含氟聚氨酯的研究进展

综述了溶剂性、水性含氟聚氨酯的合成及研究，并进行了讨论。     

淀粉聚醚多元醇的合成研究

近年来由于石油价格的上涨,严重地限制了聚氨酯工业的发展。因此用价廉易得的再生资源淀粉代替部分化工产品合成聚醚多元醇,减少对石油产品的依赖性,降低成本,对发展聚氨酯工业和给淀粉寻找新的出路,具有十分重要的现实意义和新的战略意义。     

水性含氟聚氨酯的研究进展

水性含氟聚氨酯具有低的VOC排放,同时由于氟元素的引入,解决了传统水性聚氨酯耐水、耐油性差的缺点,大大拓展了其在涂料、皮革、油墨等领域的应用范围,因此受到广泛关注.本文综述了近年来国内外水性含氟聚氨酯的主要研究进展,综合比较了两种合成水性含氟聚氨酯主要方法,即核壳乳液聚合法和缩聚共聚法的各自特点,并对由两种不同方法制备的水性含氟聚氨的性能进行了讨论.     

高活性阻燃聚醚多元醇的合成

五溴苯基缩水甘油醚;阻燃PU泡沫;高活性阻燃聚醚多元醇的合成     

聚醚多元醇对环氧树脂的增韧改性

通过力学性能、热性能以及扫描电镜等方法研究了聚醚多元醇对环氧树脂-酸酐体系的增韧效果。结果表明:聚醚多元醇在环氧固化过程中分相析出,呈现出较好的增韧效果;在环氧-酸酐体系中,大分子量聚醚多元醇的增韧效果不如小分子量的;而由环氧乙烷封端的聚醚多元醇,由于含有与环氧树脂相容的聚环氧乙烷(PEO)链段,分散相与环氧母体间能够形成良好的界面作用,也体现出良好的增韧效果。     

新型含氟聚醚链修饰的咪唑离子液体的合成及其热稳定性

含氟聚醚链修饰的咪唑与碘代烷烃经季铵化反应高产率地制备了4个新型的含氟聚醚链修饰的咪唑碘盐(3a ～3d);通过3的复分解反应合成了一系列新型的含氟聚醚链修饰的咪唑离子液体盐(4a ～4d,5a～5d),其结构经1 H NMR,19F NMR,IR和元素分析确证.热重分析研究表明,4和5具有较高的热稳定性.     

杂多酸催化合成淀粉聚醚多元醇及其反应中间体稳定性

采用可溶性固体杂多酸做均相反应催化剂，两步反应使用一种催化剂，在中温、常压条件下，合成了产率较高的符合工业技术指标的淀粉聚醚多元醇，而且催化剂能得到95％以上的回收，简化了工艺过程，提高了产品质量，降低了成本，用元素分析、IR、^1HNMR和羟值的测定确定了产物的组成和相对分子质量，对中试实验进行了初步探索，得出最佳合成条件。     

~1H-NMR测定聚醚多元醇分子量——共聚醚和混聚醚分子量测定

本文研究了用~1H-NMR测定共聚醚和混聚醚数均分子量的方法.根据测得的与酯氢峰面积对聚合段相应峰面积积分比率计算分子量,测得数据与端基化学法测量分子量对照,所获结果令人满意.     

~(19)F-NMR法测定聚醚多元醇中伯羟基的相对含量

<正> 聚醚多元醇是聚氨酯材料的主要原料之一.多元醇中伯羟基含量的多少对反应活性有着直接的影响,因此,准确地测定伯羟基含量已成为许多研究者关心的课题,并已报道了不少测定方法,其中主要包括化学动力学方法、~1H-核磁共振(NMR)法和~(19)F-NMR法,~1H-NMR法系利用不同的酰化剂,将聚醚多元醇酰化后测其酰化物的~1H-NMR谱,从伯、仲羟基相应的酯基氢的积分比例来计算伯羟基的相对含量,但由于体系中存在其它含氢基因,且是大量的,使测量困难或应用受到限制.~(19)F-NMR法测伯羟     

含氟聚酰亚胺及其在微电子工业中的研究进展I含氟单体及聚酰亚胺的合成

综述了近年来国内外在含氟聚酰亚胺(PI)研究及应用领域中的最新进展情况。主要从含氟二胺单体、二酐单体及含氟聚酰亚胺在合成方面的研究进展情况进行了详细的综述。重点阐述了中国科学院化学研究所305组近几年在这方面的研究进展情况，并指出为了推动含氟聚酰亚胺这类具有优良综合性能的功能材料在工业上的广泛应用，就必须首先解决含氟单体种类较少这个制约含氟聚酰亚胺发展的瓶颈问题。     

Synthesis of Novel Polyether Polyol by Using Double Metal Cyanide

Hydroxyl-terminated novel polyether polyols were synthesized by polymerization of epichlorohydrin (ECH) catalyzed by double metal cyanide (DMC) catalyst. The effects of reaction temperature and catalyst concentration on the polymerization of Polyether Polyol were studied. The molecular structure and the damping properties were measured by IR spectra, ¹H-NMR spectra and the dynamic mechanical analysis.     

聚醚中聚合物分散粒子的形态对体系稳定性和粘度的影响

以苯乙烯和丙烯腈在聚醚中的分散聚合制备了聚合物聚醚，用电镜观察了不同合成条件下分散粒子的形态轨现工艺因素可改变分散粒子的形态，从而影响ＰＯＰ的性质。颗粒聚集是影响体系稳定性和粘度的主要因素。在适宜的合成条件下，可获得稳定的表面光滑的孤立圆球，相应的ＰＯＰ具有低的粘度。     

电子束固化含氟聚氨酯丙烯酸酯的制备与性能

以六亚甲基二异氰酸酯三聚体、丙烯酸羟乙酯及羟基含氟丙烯酸酯为原料制备了电子束固化含氟聚氨酯丙烯酸酯预聚物. 通过傅里叶变换红外光谱(FTIR)和核磁共振氢谱(¹H NMR)对产物进行了表征. 研究了产物与溶剂组成的两相混合体系的流变性能、电子束固化行为及固化后涂层性能. 结果表明, 产物与溶剂混合体系具有正触变性, 绝对黏度变化符合Sedden公式, 黏流活化能约为44.8 kJ/mol. 电子束固化后涂层性能(如热稳定性、硬度、附着力和光泽度)优良.     

Synthesis and characterization of fluorinated polyurethane with fluorine-containing pendent groups

A novel fluorinated polyurethane （FPU） with fluorine-containing pendent groups was prepared by using fluorinated polyether glycol （PTMG-g-HFP） as a soft segment, 1,6-hexamethylene diisocyanate （HDI） or toluene diisocyanate （TD1） as a hard segment and 1,4-butanodiol （BDO） as a chain extender. FTIR, ^1H NMR, ^13C NMR and GPC were used to characterize the structure of the fluorinated polyurethane. Thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by TGA. XPS analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. The results showed the fluorine enrichment on the surface of FPU.     

Production of Polyether Polyols Using Phosphate Calcium Salt

The synthesis of bifunctional polyols using glycerol phosphate calcium salt hydrate as initiator and caesium hydroxide and potassium tert-butoxide as catalyst by means of anionic polymerization was achieved. If a phosphate salt is used as initiator, this reaction allows us to obtain polyols with phosphate groups in its structure not previously described. The relationship to catalyst type was also studied. The kinetic studies revealed that there was a linear relationship between the propylene oxide consumption and time. Both the polydispersity indexes of the polyol and the reaction time decreased using caesium hydroxide instead of potassium tert-butoxide under the same synthesis conditions. The incorporation of phosphorus in the polyol chain was confirmed by MALDI-TOF spectra and ³¹P-NMR spectra. GPC analyses showed an additional small peak in the product, attributed to the allyl adduct. The purification procedure of polyether polyols was also studied by means of liquid-liquid extraction, desorption and ion exchange.     

侧链液晶聚醚螯合树脂研究进展

相对于传统聚醚螯合树脂,侧链液晶聚醚型螯合树脂由于刚性介晶基元的引入,赋于了聚醚分子更好的使用性能,具有热稳定性好、吸附容量大、离子选择性高、易于设计与合成等优势,成为近年来树脂领域研究的热点之一。本文介绍了近年来国内外侧链液晶聚醚螯合树脂的合成、性能与应用现状。最后依据对侧链液晶聚醚螯合树脂机械性能、吸附选择性、再生性能以及环保性能的使用要求,对其分子设计与合成方法及新应用领域进行了展望。     

Synthesis of Polyether Polyols using Glycerol Phosphate Disodium Salt as Initiator

The employment of glycerol phosphate as initiator for the synthesis of polyether polyols is explored in order to open the possibility of preparing a new range of products with enhanced flame retardant properties. For this purpose, glycerol phosphate disodium salt was employed as initiator, caesium hydroxide was selected as catalyst and dimethyl sulfoxide as the aprotic solvent. The influence of the operative conditions on the polymerization rate and the product properties was studied. This study revealed that the employment of dimethyl sulfoxide allows the activation of the initiator and the start-up of the propylene oxide incorporation to the polyol chain. The optimal ratio between the catalyst and the initiator resulted to be 1:6 using CsOH. MALDI-TOF MS, ¹H-NMR and ³¹P-NMR results confirmed that the phosphate was incorporated into the polymer chain. Finally, the thermal stability of the phosphorylated polyols was confirmed by thermogravimetric analysis.     

Synthesis, characterization and properties of a novel fluorinated polyurethane

A novel fluorinated polyurethane (FPU) was prepared by fluorinated polyether glycol (PTMG-g-HFP) as a soft segment, 1,6-hexamethylene diisocyanate (HDI) or toluene diisocyanate (TDI) as a hard segment and 1,4-butanodiol (BDO) as a chain extender. Fourier transform infrared spectroscopy (FTIR), ¹H NMR, ¹³C NMR and gel permeation chromatography (GPC) were used to characterize the structure of the fluorinated polyurethane. The thermal stabilities of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were studied by thermogravimetric analysis (TGA). X-ray photoelectron spectroscopy (XPS) analysis at two different sampling depths for the fluorinated polyurethane was used to investigate the surface compositions of FPU. And the mechanical properties of the fluorinated polyurethane and the corresponding hydrogenated polyurethane were also measured. Chemical resistance of polyurethane films was estimated through spot tests with different solvents. The results showed that FPU had high thermal stability, strain-hardening property and good chemical resistance. The XPS measurements showed the fluorine enrichment on the surface of FPU.     

Hydroxyalkylation and Polyether Polyol Grafting of Graphene Tailored for Graphene/Polyurethane Nanocomposites

Graphene functionalization by hydroxyalkylation and grafting with polyether polyols enables polyurethane (PU) nanocomposites formation by in situ polymerization with isocyanates combined with effective covalent interfacial coupling. Functionalized graphene (FG) hydroxylation is achieved either by alkylation, transesterification, or grafting of thermally reduced graphite oxide. In the presence of K₂CO₃ as catalyst the reaction of FG‐OH with ethylene carbonate at 180 °C affords hydroxyethylated FG, whereas transesterification with castor oil produces riconoleiate‐modified FG polyols. In the “grafting‐from” process, FG‐alkoholate macro initiators initiate the graft polymerization of propylene oxide to produce hybrid FG polyols containing 38 and 59 wt% oligopropylene oxide. In the “grafting‐to” process 3‐ethyl‐3‐hydroxymethyl‐oxetane is cationically polymerized onto FG‐OH, producing novel hyperbranched FG‐based polyether polyols. Whereas hydroxylation and grafting of FG greatly improve FG dispersion in organic solvents, polyols and even PU, as confirmed by transmission electron microscopy, matrix reinforcement of FG/PU is impaired by increasing alkyl chain length and polyol graft copolymer content.