1H nuclear magnetic resonance study of polyurethane prepolymers from toluene diisocyanate and polypropylene glycol

Polyurethane prepolymers prepared from toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, and polypropylene glycol with a ratio between the isocyanate and hydroxyl groups equal to 2 were analyzed by ¹H nuclear magnetic resonance (NMR) spectroscopy in acetone‐d₆. Different temperatures and concentrations were used. Toluene 2,4‐dimethylurethane and toluene 2,6‐dimethylurethane were synthesized and used as model compounds to assign prepolymers signals. Measurements of spin–lattice relaxation time T₁ by “inversion recovery” experiments were carried out on toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, toluene 2,4‐dimethylurethane, toluene 2,6‐dimethylurethane, and polyurethane prepolymers. Differences in T₁ times were used to interpret prepolymers spectra, by means of the strong observed effect on protons due to the presence of adjacent isocyanate groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 347–357, 2003     

Properties of aqueous solutions for two binary mixed systems between two kinds of bile salts and nonionic surfactants

The micellar properties of aqueous binary mixed solutions for two systems consisting of sodium cholate (NaC)-octaoxyethylene glycol mono n-decyl ether (C₁₀E₈) and sodium glycocholate (NaGC)-C₁₀E₈ have been studied on the basis of surface tensions, polarity of the micelle interior and the mean aggregation number. Application of two theoretical treatments, based on regular solution and excess thermodynamic quantities for critical micellar concentration (CMC) data from surface tension curves of two mixed systems showed that the mole fraction of each bile salt in the mixed micelles near the CMC is lower than that of the corresponding prepared mole fraction in the mixed solution. The polarity of the interior suggested that the hydrophobicity of intramicelles increased with the increase of the mole fraction of bile salt in the mixed solution and that the mixed micelles become dramatically more hydrophobic at a mole fraction of 0.68 for NaGC−C₁₀E₈ system and 0.75 for NaC−C₁₀E₈ system, respectively. This implies that the micelles become richer in the bile salt molecules and the tendency appears strongly for NaGC−C₁₀E₈ system due to the strong cohesion between the conjugated glycines in the NaGC molecules. The decrease of aggregation number with the increase of the mole fraction of bile salts shows that the micelles approach those of the single system of each bile salt. This supports the previously mentioned facts.     

Penetration behavior and subsurface grafting of dansyl cadaverine and polyethylene glycol (PEG) derivatives in poly(ethylene-co-acrylic acid) (EAA) film

Dansyl cadaverine and polyethylene glycol (PEG) derivatives were grafted on the surface of EAA film and in its subsurface region through formation of amides and esters, respectively. A two-step reaction was conducted. First, EAA film was activated with PCl₅ at room temperature. Second, the acid chloride was reacted with dansyl cadaverine or a PEG derivative to form a modified film. ATR-FTIR spectroscopy and fluorometry were employed to analyze the modified films after each step. It was found that dichloromethane yielded the highest grafting efficiency, with the dansyl cadaverine penetrating throughout the ATR-FTIR analysis region (∼400 nm) in a few minutes. As the grafting depth increased with time, so did the amount of fluorescence intensity of grafted dansyl cadaverine. ATR-FTIR spectra for PEG grafting indicated that the acid chloride peak decreased with time, while the ester peak increased. However, hydrolysis occurred at later times, consuming the acid chloride groups within the film. A marked decrease of static water contact angle was observed for EAA grafted with PEG99 (PEG that contains 99 ethylene glycol repeat units), almost 40° lower than that of neat EAA (∼99°). For other PEG-grafted films, the surface hydrophilicity was also improved.     

爪形大分子CBC—NO的合成、表征及降滤性能研究

以1,3-丁二醇、柠檬酸为原料、甲苯为溶剂,在120℃油浴中反应,合成了柠檬酸-1,3-丁二醇-柠檬酸（CBC）爪状物小分子;然后,以甲基苯磺酸为催化剂,使CBC依次与环烷酸、十八醇分别在140℃和180℃油浴下接枝,合成了新型的爪形大分子柠檬酸-1,3-丁二醇-柠檬酸-环烷酸-十八醇（CBC—NO）。采用^1H—NMR及IR对合成的两种化合物进行了结构表征。结果表明,合成的CBC和CBC—NO与所设计的分子结构相吻合。用元素分析确定了CBC的化学组成为C16H22O14。合成的CBC—NO溶于有机溶剂,不溶于水。将CBC—NO按600μg／g的加剂量添加到不同的轻柴油中,柴油的冷滤点最大可降低8℃。     

氯化钠从水到乙二醇水混合中的迁移性质

在乙二醇和水为混合溶剂中加入NaCl组成三元系,在20~40℃时,改变混合溶剂中乙二醇的质量分数,在w=0%,10%,20%和30%的条件下,测定下列电池电动势AgCl-Ag|NaCl(mA),C2H6O2(w),H2O(1-w)|Na-ISE,(A)确定混合溶剂中AgCl-Ag和Na-ISE电极对在不同温度时的标准电动势,计算了NaCl的迁移性质。结果表明,低温时NaCl在纯水中有较高的吉布斯自由能状态,而在高温时,NaCl在乙二醇和水的混合溶液中处于较高的吉布斯自由能状态。     

PLLA-PEG-PLLA三嵌段共聚物的合成及性能

以萘钾和聚乙二醇形成大分子引发剂,在超声波震荡下引发L-丙交酯开环共聚,合成出不同EO/LA物质的量比的PLLA-PEG-PLLA三嵌段共聚物。利用FT-IR和1HNMR表征了三嵌段共聚物的结构。通过接触角和吸水率测试表明共聚物的亲水性是随着EO含量的增大而增强。采用DSC和POM研究共聚物的热性能和结晶形貌表明,共聚物各段熔点比各自均聚物低且有一个Tg,由于共聚物中EO/LA物质的量比的不同,表现出某段的单独结晶或两段都不结晶。因此,可通过改变嵌段含量,制备不同性能的材料,扩大聚乳酸的应用范围。     

乙二醇再生塔操作优化

在乙二醇再生过程中,分离效果和能量消耗是两个互相制约的因素。分析影响再生塔气液平衡过程中的主要因素,研究在满足分离要求、满足生产的条件下,降低能耗、节约能源的新措施。     

单质碘催化合成丁醛乙二醇缩醛

以单质碘为催化剂,通过丁醛和乙二醇反应合成了丁醛乙二醇缩醛。探讨了单质碘对缩酮反应的催化活性,较系统地研究了醛醇物质的量比、催化剂用量和反应时间诸因素对产品收率的影响。实验表明：在n（丁醛）∶n（乙二醇）=1∶1.5、催化剂用量为反应物料总质量的0.4%、带水剂环己烷的用量为8mL和反应时间45min的优化条件下,丁醛乙二醇缩醛的收率可达77.6%.     

端活性聚丙二醇对环氧树脂的增韧改性

以端羟基聚丙二醇为基础合成了端羧基和端环氧基聚丙二醇,对不同端基聚丙二醇改性环氧树脂体系进行了DSC、DMA、冲击性能和冲断面SEM研究。随聚丙二醇端活性基与环氧树脂反应性的增强,固化体系更倾向于形成均相结构,环氧树脂固化物玻璃化温度降低更多。端羟基和端环氧聚丙二醇都能明显提高环氧树脂的冲击强度。综合分析测试结果表明聚丙二醇是通过增塑方式对环氧树脂进行增韧,而端环氧基聚丙二醇是通过提高交联网络柔性的方式对环氧树脂进行增韧。     

聚羧酸助磨剂合成及其性能

利用水泥粉磨过程中的机械力促使水解聚马来酸酐（HPMA）与聚乙二醇单甲醚（MPEG）进行酯化反应形成聚羧酸助磨剂。试验研究了HPMA、MPEG、HPMA与MPEG的混合物、HPMA与MPEG的反应合成物对水泥助磨效果以及对砂浆性能的影响。结果表明,HPMA与MPEG都有一定的助磨性,HPMA与MPEG的混合物和反应合成物具有更佳的助磨性能,且可以改善水泥砂浆的流动性能和显著提高水泥砂浆的早期强度。激光拉曼光谱测试表明HPMA与MPEG的混合物和反应合成物与水泥共同粉磨后吸附在水泥颗粒表面,具有相似的拉曼位移图谱。