙烯酸甲酯链的纳米TiO2杂化粒子(纳米TiO2-PMMA杂化粒子).红外光谱、热失重分析与电镜的结果都表明PMMA已经被接枝到纳米TiO2粒子表面,且接枝率随着聚合时间的延长而逐渐增大,PMMA链的引入有助于降低纳米TiO2粒子微球的团聚程度、增强与有机溶剂分子的范德华力,从而提高分散稳定性.反应溶液中没有游离均聚物形成.     

超支化聚合物接枝改性碳纳米管及其分散性能

将碳纳米管用c(K2Cr2O7)=0.25 mol/L,c(H )=1 mol/L混合溶液进行处理,制得表面含有活性羟基的碳纳米管. 在催化剂的存在下,以CNTs为反应中心核,氧化处理后的CNTs表面上的活性羟基与A2B型单体发生一步缩聚反应,将超支化聚合物接到碳纳米管的表面上,实现了碳纳米管的表面修饰. 探讨了反应条件对接枝在CNTs表面上的超支化聚合物(HPAE)量的影响,当反应温度为120 ℃,反应时间为10 h,反应配料比n(CNTs-OH):n(A2B单体)=1:6时,固载量达到0.255. FTIR、XPS、TEM的表征结果证明,CNTs接枝上了超支化聚合物. 透光度的测定和静置实验表明,超支化聚合物接枝改性CNTs在丙酮、乙醇、水等溶剂中具有很好的分散性能.     

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.     

Organic/inorganic hybrid nano-microstructured coatings on insulated substrates by electrospray deposition

Organic/inorganic hybrid nano-microstructured coatings on insulated polymer films were prepared by electrospray deposition (ESD) from an acrylic resin/silica sol blend solution. The surface morphologies of the coated films were observed using scanning electron microscopy (SEM). The SEM images showed that a nano-microscaled fibrous structure was formed on the film. The fiber diameter decreased from 4.4 microm to 600 nm with the increase in the silica sol content. Energy-dispersive X-ray analysis also revealed that silica atoms were homogeneously distributed in the fibrous structure on the polymer film. These results indicated that the ESD method is potentially a useful option for producing nano-microstructured coatings on not only conductive, but also insulating surfaces.     

Fabrication and characterization of superhydrophobic silica nanotrees

Superhydrophobic silica nanotrees were obtained by sol–gel method with hybrid silica sol and jelly-like resorcinol formaldehyde resin. Rough surfaces were obtained by removing the organic polymer at high temperature. After the films with rough surface were modified by trimethylchlorosilane (TMCS), the wettability of the film changed from superhydrophilic to superhydrophobic. The surface roughness of the silica nanotrees film is about 20 nm, and it is transparent and superhydrophobic with a water contact angle higher than 150°.     

液化膜对胶体悬浮液粘度的影响

Viscosity is one of the most important properties of colloids in mixing, transportation, stabilization, energy consumption, and so on. According to Einstein‘s viscosity equation, the viscosity of a colloidal dispersion increases with the increase of particle concentration. And the equation can be applicable to all micro-particle dispersions, because the effect of solvation films coated on particles can be neglectable in that case. But with the decrease of particle size to nano-scale, the formation of solvation films on nano-particles can greatly affect the viscosity of a dispersion, and Einstein‘s equation may not be applicable to this case. In this work, one kind of micro-size silica particle and two kinds of nano-size silica particles were used to investigate the effect of solvation films on dispersion viscosity, dispersed in water and ethyl alcohol solvents, respectively. The results of theoretical calculation and experimental investigation show that the increase of viscosity is contributed from solvation films by more than 95 percent for nano-particle dispersions, while less than 10 percent for micro-particle dispersions.     

The maleimide modified epoxy resins for the preparation of UV‐curable hybrid coatings

In the present study, maleimide‐modified epoxide resin containing UV‐curable hybrid coating materials were prepared and coated on polycarbonate substrates in order to improve their surface properties. UV‐curable, bismaleimide‐modified aliphatic epoxy resin was prepared from N‐(p‐carboxyphenyl) maleimide (p‐CPMI) and cycloaliphatic epoxy (Cyracure‐6107) resin. The structure of the bismaleimide modified aliphatic epoxy resin was analyzed by FTIR and the characteristic absorption band for maleimide ring was clearly observed at 3100 cm^?1. Silica sol was prepared from tetraethylorthosilicate (TEOS) and methacryloxy propyl trimethoxysilane (MAPTMS) by sol–gel method. The coating formulations with different compositions were prepared from UV‐curable bismaleimide‐based epoxy oligomer and sol–gel mixture. The molecular structure of the hybrid coating material was analyzed by ²⁹Si‐CP/MAS NMR spectroscopy techniques. In the ²⁹Si CP/MAS NMR spectrum of the hybrid coating, mainly two kinds of signals were observed at ?68 and ?110 ppm that correspond to T³ and Q⁴ peaks, respectively. This result shows that a fully condensed structure was obtained. The thermal and morphological properties of these coatings materials were investigated by using TGA and SEM techniques. Hardness and abrasion resistance properties of coating materials were examined and both were found to increase with sol–gel precursor content of the coating. The photopolymerization kinetics was investigated by using RT‐IR. 70% conversion was attained with the addition of 15 wt% of BMI resin into the acrylate‐based coating formulation. It was found that the UV‐curable organic–inorganic hybrid coatings improved the surface properties of polycarbonate. Copyright © 2009 John Wiley & Sons, Ltd.     

亲水单体对聚氨酯-含氟丙烯酸酯复合乳液颗粒和表面性能的影响

为了提高聚氨酯-丙烯酸酯聚合物的耐水性和耐溶剂性, 将N-甲基二乙醇胺(MDEA)扩链的交联聚氨酯丙酮溶液作为反应介质, 以苯乙烯、丙烯酸丁酯、含氟丙烯酸酯(FA)为单体, 过氧化苯甲酰为引发剂, 通过溶液聚合相转化法制得新型阳离子聚氨酯-含氟丙烯酸酯复合乳液. 研究了MDEA对聚合物水分散液的乳胶粒径、Zeta电位以及乳胶膜表面性能的影响, 并用FTIR, TEM对聚合物的结构和乳胶粒形态进行了表征. 结果表明, MDEA的添加利于降低乳胶粒径, 但对乳胶膜的疏水性能有不利影响, 当MDEA的质量分数为13.15%时, FPUA乳胶粒的形态呈球形, 粒径约为253 nm, 乳胶膜的表面自由能低于25.1 mJ/m², 接触角衰减速率约为0.38 (º)/min. 另外, 乳胶膜的高温处理能够使表面自由能降低11.5%以上.     

Preparation of hybrid microcapsules and application to self‐healing agent

It was tried to prepare hybrid microcapsules composed of porous inorganic particles and epoxy resin shell and to apply to the self‐healing agent. A water soluble imidazole of gelation promoting agent as the core material was microencapsulated in the porous inorganic particles, which were coated with epoxy resin. The porous inorganic particles were prepared with the interfacial reaction between sodium silicate and calcium ion in the (W/O) dispersion. In the experiment, the concentration of sodium silicate and the mixing speed to form the (W/O) dispersion were mainly changed. The porous inorganic particles were immersed in the aqueous solution dissolving imidazole and then, added in the corn oil dissolving epoxy resin to be microencapsulated with gelated epoxy resin. The hybrid microcapsules containing imidazole with the mean diameters from 200 to 400 µm were able to be prepared and to induce the gelation reaction of epoxy resin by breaking the hybrid microcapsule shell due to heating. Copyright © 2013 John Wiley & Sons, Ltd.     

环氧树脂复合水分散乳液的制备及其性能研究

通过溶液聚合法制备了丙烯酸单体改性的高相对分子量的环氧树脂复合水分散乳液.利用傅立叶变换红外光谱仪测试了改性聚合物的结构,用ZETA电位分析仪测定了水分散液的粒径及其分布,用透射电子显微镜观察了乳液粒子形态.实验结果表明,改性树脂在水等极性溶剂中有较好的溶解性;随着改性树脂中羧基中和程度的加大,水分散液粒径减小,并成为形状规则的单分散乳液.作者同时进行了改性树脂稀释行为的研究.     

Acrylic polymer/silica organic–inorganic hybrid emulsions for coating materials: Role of the silane coupling agent

Acrylic polymer/silica organic–inorganic hybrid emulsions were synthesized by a simple method, that is, a conventional emulsion polymerization and subsequent sol–gel process, to provide water‐based coating materials. The acrylic polymer emulsions contained a silane coupling agent monomer, such as methacryloxypropyltriethoxysilane, to form highly solvent‐resistant hybrid films. On the other hand, the hybrid films from the surface‐modified polymer emulsions, in which the silane coupling agent was located only on the surface of the polymer particles and the particle core was not crosslinked, did not exhibit high solvent resistance. A honeycomblike array structure, which was derived from the polymer particles (diameter ≈ 50 nm) and the silica domain, on the hybrid film surfaces was observed by atomic force microscopy. The crosslinked core part and silane coupling agent containing the shell part of the polymer particles played important roles in attaining high solvent resistance. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4736–4742, 2006