可交联的PMMA型和PS型高热稳定性二阶非线性光学材料的合成与表征

采用封管反应的方法,以较高产率(80%以上)合成了一系列含环氧基团的可交联PMMA型和PS型极化聚合物材料,该材料具有很好的成膜性.用DSC和T_gA等方法研究了聚合物固化前后的热性能,结果表明,由于聚合物在极化后期经热固化使引入的环氧基团开环交联,聚合物的玻璃化转变温度(T_g)较固化前明显提高30～50K.同时,固化后的聚合物具有较高的热分解温度(T_d>543K).对聚合物的二阶非线性光学性质的测试结果表明,在室温下放置100h后,聚合物的电光系数r₃₃值均保持在初始值的75%以上.这是由于环氧基团的开环使固化后的聚合物本身产生一定程度的交联,导致取向后的发色团被聚合物的交联网禁锢而不易弛豫,从而使这类PMMA型和PS型二阶非线性聚合物材料的热稳定性能得以提高.     

高热稳定性氟化聚酰亚胺的合成及在热光开关中的应用

用一种新型超支化氟化聚酰亚胺(FHBPI)作为波导材料制备了聚合物热光开关. 采用DSC, TGA, 近红外吸收谱和原子力显微镜(AFM)等方法对FHBPI的热稳定性及光学特性进行了表征. 结果显示, FHBPI的玻璃化转变温度为189 ℃, 在空气中5%的热失重温度为596 ℃, 表明具有良好的热稳定性; 旋转涂膜法制备的FHBPI薄膜具有良好的成膜性; 薄膜表面粗糙度为0.54 nm; FHBPI在光通信波段有较小的吸收损耗, 适合制备低损耗的光波导器件; 用FHBPI-50为波导芯层材料, FHBPI-30为包层材料, 设计制作的热光开关响应上升时间为267.9 μs, 下降时间为254.1 μs.     

环氧液晶弹性体材料的制备与力学性能研究

传统的液晶弹性体材料多采用丙烯酸酯类或聚硅氧烷类分子,通过自由基聚合制备.然而由于自由基聚合易被氧气阻聚,固化过程收缩率高且内应力大,传统液晶弹性体材料的力学性能并不是很优异.为解决这一问题,本文合成了带有环氧基团的液晶单体和交联剂,使用碘鎓盐作为引发剂,通过光引发阳离子反应,用原位聚合交联法制备了环氧液晶弹性体材料.光引发阳离子聚合和传统自由基聚合相比,不受氧气影响且弹性体固化时体积收缩率小.对制备出的液晶弹性体材料的晶相和力学等性能进行探究和表征,发现其比传统的丙烯酸酯类或者聚硅氧烷类液晶弹性体材料具有更优异的力学性能,在清亮点以上,其弹性模量达到了0.92 MPa.     

新型光交联互穿网络体系的合成与非线性光学性能

设计合成了侧链上接有肉桂酸酯基团功能化聚合物(E51-DO3-C)和侧链同时含有环氧基团和偶氮苯生色团的功能化低聚物(PPGF-DO3-50),这两种功能化聚合物可分别以环加成反应和阳离子光引发机制进行交联反应形成先交联IPN体系,研究了E51-DO3-C、PPGFDO3-50体系和光IPN体系的极化交联后材料的二阶非线性光学(NLO)性能。研究含DO3生色团的酚醛环氧甘油醚低聚体在BDS·2PF_6阳离子光引发下的光交联过程以及NLO性能,非线性光学系数d_(33)值稳定性较差。利用这两种体系的相容性,设计获得了复合物E51-DO3-C/PPGF-DO3-50,其d_(33)值稳定性有显著提高,室温下30天后d_(33)值保持初值的80％左右。     

含香豆素基团超支化星形聚合物的合成与表征

设计并合成了含有香豆素基团的自引发单体, 与2-(2-甲氧基乙氧基)乙基甲基丙烯酸酯(MEO₂MA)进行自缩合乙烯基共聚合后得到超支化聚合物H-PMEO₂MA. 以其作为大分子引发剂, 进行二甲氨基乙基甲基丙烯酸酯(DMAEMA)的原子转移自由基聚合, 合成了具有温度响应性的超支化星形聚合物H-PMEO₂MA-star-PDMAEMA. 将此超支化星形聚合物在水中自组装成胶束后, 利用支化点处香豆素基团的光二聚性能, 在λ=320 nm的紫外光照射下进行香豆素间的光交联反应, 形成核交联胶束. 此核交联胶束在254 nm紫外光照射下则会发生解交联反应. 采用尼罗红作为模型药物, 将其装载到超支化星形聚合物胶束中, 研究了不同条件下的药物释放行为.     

一种光交联电光聚合物的合成及其外部电光测量

合成了一种新的带有光交联基团的电光聚合物,其高分子基体是双酚A环氧树脂,二阶非线性生色团对硝基苯胺和光交联基团肉桂酰氯都键接在高分子链上.将聚合物溶解后旋涂成膜,对薄膜进行电晕极化.极化的后阶段用紫外光照射,使聚合物体系交联成网络结构,形成生色团取向长时间稳定的聚合物电光薄膜.用这种聚合物电光薄膜构成外部电光调制系统,测量了共面波导上的电信号.     

高折射率聚合物-无机纳米光学杂化材料的设计与制备及其应用

传统的高折射率聚合物光学材料,可以通过向聚合物中引入一些芳香环,含硫基团以及除氟以外的其他卤素原子来提高聚合物光学材料的折射率,但是就目前的研究现状来看,这类纯聚合物光学材料的折射率一般都低于1.8.而将具有高折射率的无机纳米粒子引入到聚合物中,所制备的聚合物-无机纳米光学材料的折射率能够达到1.8以上.而且这类高折射率聚合物-无机纳米光学杂化材料同时具有高分子光学材料和无机材料的双重优点,具有广泛的应用前景.鉴于当前高折射率聚合物-无机纳米光学杂化材料发展之迅速和其研究与开发的重要性,并结合目前国内外的研究现状,本文就高折射率聚合物-无机纳米光学杂化材料的设计、制备方法及其相关应用做一个比较系统的介绍,同时对这类材料在未来研究中所应注意的问题也提出了相应的看法.     

紫外/可见光谱在有机光纤研制中的应用

有机光导纤维是近十几年来在新型光功能性高分子材料领域中的一支独秀.相对于玻璃光导纤维,有机光导纤维加工容易、口径大、轻而柔软、抗挠曲、抗冲击、耦合容易,更重要的因素是制作成本低和用途广泛.通常光导纤维是一种带包层的透明圆柱型的细丝.芯子的折射率高于包层并且是不变的,这种纤维称为突变型(SI)光纤.由于SI型光纤的带宽小,不能满足高信息量传输的需要,因而渐变型(GI)有机光纤得以发展.在这种光导纤维中,纤芯的折射率是呈抛物线型分布的,其轴心的折射率最大,折射率由纤维轴心沿径向到包层逐渐变小,在芯/包层界面处折射率无突变,光线在这种光纤的传播路径近似正弦波.沿正弦波处的折射率均小于轴心区的折射率.由于光速是反比于折射率的,因此当光沿着正弦途径传输时,其速度大于光沿着轴心传输的速度.于是,较长的光路被较大的光速所补偿,结果是光在正弦波处的传输时间与在轴心处的传输时间上没有大的区别,而脉冲加宽是正比于传输时间的差值,因此有望在GI型有机光纤中得到较小的脉冲加宽.GI型有机光纤的制备一般可在GI型有机预制棒的基础上通过熔融热拉技术拉制而成.因此,制备GI型有机预制棒及其折射率分布的检测成为关键步骤.折射率分布的测量方法有很多,如近场扫描法、折射近场法、切片干涉法等.本文首次介绍了将紫外/可见吸收光谱应用于预制棒折射率分布的定性测试上,得到了在预制棒芯区沿径向掺杂剂分子溴苯的吸收强度呈抛物线型分布.因测试折射率分布的其他方法较为繁杂以及受仪器的限制,所以利用紫外/可见吸收光谱这一非常普通的仪器来估计折射率分布的情况不失为一种简单易行的方法.     

新型全息用光致聚合物的研究

研制了一种新型全息用光致聚合物材料,其成膜树脂为胺固化环氧体系,全息记录组分为光引发自由基聚合体系.用新合成的高效光敏染料DEAMC做光敏剂,通过配方调整,制备了一系列的样片,以457 nm的蓝光为记录光,632.8 nm的红光为探针光,研究了样片的衍射效率、灵敏度、折射率调制度等全息性能.结果表明,通过调整材料的配方组成、各组分的含量及样片的膜厚等因素,可以优化样片的全息性能.对样片的信噪比损失(LSNR)测试结果表明,在全息存储的曝光量范围内对样片曝光引起的图像信噪比损失仅有0.40 dB,说明样片的光学质量高,在全息存储上将具有很好的应用前景.     

超交联微孔聚合物研究进展

超交联微孔聚合物是一类重要的多孔聚合物材料, 由于其具有高比表面积、合成条件温和、单体来源广泛等优点而成为研究的热点. 根据不同阶段合成方法的差异, 超交联聚合物主要由以下三种方法制备得到: (1)含官能团聚合物前体的后交联; (2)功能化小分子单体的一步法自缩聚; (3)通过外交联剂“编织”刚性的芳香族单体. 本文介绍了超交联聚合物的发展过程, 着重对三种合成超交联聚合物的方法、同时对微孔聚合物微观形貌的控制以及其在气体储存、分离、催化等方面的应用进行了总结. 最后提出了超交联聚合物的缺陷和所面临的挑战, 并对未来超交联微孔聚合物的发展前景进行了展望, 指明了超交联聚合物发展的新方向.     

Fabrication of triple-shelled hollow spheres with optical properties via RAFT polymerization

<正>The triple-shelled hollow spheres with optical properties were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization.After removal the core templates of the poly(styrene),the hollow silica spheres were obtained.The coating process of poly(methyl methacrylate)(PMMA) on the hollow silica spheres surface via surface RAFT polymerization was performed subsequently.The polymers coated on the hollow spheres surfaces were end-functionalized by trithiocarbonate,and they were used as RAFT agent to proceed the chain extension polymerization using Tb complex as monomer.The samples were characterized by FT-IR,SEM and luminescence spectroscopy respectively.The results indicated that the triple-shelled hollow spheres had been prepared successfully and the average diameter of the hollow core was about 1μm.     

塑料芯片毛细管电泳电化学检测系统及其性能评价

近年来,高分子芯片毛细管电泳技术发展迅速,以聚甲基丙烯酸甲酯(PMMA)为代表的塑料电泳芯片由于其低廉的制作成本与良好的电渗性能,已经成为芯片电泳技术发展的一个重要方向,电化学检测具有灵敏度高、选择性好和易于微型化等优点,因此在塑料芯片电泳领域中具有较好的应用前景。     

The Role of inclusion size in toughening of epoxy resins by spherical micelles

We report our finding of an optimal length scale for toughening of epoxies using spherical micelles formed by block copolymers. The amphiphilic diblock copolymer poly(hexylene oxide)‐poly(ethylene oxide) (PHO‐PEO) with 30 wt % PEO self‐assembled to form spherical micelles in a bisphenol A epoxy resin with a phenol novolac hardener. We systematically increased the size of the spherical micelles from 20–30 nm to 0.5–10 μm by swelling their PHO core using PHO homopolymer. Although all the blends were tougher than the unmodified epoxy, the largest enhancement of fracture resistance was measured in blends containing 0.1–1 μm spherical inclusions. This enhanced toughness was correlated with plastic deformation by shear banding in tensile test and greater roughness of the fracture surface. Smaller micelles neither induced plastic deformation nor contributed to surface roughness significantly whereas larger micelles acted as local defects resulting in early failure. These findings provide a framework in assessing the toughening effects of blended block copolymers on epoxy resins. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1125–1129, 2009     

Specific interactions in blends of poly(ethylene oxide) and poly(bisphenol A-co-epichlorohydrin): FTIR and thermal study

Blends of poly(ethylene oxide) (PEO) of high molecular weight with poly(bisphenol A-co-epichlorohydrin) (PBE) with high epoxy equivalent were studied spectroscopically, thermally and morphologically. As similar systems of low molecular weight, a single T_g was observed for all blends, indicating miscibility. A progressive decrease in the degree of crystallinity and in the size of the PEO spherulites as the PBE is added is also observed. Quantitative analysis from FTIR spectra provided determination of specific interactions between the constituents and their variation with PEO content. Simulations were performed utilising the spectra of the pure polymers to confirm that the observed changes in the experimental spectra of the blends were due to interaction between the polymers.     

Recovery stress and work output in hyperbranched poly(ethyleneimine)‐modified shape‐memory epoxy polymers

In this study a series of hyperbranched modified shape‐memory polymers were subjected to constrained shape recoveries in order to determine their potential use as thermomechanical actuators. Materials were synthesized from a diglycidyl ether of bisphenol A as base epoxy and a polyetheramine and a commercial hyperbranched poly(ethyleneimine) as crosslinker agents. Hyperbranched polymers within the structure of the shape‐memory epoxy polymers led to a more heterogeneous network that can substantially modify mechanical properties. Thermomechanical and mechanical properties were analyzed and discussed in terms of the content of hyperbranched polymer. Shape‐memory effect was analyzed under fully and partially constrained conditions. When shape recovery was carried out with fixed strain a recovery stress was obtained whereas when it was carried out with a constraining stress the material performs mechanical work. Tensile tests at Tg^E′ showed excellent values of stress and strain at break (up to 15 MPa and almost 60%, respectively). Constrained recovery performances revealed rapid recovery stress generation and unusually high recovery stresses (up to 7 MPa) and extremely high work densities (up to 750 kJ/m³). The network structure of shape‐memory polymers was found to be a key factor for actuator‐like applications. Results confirm that hyperbranched modified‐epoxy shape memory polymers are good candidates for actuator‐like shape‐memory applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1002–1013     

Highly sensitive detection of transient absorption in dye-doped ultrathin polymer films by the TiO(2)/K(+) composite optical waveguide method upon pulsed laser excitation

A composite optical waveguide (OWG) composed of a 10–18 nm thick titanium dioxide (TiO₂) film sputtered on a conventional K⁺-doped optical waveguide was first applied to detect transient absorption of organic dyes in ultrathin polymer films upon excitation with ns laser. The thickness of the TiO₂ film considerably affected the relative sensitivity of the composite OWG. The composite OWG with 10 nm thick TiO₂ gave much stronger transient absorption for 30–415 nm thick polymer films containing organic dyes than that with 18 nm TiO₂. Transient absorption of phthalocyanine and spiropyran in 20–135 nm thick polymer films was detected 3–20 times more sensitively by the composite OWG with 10 nm TiO₂ than the conventional K⁺-doped OWG which showed a 150-fold sensitivity as compared with the usual normal incidence method. The relative sensitivity of the composite waveguide was also affected by the thickness and refractive index of polymers.     

Thermal decomposition of polymer mixtures of PVC,PET and ABS containing brominated flame retardant: Formation of chlorinated and brominated organic compounds

The thermal decomposition of various mixtures of acrylonitrile butadiene styrene copolymer (ABS), ABS containing brominated epoxy resin flame retardant and Sb₂O₃, poly(ethylene terephthalate) (PET) and poly(vinyl chloride) (PVC) has been studied in order to clarify the reactions between the components of mixed polymers. More than 40 halogen-containing molecules have been identified among the pyrolysis products of mixed samples. Brominated and chlorinated aromatic esters were detected from the mixtures containing PET and halogen-containing polymers. A series of chlorinated, brominated and mixed chlorinated and brominated phenols and bisphenol A molecules have been identified among the pyrolysis products of polymer mixtures containing flame retarded ABS and PVC. It was established that the decomposition rate curves (DTG) of the mixtures were not simple superpositions of the individual components indicating interactions between the decomposition reactions of the polymer components. The maximal rate of thermal decomposition of both ABS and PET decreases significantly if the mixture contains brominated epoxy flame retardant and Sb₂O₃ synergist. The dehydrochlorination rate of PVC is enhanced in the presence of ABS or PET.     

苯乙炔封端的可交联含氟聚芳醚的合成及性能

从光电集成器件对于材料性能的需要出发 ,我们相继合成了一系列可溶性的含氟聚芳醚和聚芳醚酮[1～ 5] .为了满足器件的多层化制备过程以及使器件成型后具有优异的性能 ,本文在间三氟甲基苯取代的聚芳醚 (1 1 F- PAE)中引进可交联的苯乙炔端基 ,合成了可热交联的高含氟量聚芳醚 ,并对其性能进行了初步研究 .1　实验部分1 .1　试剂与仪器　 4-苯乙炔苯酚 (PEP)按文献 [6 ]方法制备 ;3 -氟甲基苯代对苯二酚 (3 F- PH)按文献[2 ]方法制备 ;十氟联苯 ,Aldrich公司 ,99%;无水碳酸钾 ,A.R.级 ,天津化学试剂厂 ;甲苯 ,A.R.级 ,北京化工厂 ;N-…     

NOVEL HYPERBRANCHED POLY（PHENYLENE OXIDE）S WITH PHENOLIC TERMINAL GROUPS： EFFECTS OF REACTION TIME AND CORE MOLECULES ON THE MOLECULAR WEIGHT AND POLYDISPERSITY

A novel hyperbranched poly（phenylene oxide） （HPPO） with phenolic terminal groups was prepared from 4-bromo-4＇,4＂-dihydroxytriphenylmethane as AB2 monomer in dimethylsulfoxide （DMSO） via a modified Ullmann reaction. The molecular weight and polydispersity （PD） of the resulting polymers increased with increasing reaction time. In the presence of core molecules （bisphenol A and 1,3,5-trihydroxybenzene）, which have the similar molecular backbones to the reactive monomer, the molecular weight could be controlled by varying the core-to-monomer ratio. Incorporation of a very small amount of core molecules could lead to a higher molecular weight as compared with that without the addition of core molecules. However, when the core content reached certain extent, the molecular weight would decrease with the further increase in the core content. A new similar behavior of control over the PD was also obtained. The resulting polymers were characterized by ^1H-NMR, ^13C-NMR, FT-IR, and GPC.