超支化聚合物的性能、合成及其功能化应用研究

超支化聚合物，具有多端基的“缺陷核壳”空间结构，化学反应性活泼，易于改性，与相应的线型聚合物相比，拥有特殊的性能，在多领域展现出广阔的应用前景。随着合成技术的进步，它们的应用研究，尤其是功能化的应用研究，成为多年来的研究热点。主要介绍超支化聚合物的结构、性能、合成及其功能化应用研究概况。     

Composite polymer electrolytes based on the low crosslinked copolymer of linear and hyperbranched polyurethanes

Low crosslinked copolymer of linear and hyperbranched polyurethane (CHPU) was prepared, and the ionic conductivities and thermal properties of the composite polymer electrolytes composed of CHPU and LiClO₄ were investigated. The FTIR and Raman spectra analysis indicated that the polyurethane copolymer could dissolve more lithium salt than the corresponding polymer electrolytes of the non crosslinked hyperbranched polyurethane, and showed higher conductivities. At salt concentration EO/Li = 4, the electrolyte CHPU30‐LiClO₄ reached its maximum conductivity, 1.51 × 10^?5 S cm^?1 at 25°C. DSC measurement was also used for the analysis of the thermal properties of polymer electrolytes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3607–3613, 2007     

超支化聚酯的合成及光固化性能研究

通过甲基四氢苯酐和环氧丙醇的开环聚合反应，一步法制备超支化聚酯，聚酯的数均摩尔质量为1450～2600g／mol，支化度在0．41～0．71之间。用甲基丙烯酸缩水甘油酯改性，合成了UV固化超支化聚酯，并对其光固化性能进行了初步研究，发现超支化聚酯能有效降低固化膜的线收缩率，聚酯的官能度越高，固化膜的硬度越大，固化速度越快，在约1s的固化时问内凝胶率超过75％。     

Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

超支化聚合物

综述了超支化聚合物的发展历史和最新发展趋势。介绍了超支化聚合物与一般线形聚合物比较所具有的独特性能,各个组分对于超支化聚合物性能的影响以及超支化聚合物在各个领域的应用。     

Hyperbranched Polymers Containing Cyclopentadienyliron Complexes

A number of hyperbranched polymers containing cyclopentadienyliron moieties were prepared using the A₂+B₃ method. The A₂ compounds used were common diols, dithiols or dichloroarenecomplexes. B₃ compounds included either prepared star-shaped molecules or a purchased triol. The effect of the reaction conditions on the properties of the products was probed. Analysis of the prepared polymers was conducted using ¹H and ¹³C NMR, viscometry, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Viscometry values were generally found to be low, in the range of 0.175–0.300 dl/g. TGA showed losses starting at approximately 230°C and ending at 280°C, corresponding to the decomposition of the cyclopentadienyliron moiety. Degradation of the polyether backbone was found to occur starting at 390–567°C. Glass transition temperatures were found to be between 60 and 134°C, whereas melting temperatures ranged from 155 to 190°C.     

含三苯基膦结构可溶性超支化聚芳醚酮的合成与表征

以双（4–（对氟苯甲酰基）苯基）苯基氧化膦为A2单体,11,,1–三（4–羟基苯）乙烷为B3单体,通过A2＋B3方法合成了含三苯基膦结构可溶性超支化聚芳醚酮（HPEKKs）,有效地避免了凝胶化现象.通过改变A2/B3的比率改变HPEKKs的封端基团,并通过1H NMR和FTIR对其结构进行了表征.1H NMR测量羟基封端HPEKKs（HPEKK-OH）的支化度和氟原子封端的HPEKKs（HPEKK-F）支化度分别达到0.62和0.85.DSC测量HPEKK-OH和HPEKK-F的玻璃化转变温度分别为151℃和131℃.TGA测量HPEKKs在失重率为5%时热分解温度达到500℃以上.HPEKK-OH和HPEKK-F可以很好地溶解于N–甲基吡咯烷酮、N,N–二甲基乙酰胺和二甲基亚砜等多种有机溶剂.     

Synthesis and properties of UV-curable hyperbranched polyurethane and its application in the negative-type photoresist

UV-curable hyperbranched polyurethane(UV-HBPU) containing carboxyl groups was synthesized from isophorone diisocyanate(IPDI), diethanolamine(DEOA), polyethylene glycol(PEG-400), hydroxyethyl acrylate(HEA), and 2,2-bis(hydroxymethyl) propionic acid(DMPA). The UV-HBPU was used as a negative-type photoresist for a printed circuit board(PCB). Fourier-transform infrared spectroscopy(FTIR) and proton nuclear magnetic resonance(1HNMR) spectroscopy of UV-HBPUs indicated that the synthesis was successful. Differential scanning calorimetry(DSC) and thermogravimetric analysis(TGA) showed that the thermal stability of the UV-HBPUs decreased as the HEA content increased. The polymer exhibited excellent photoresist properties, and the resolution of circuits based on this negative-type photoresist reached 10 μm.     

Thiol-terminated hyperbranched polymer for DLP 3D printing: Performance evaluation of a low shrinkage photosensitive resin

In order to lower the volume shrinkage of the DLP 3D printing photosensitive resins during printing, a thiol-terminated hyperbranched polymer (T-HBP) was synthesized and introduced into the bisphenol A epoxy acrylate (EA) based photosensitive resin system. The obtained T-HBP was characterized by FTIR and ¹H NMR spectra, and the grafting rate of sulfhydryl was determined. The mechanical properties of the photosensitive resins were measured by tensile and impact strength measurement. The glass transition temperature of the photosensitive resins was analyzed by DSC and the impact fracture surface was observed by SEM. T-HBP exhibited a much lower viscosity than its linear counterparts, and the addition of thiol improved the curing speed of the photosensitive resins. When the amount of T-HBP added was 20 wt%, the shrinkage of the photosensitive resins was reduced by about 45.5% and the impact strength increased by 33.9% compared with the control. The macromolecular spherical structure of T-HBP effectively reduced the functional group density of the photosensitive resins. In addition, the thiol-acrylate photopolymerization introduced by T-HBP further reduced the volume shrinkage of the photosensitive resins.