丙烯酸酯改性水性聚氨酯乳液的制备及性能研究

采用共聚的方法制备出丙烯酸酯改性的水性聚氨酯共聚乳液(PUA乳液),并对PUA乳液的制备方法和工艺、耐溶剂性、机械稳定性进行了初步的研究。结果表明,具有IPN结构的PUA乳液耐溶剂性、机械稳定性比水性PU有明显的提高。     

有机硅蒙脱土复合改性水性聚氨酯的研究

采用插层聚合制备了改性的水性聚氨酯乳液。X射线研究表明,蒙脱土以层间距5．19nm分散在水性聚氨酯基体中。硅烷和蒙脱土改性水性聚氨酯具有性能互补的效果,当有机蒙脱土和有机硅烷的质量分数分别为O．01及O．02时,聚氨酯乳液涂膜的拉伸强度和断裂伸长率比未改性时分别提高了70％、18％,吸水率降低了49％。     

蒙脱土硅氧烷双重改性水性聚氨酯

蒙脱土硅氧烷双重改性水性聚氨酯;水性聚氨酯;蒙脱土;硅烷偶联剂;乳液     

聚丙烯酸酯改性水性聚氨酯的制备

在回顾聚丙烯酸酯改性水性聚氨酯的研究历史基础上，系统地介绍了聚丙烯酸酯改性水性聚氨酯乳液（PUA）的制备方法，其中包括聚氨酯（PU）和聚丙烯酯（PA）的直接掺混法、PU和PA的乳液共聚法，接枝法，互穿网络法，核壳聚合法，对这些方法做了简单的评述，对其应用范围及前景进行了初步探讨。     

中和度对聚酯型阴离子水性聚氨酯性能的影响

采用预聚体法,以聚酯多元醇、甲苯二异氰酸酯、二羟甲基丙酸（DMPA）制备了聚酯型阴离子水性聚氨酯乳液,考察了中和度对乳液的粒径、运动黏度以及胶膜力学性能的影响。结果表明,随着中和度的增加,水性聚氨酯乳液的粒径减小;运动黏度增大;水性聚氨酯胶膜的耐水性先增大后减小;胶膜的拉伸强度提高,但其断裂伸长率降低。以三乙胺为中和剂...     

水性丙烯酸—聚氨酯微乳液的制备及粒子形态

水性聚氨酯作为一种环境友好材料近年来得到了迅速的发展，并以其优良的性能在皮革业、涂料、印刷、油墨等行业呈现广阔的应用前景［‘’‘j．通常采用IPN等技术制备出复合型水性树脂「‘，‘’，其中具有核壳结构的微乳液尤其受到重视．但研究多集中于微米级乳液的实际应用开发，对于纳米级、杂化型聚氨酯微乳液微观结构的研究却少见报道．本文通过在自乳化聚氨酯中自由基引发聚合丙烯酸类单体，制备出了具有核／壳结构的复合型丙烯酸一聚氨酯微乳液，并对微乳液的粒径、粒径分布、粒子形态及交联结构进行了研究．聚己内酯（220AL），日…     

四甲基苯二甲基二异氰酸酯基水性聚氨酯的合成和性能

采用四甲基苯二甲基二异氰酸酯、聚酯二元醇和二羟甲基丙酸为原料,合成了一系列具有不同异氰酸根与羟基摩尔比（n(-NCO)/n(-OH)）的聚氨酯乳液。 研究了n(-NCO)/n(-OH)对水性聚氨酯性能的影响。 结果表明,当该比值增加时,乳液的粒径增大,分布变宽,结晶性降低,耐热性下降,耐水性能呈现降低的趋势。 当异氰酸根与羟基摩尔比为3时,四甲基苯二甲基二异氰酸酯基水性聚氨酯的乳液粒径为10～30 nm,膜的分解温度达到275 ℃,24 h吸水率低于10%。     

聚氨酯-丙烯酸酯杂化乳液结构与性能的影响

以聚四氢呋喃醚二醇（PTMG）、异氟尔酮二异氰酸酯（IPDI）、亲水单体二羟甲基丙酸（DMPA）,乙二胺为主要原料,制备了稳定的水性聚氨酯乳液.然后以苯乙烯（St）、丙烯酸丁酯（BA）为单体,过硫酸钾为引发剂,在不外加乳化剂的条件下,运用物理共混、化学复合和化学共聚三种方法对该水性聚氨酯乳液进行改性研究.用FTIR技术对聚氨酯-丙烯酸酯杂化乳液的结构进行了对比与表征;通过粘度测定、粒度分析、力学性能和耐水性能测试、DSC分析,研究了不同改性方法对乳液及其胶膜性能的影响.结果表明,化学共聚的改性方法对原水性聚氨酯的耐水性的改良效果最好,能够得到稳定且综合性能较优的聚氨酯-丙烯酸酯杂化乳液.     

双重自交联聚氨酯-丙烯酸酯复合乳液的合成

自交联;水性;聚氨酯;丙烯酸酯;复合乳液     

单油酸三羟甲基丙烷酯改性水性聚氨酯

利用单油酸三羟甲基丙烷酯(TMPM)、异佛尔酮二异氰酸酯(IPDI)和聚氧化丙烯(PPG)等制备水性聚氨酯。采用透射电镜(TEM)、动态激光光散射(DLLS)、红外光谱(FT-IR)、热重分析(TGA)和表面张力仪表征了乳液胶束形态、产物结构及性能。结果表明:水性聚氨酯(PU)分子上引入脂肪侧链容易在水中形成规整的胶束,但TMPM改性的水性聚氨酯胶束粒径随TMPM含量的增加不断增大,当w(TMPM)=0.07时,乳液不稳定;脂肪侧链的引入降低了水性聚氨酯乳液的表面张力,表面张力随着反应体系中—NCO和—OH摩尔比的增大而降低,随交联度的增大先增加后减小;TMPM的引入可以提高胶膜的热稳定性。     

A Review on the Mechanism of Pigment Dispersion

In the quest of ensuring successful pigment dispersion, additives are used to aid dispersion and stabilization of pigment particles through attraction forces of various chemical nature including van der waals and “liquid bridge” forces as well as anchor groups with high affinity for pigment surface. On the other hand, dispersion efficiency is significantly dependent on the effectiveness of various dispersion equipment and their energy transfer, dispersion force and effectiveness. The common denominator for all this equipment are that; dispersion is achieved by shearing forces produced by the application of high positive and negative attrition. This article reviews and explores the nature and the significance of the various methods and forces in pigment dispersion and the various stabilization mechanisms adopted in producing stably fine pigment particles, dispersion application as well as future prospects.     

Material design of retardation films with extraordinary wavelength dispersion of orientation birefringence: a review

Orientation birefringence and its wavelength dispersion for various types of cellulose esters are reviewed. Cellulose esters such as cellulose acetate propionate and cellulose acetate butyrate show positive orientation birefringence with extraordinary wavelength dispersion, which is determined mainly by the ester groups rather than the main chains. The acetyl group provides negative orientation birefringence with strong ordinary wavelength dispersion, whereas the propionyl and butyryl groups give positive orientation birefringence with weak wavelength dispersion. Although all groups show ordinary wavelength dispersion, the summation of their orientation birefringences gives extraordinary dispersion. Moreover, the wavelength dispersion is dependent on the stretching ratio due to the difference in the orientation relaxation of each group. On the contrary, cellulose triacetate (CTA) shows negative birefringence with ordinary wavelength dispersion because it has no positive contribution. However, doping a plasticizer having positive orientation birefringence changes the orientation birefringence of CTA from negative to positive, and the wavelength dispersion from ordinary to extraordinary. This is attributed to the cooperative orientation of plasticizer molecules to the stretching direction with CTA chains, known as nematic interaction upon a hot drawing process.     

表面活性剂对分散体系粘度影响的特殊性

通过液体石蜡的水基化分散对影响分散体系粘度的粒子大小、表面活性剂胶束和界面膜等因素进行了研究.结果表明,表面活性剂胶束对分散体系粘度的影响极为有限,而在分散相粒子界面上由表面活性剂分子所形成的界面膜是导致分散体系粘度产生变化的重要因素.实验数据表明,对于分散体系的稳定性,存在一个表面活性剂浓度变化的临界值,而该临界值所对应的是表面活性剂分子在粒子表面以最紧密和规整的方式形成的界面膜,该种界面膜使分散体系粘度达到最大值,从而最大限度地保证了分散体系的稳定性.     

Influence of the elasticity of cellulose solutions on the dispersion of carbon black agglomerates

A counter-rotating rheo-optical tool was used to study the dispersion process of carbon black agglomerates in different suspending media, including the solutions of different types of cellulose, aqueous hydroxypropylcellulose solutions, and polyisobutylene. For each suspending fluid, the mechanism of dispersion (erosion or rupture) was identified, and the macroscopic critical shear stress necessary for dispersion was measured. Checking that the impacts of fluid infiltration and agglomerate size on the macroscopic critical shear stress for dispersion were negligible in our case, we showed that elasticity is a major factor acting on dispersion physics. At a constant viscosity, the higher the elasticity is, the more difficult dispersion is, giving higher critical shear stresses for initiating dispersion. There is a linear correlation between the suspending fluid elasticity and this critical shear stress, independent of temperature. An explication of the influence of matrix elasticity on agglomerate dispersion based on recent numerical simulation is given.     

TATB二聚体分子间作用力及其气相几何构型研究

采用对称性匹配微扰理论(SAPT)定量地求得TATB分子间的静电、交换排斥、诱导和色散等分子间作用能项, 从理论上揭示了TATB分子间作用本质; 在此基础上, 阐明了密度泛函在研究TATB二聚体时的适合性问题. 结果表明: (1)在有分子间氢键的TATB二聚体中, 库仑力足以与交换排斥力相抗衡, 起主导作用. (2)含分子间氢键的气相TATB二聚体的合理几何构型为平面型结构, 此结构的产生与色散力无关, 因此不管泛函是否含有近程色散作用, 均应预测到这种强极性的平面型结构. (3)在无分子间氢键的TATB二聚体中, 库仑力难以与交换排斥力相抗衡, 色散作用起到了关键作用; (4)在这种情况下, 未含有近程色散作用的密度泛函不可能给出合理构型. 恰好相反, 含有近程色散作用的密度泛函PBE0却能正确地预测到具有“平行重叠”结构且呈微弱极性的TATB二聚体, 色散力是导致这种构型产生的根本原因. “平行重叠”TATB二聚体是典型的色散体系, 其色散力占绝对主导地位并极有可能起源于两个TATB分子上π电子的相互作用. (5)对于所有TATB二聚体, 色散力或很显著或起主导作用. 由于密度泛函或未含有近程色散, 或只能部分地把近程色散表达出来, 这样使得当前所有密度泛函不可能精确求得这些二聚体的作用能.     

有组织介质中的偶合反应Ⅰ.油溶性成色剂的偶合活性

本文采用连续流动装置测量,并配合数值模拟法得到表征五种油珠分散状叔戊酰苯胺型成色剂的油珠偶合活性的偶合反应比速率常数和表观偶合速率常数,同时测定了叔戊酰苯胺型成色剂油珠在胶片层中的照相活性以及表征它们在非水溶液中分子偶合活性的解离常数pKa值,并且比较了上述结果。研究表明,油珠状成色剂的反应规律与分子状成色剂的反应规律是不相同的,这是由于经过“分子组装”后的成色剂油珠在反应时不再以分子为反应单元而是以分子组装体为单元。     

水性聚氨酯甲阶酚醛水分散液微观形态及杂化膜的性能

以自乳化型聚氨酯和甲阶酚醛制备了聚氨酯 酚醛复合水分散液 .pH值与酚醛溶解度的关系表明甲阶酚醛的溶解是酚羟基电离的结果 .聚氨酯 甲阶酚醛水分散液粒子的形态有核壳结构、不完善的核壳结构及纯聚氨酯颗粒三种 ,后者粒径最小 .随着酚醛用量的增大 ,粒子平均粒径增大 .酚醛含量增加使体系热稳定性、机械稳定性、冻融稳定性及临界聚沉值下降 ,pH值稳定范围变窄 .分散液稳定性和电性能考察证明 ,本复合分散液的稳定性主要由分散液的电性能所决定 ,属真溶胶 ,但在一定程度上也具有大分子溶液的特性 .复合液涂膜的性能较纯聚氨酯有所改善 ,尤其在添加了硅溶胶之后     

Contribution of axial dispersion to band spreading in perfusion chromatography

A new interpretation of the band spreading data in perfusion chromatography is proposed by investigating the relative importance of axial dispersion in perfusive beds. Elution chromatography of proteins (bovine serum albumin and lysozyme) under non-retained conditions on two kinds of reversed-phase perfusive supports (POROS R1/H and POROS R2/H), which have different pore structures, were carried out to obtain the axial dispersion data. The Knox equation and some empirical correlations for dispersion coefficients in porous media were applied to correlate the experimental data. The influences of particle properties, solute molecular sizes and flow velocity on the dispersion coefficient were elucidated. Axial dispersion was recognised to be the main contributor to peak broadening in perfusion chromatography. The dependence of the height equivalent to a theoretical plate on flow-rate was found to be the result of the velocity dependence of the axial dispersion. The dispersion coefficient in a perfusive column can be well represented both by a power-law relationship and a correlation derived based on stochastic theory. Pursuant to these, it was found that pore size distribution of the perfusive particles and solute molecular size are important parameters, which influenced the dispersion results significantly.     

THE EFFECT OF CLAY DISPERSION ON THE CRYSTALLIZATION AND MORPHOLOGY OF POLYPROPYLENE／CLAY COMPOSITES

PP/clay composites with different dispersions, namely, exfoliated dispersion, intercalated dispersion and agglomerates and particle-like dispersion, were prepared by direct melt intercalation or compounding. The effect of clay dispersion on the crystallization and morphology of PP was investigated via PLM, SAXS and DSC. Experimental results show that exfoliated clay layers are much more efficient than intercalated clay and agglomerates of clay in serving as nucleation agent due to the nano-scale dispersion of clay, resulting in a dramatic decrease in crystal size (lamellar thickness and spherulites) and an increase of crystallization temperature and crystallization rate. On the other hand, a decrease of melting temperature and crystallinity was also observed in PP/clay composites with exfoliated dispersion, due to the strong interaction between PP and clay. Compared with exfoliated clay layers, the intercalated clay layers have a less important effect on the crystallization and crystal morphology. No effect is seen for samples with agglomerates and particle-like dispersion, in regard to melting temperature, crystallization temperature, crystal thickness and crystallinity.