建筑防水涂料用硅丙乳液的制备与性能

介绍了有机无机复合建筑防水涂料用硅丙乳液的研制背景、制备方法及主要性能。所制备的硅丙乳液有机硅含量达12％，其与水泥和细砂集料混合均匀后形成的有机无机复合防水涂料对常用建筑材料粘接力强，形成的弹性胶膜吸水率低、防水性好、耐老化性高、产品性能稳定。     

后酯化法制备聚羧酸盐系高效减水剂的研究

通过丙烯酸与烯丙基磺酸钠的自由基共聚制备了含有羧基和磺酸基团的共聚物,然后将其与聚乙二醇单烷基醚进行酯化反应,合成了可用作高效减水剂的聚羧酸盐接枝共聚物。通过CPC、红外光谱和化学滴定等方法对接枝共聚物的结构进行了表征。在此基础上讨论了接枝共聚物主链分子量、支链长度以及羧基、磺酸基和聚氧乙烯支链三者的摩尔比等因素对减水剂性能的影响。并研究了减水剂掺量对水泥净浆和砂浆性能的影响。     

含氟丙烯酸酯聚合物乳液的合成及涂膜性能研究

采用核-壳乳液聚合法制备了含氟丙烯酸酯聚合物乳液,讨论了含氟单体——甲基丙烯酸六氟丁酯(HFMA)用量、复合乳化剂体系用量、引发剂用量、N-羟甲基丙烯酰胺(NMA)用量、聚合反应温度、反应时间、搅拌速度对聚合反应最终单体转化率以及乳液聚合稳定性的影响;测试了涂膜的吸水率和乳液的黏度,以考察涂膜的耐水性。通过傅立叶红外光谱(FT-IR)对乳胶膜的组成和结构进行表征,结果表明,含氟单体HFMA通过接枝共聚反应与丙烯酸酯进行了有效的结合。     

3,3-二叠氮甲基氧丁环与3-叠氮甲基-3-甲基氧丁环均聚物的嵌段共聚物热分解机理及非等温裂解动力学分析

3,3-二叠氮甲基氧丁环与3-叠氮甲基-3-甲基氧丁环均聚物的嵌段共聚物(BAMO-AM-MO)是一种含能黏合剂,为了解其受热分解机理及分解动力学情况,采用DSC法、TG-DTG法、固相原位池-FTIR联用技术和DSC-TG-MS联用技术探讨了BAMO-AMMO的热分解过程及机理.研究结果表明,BAMO-AMMO受热分...     

FT-IR法研究PBT粘合剂的固化反应动力学

为明确3,3-双(叠氮甲基)氧丁环-四氢呋喃共聚醚(PBT)粘合剂与常用固化剂的反应过程,利用傅里叶变换红外(FT-IR)光谱法研究了PBT/多异氰酸酯(N100)、PBT/甲苯二异氰酸酯(TDI)和PBT/TDI/N100体系,50～80℃、TPB催化下的固化反应动力学。结果表明:PBT/N100在整个固化过程中遵循二级反应动力学规律,表观活化能63.10 kJ·mol~(-1),指前因子A=1.63×10~7h~(-1)。含有TDI的体系的固化过程均分为两段,但分段机理不同。PBT/TDI体系整个固化反应遵循二级反应动力学规律,但由于TDI上不同位置—NCO活性的差异,以转化率60%为界线分为两个阶段,转化率小于60%为第一阶段,转化率大于60%为第二阶段,相同温度下,第一阶段的反应速率明显高于第二阶段,两阶段的表观活化能分别为54.71 kJ·mol~(-1)和56.50 kJ·mol~(-1),指前因子分别为4.38×10~7h~(-1)和1.24×10~7h~(-1)。PBT/TDI/N100体系反应由于TDI和N100上—NCO活性的差异也分为两个阶段,转化率小于65%主要发生TDI扩链,表现为二级反应动力学,表观活化能为71.17 kJ·mol~(-1),指前因子A=4.58×10~8h~(-1);转化率大于65%主要发生N100交联,反应速率受扩散控制。TDI/N100复配时,指前因子较单一N100体系和单一TDI前后两阶段分别扩大了28,10,37倍,表明固化剂复配后反应活性位点增加。     

沸石对丁苯共聚物/水泥凝结硬化及早期水化的影响

为了解决丁苯共聚物/水泥复合胶凝材料凝结硬化慢的问题,将沸石作为调凝材料,讨论其对复合胶凝材料凝结时间和早期强度的影响,并从水化放热速率和水化产物的角度分析沸石调节凝结硬化的机理.结果表明:沸石能够加速丁苯共聚物/水泥复合胶凝材料的水化,通过促进C_3A和C_3S的水化,缩短复合胶凝材料的水化诱导期,提高加速期最大放热速率,促进AFt和Ca(OH)_2的生成,从而加速复合胶凝材料的凝结硬化,缩短凝结时间,提高早期强度.     

PET/PEG共聚酯连续熔融终缩聚过程两相稳态模型分析

针对高性能共聚酯PET/PEG缩聚过程,建立了圆盘反应器中连续熔融聚合两相稳态模型,模拟分析了缩聚反应温度、压力、停留时间以及传质系数对气相组成、共聚酯数均分子量、端羧基浓度以及副产物二甘醇和水浓度的影响。结果表明：挥发组分主要在反应器的前半部分产生,在z > 0.4后气相挥发总量已经很小;乙二醇占气相组成的比例极高,约为90%,而二甘醇的含量极低,只为0.5%左右;随反应器温度、真空度、停留时间、传质系数的增加,共聚酯产物的分子量增大,当传质系数大于0.1 s^-1后,反应器出口的共聚酯分子量几乎不再变化,此时已不受传质控制,最终产物的分子量约26000。     

Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84–87 nm for 14–20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100–130 nm (lattice constant 115–150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm.     

Morphological and mechanical study of nanostructured epoxy systems modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide)triblock copolymer

Thermosetting systems based on DGEBA epoxy resin and poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) triblock copolymer were prepared and investigated. Different mixtures were obtained by using different contents of EPE block copolymer in order to study the influence of the modifier on the properties of the final materials. All thermosetting systems were prepared without using any solvent and were cured at ambient temperature, taking into account the lower critical solution temperature (LCST) behavior of the block copolymer. DSC results indicated that the addition of block copolymer affected to the curing reaction time and to the glass transition temperature of the mixtures and also the miscibility of EPE triblock copolymer in the epoxy resin was proved. The morphologies studied by AFM and TEM showed clear nanostructuration up to 25 wt % EPE content. The addition of 5 and 15 wt % of EPE block copolymer led to a considerable improvement in the toughness of the materials. When EPE block copolymer was added to the epoxy resin, the surface became more hydrophilic and the UV–vis transmittance decreased slightly maintaining a high level of transparency.     

Perpendicular oriented cylinders via directional coalescence of spheres embedded in block copolymer films induced by solvent annealing

Polystyrene-b-poly(methyl acrylate) (PS-b-PMA) block copolymer with PS volume fraction of 25.2 vol% was synthesized by atom transfer radical polymerization. Non-pretreated silicon wafers were used as the substrates to prepare perpendicular oriented PS cylinders in PMA matrix via solvent annealing which could induce the transformation of spheres to vertically oriented and hexagonally packed cylinders. The spherical microdomains were formed after the evaporation of solvents from the solutions of the block copolymer in selective solvents mixed from methanol, acetone and dichloromethane. The thickness of films could be as thick as 1000 nm, which were much thicker than usual cases and the cylinders came from the directional coalescence of the spheres, thus any pre-treatments of the substrates were not required for perpendicular orientation. The structures were characterized by small angle X-ray scattering (SAXS), transmission electron microscope (TEM), atom force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS).