高热稳定性和可逆交联性质的含新型偶氮发色团电光聚合物的研究

制备了两种新型的分别含有以三苯胺为电子给体的偶氮类发色团作为特征活性官能团和3-呋喃甲酸及受保护的马来酰亚胺的可交联型聚合物体系．通过研究表明利用该制备方法，发色团在聚合物中的含量得到了极大的提高，分别达到32．1％（NLO1_P1）和44．4％（NLO1_P2）．该聚合物体系以“DielsAlder”[4＋2]环加成反应作为其交联特征，具有高温非交联、低温交联的特点，其过程与以往的热交联型聚合物相反，可解决传统电光交联聚合物中存在的热交联对极化效率影响的问题并用热失重分析法（TGA）和差示扫描量热法（DSC）分析了这一过程．此外DA交联型聚合物，不需要引入额外的助交联剂，克服了传统热交联聚合物分离难的问题，最大程度的保证了材料的纯度．     

用于合成革面料的水性聚氨酯-丙烯酸酯树脂及其制备方法

本发明公开了一种用于合成革面料的水性聚氨酯-丙烯酸酯树脂及其制备方法,其特征是在聚氨酯分子主链上含有有机氟和有机硅元素,在聚氨酯分子侧链上含有可交联的双键基团,在聚氨酯侧链上含有亲水基团。其制备特征是以氟醚封端的硅氧烷二元醇为大分子多元醇将有机     

含有偶氮苯发色团的PMMA的研究进展

综述了近年来含有偶氮苯发色团的聚甲基丙烯酸甲酯(PMMA)的研究状况和技术进展,重点讨论了掺杂型偶氮PMMA和共聚型偶氮PMMA以及其在光电材料领域的主要应用。分析并展望了含偶氮苯发色团的PMMA的发展趋势及应用前景,指出了含偶氮苯光学活性基团的聚合物的研究方向将主要集中在开发具有较高玻璃化转变温度,适中的偶氮发色团含量以及较好的成膜性的功能高分子材料方面。     

利用FRET技术探究水性聚氨酯成膜过程中粒子间分子链相互扩散过程

以芘丁酸与缩水甘油为原料,合成了芘丁酸甘油单酯,作为二羟扩链剂,成功制备了含有荧光能量共振转移（ FRET）功能的荧光探针的水性聚氨酯。将含有荧光探针聚氨酯与常规水性聚氨酯混合成膜,采用稳态荧光光谱测试涂膜,计算荧光共振能量转移效率,追踪成膜过程中粒子间分子链扩散的过程。采用这种技术研究了水性聚氨酯成膜过程,研究发现：粒径、成膜温度、交联度对成膜过程粒子间分子链相互扩散有非常大的影响。     

环氧粉末涂料交联型流平剂的研究

一、前言目前国内环氧粉末涂料的流平剂,就丙烯酸酯类聚合物而言,是一种分子链上无活性官能团的线型高分子聚合物。即参与共聚的单体分子链上无交联性的活性基团存在,对环氧粉末涂料的成膜仅起流平作用,而无化学过程。     

一类崭新的聚合型色素的合成与应用

聚合型色素由于分子中带有可聚合基团,可通过与高分子单体的共聚反应将发色母体以高浓度结合于聚合物分子主链或侧链上,从而具有优异的耐迁移性、耐溶剂性、与高分子材料的良好相容性以及较高的生理安全性等,并已被成功地开发应用于合成材料着色和功能材料等领域。本文综述了这一类色素的合成及应用。     

一类崭新的取合型色素的合成与应用

聚合型色素由于分子中带有可聚合基因，可通过与高分子单体的共聚反应将发色母体以高浓度结合于聚合物分子主链或侧链上，从而具有优异的耐迁移性，耐溶剂性，与高分子材料的良好相容性以及较高的生理安全性等，并已被成功地开发应用于合成材料着色和功能材料等领域，本文综述了这一类色素的合成及应用。     

苯基生色团修饰壳聚糖甲酸溶液中手性研究

在甲基磺酸体系中,分别将苯甲酰氯、对氯苯甲酰氯与壳聚糖反应,制备了具有发色团的苯甲酰化壳聚糖和对氯苯甲酰化壳聚糖。紫外光谱表征表明产物具有目标产物的结构特征。苯甲酰化壳聚糖、对氯苯甲酰化壳聚糖分别在254 nm和258 nm处具有苯基特征吸收峰。温度25℃,在质量浓度为250 mg/L时,苯甲酰化壳聚糖和对氯苯甲酰化壳聚糖甲酸溶液的圆二色谱信号均出现以苯基相应紫外吸收最大波长为中心的耦合裂峰（一个正峰和一个负峰）,表明发色团在壳聚糖螺旋链有序规则排列,壳聚糖分子链为左旋构象。对氯苯甲酰基发色团更适合测量甲酸溶液中壳聚糖构象特性。苯甲酰化壳聚糖和对氯苯甲酰化壳聚糖分子链构象受温度影响。     

离子交联聚合物──一类新型塑料及热塑性橡胶

离子交联聚合物──一类新型塑料及热塑性橡胶潘少波，谢洪泉（湖北工学院化学工程系，４３００６４）ｌ引言离子交联聚合物，简称为离聚体，是一类既有重要科学意义又有明显商业价值的聚合物。所谓离子交联聚合物就是分子链上连接有一定量无机盐基的聚合物。一般定义为含...     

空间稳定的硅氧烷改性丙烯酸酯聚合物乳液的制备研究

以分子链一端为巯基的聚乙烯醇（PVA-SH）为保护胶体，合成了空间稳定的硅氧烷改性丙烯酸酯聚合物乳液。在微碱性乳液聚合条件下，成功制备出异丙氧基硅烷含量高达11．2％（质量分数）的硅丙聚合物。经傅里叶变换红外光谱测定证明，在种子乳液聚合阶段，PVA-SH与MMA单体发生了接枝反应，形成具有PVA-S-PMMA结构的线型两亲接枝聚合物。TEM观察显示，所得到的乳胶粒大小均匀并且PVA-SH对其包覆均匀完整。凝胶渗透色谱（GPC）的测试结果表明，PVA-SH和（或）PVA-S-PMMA稳定的硅氧烷改性丙烯酸酯聚合物的数均相对分子质量（Mn）可以控制在60000-70000之间。在水解性能十分稳定的异丙氧基硅烷改性丙烯酸酯聚合物乳液的成膜过程中，可以通过调节pH值到微酸性，催化硅氧烷基团的水解反应，提高聚合物膜的交联速率和密度。PVA-SH稳定的异丙氧基硅烷改性P（MMA-BA）共聚物乳液能够经受24000r／min（约62m／s）的高速剪切作用而保持粒径的稳定性。这种聚合物乳液能获得性能良好的涂膜，是潜在的新型建筑涂料的成膜物质。     

Synthesis and electro‐optical properties of novel Y‐type polyurethanes containing dioxynitrostilbene

3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene (2) was prepared by the reaction of 2‐iodoethanol with 3,4‐dihydroxy‐4′‐nitrostilbene. Diol 2 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate and 1,6‐hexamethylenediisocyanate to yield novel Y‐type polyurethanes 3–5 containing dioxynitrostilbene as a non‐linear optical (NLO)‐chromophore. Polymers 3–5 were soluble in common organic solvents, such as acetone and DMF. These polymers showed thermal stability up to 280 °C in TGA thermograms with T_g values in the range of 100–143 °C in DSC thermograms. The approximate lengths of aligned NLO‐chromophores of the polymers estimated from AFM images were around 2 nm. The SHG coefficients (d₃₃) of poled polymer films were around 4.5 × 10^?8 esu. Poled polymer films had improved temporal and long‐term thermal stability owing to the hydrogen bonding of urethane linkage and the main‐chain character of the polymer structure, which are acceptable for NLO device applications. Copyright © 2004 Society of Chemical Industry     

Thermally stable interpenetrating polymer networks for second‐order nonlinear optical materials

We report several kinds of interpenetrating polymer networks (IPNs) with nonlinear optical (NLO) properties. DMA spectra show that the two components of the IPNs have good compatibility with each other. The NLO materials have good optical transparency. The thermal stability of alignment was improved and the poled order remained very high. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 7–9, 1999     

Novel second-order nonlinear optical main-chain polyurethanes: Adjustable subtle structure, improved thermal stability and enhanced nonlinear optical property

A series of main-chain polyurethanes containing sulfonyl-based NLO chromophores in the polymer backbone were prepared, the subtle structure of the chromophore moieties could be easily modified to adjust the property of the resultant polymers. The polymers exhibit improved stability of their enhanced NLO effects, besides their good processability, thermal stability, and relatively good transparency. The tested NLO properties of the polymers demonstrate that there is a suitable isolation group present for the sulfonyl-based chromophore to boost its microscopic β value to possibly higher macroscopic NLO property efficiently, and BOP moieties are the best choice for this series of polymers to achieve optimized properties.     

Molecular design,synthesis, and electro‐optic properties of novel Y‐type polyesters with high thermal stability of second harmonic generation

3,4‐Di‐(2′‐hydroxyethoxy)‐4′‐nitrostilbene was prepared and condensed with terephthaloyl chloride, adipoyl chloride, and sebacoyl chloride to yield novel Y‐type polyesters containing NLO‐chromophore dioxynitrostilbenyl groups, which constituted parts of the polymer backbone. Polymers were found soluble in common organic solvents such as acetone and N,N‐dimethylformamide. They showed thermal stability up to 300 °C in thermogravimetric analysis with glass‐transition temperatures obtained from differential scanning calorimetry in the range 110–152 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at a 1064 cm^?1 fundamental wavelength were around 3.51 × 10^?8 esu. The dipole alignment exhibited high thermal stability even at 10 °C higher than the glass‐transition temperature, and there was no SHG decay below 120 °C for one of these polymers due to the partial main‐chain character of polymer structure, which was acceptable for NLO device applications. Copyright © 2005 Society of Chemical Industry     

Thermally stable nonlinear optical polyimide functionalized by N,N‐diallylamino‐substituted chromophore

Thermally stable nonlinear optical (NLO) polyimide prepolymers with different chromophore‐loading levels were prepared through an addition reaction of bismaleimide 1 and N,N‐diallylamino‐substituted chromophore 2. The prepolymers were used to prepare NLO polyimide in a simultaneously poling/curing process. These prepolymers exhibited excellent film‐forming quality and good solubility in low boiling‐point solvents. Kinetic parameters (n, ln A,Ea) of their solidification reaction were determined by the dynamic method. Thermal and NLO properties of the cured polyimides with various chromophore‐loading levels were studied. With increase of the chromophore‐loading level, the glass transition temperature (T_g) and the thermal stability of the polyimides decreased, but the second‐order nonlinearity of the poled film increased. The largest d₃₃ coefficient obtained was 76.2 pm/V at 1064 nm. The SHG signal was rather stable up to 120°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2939–2947, 2000     

Nonlinear optical materials by electrospinning technique

The possibility of using electrospinning to deposit, and simultaneously electrically pole, polymeric mats containing nonlinear optical (NLO) molecules is studied. Disperse Red 1 (DR1) chromophore dispersed into polymethyl methacrylate (PMMA) fibers is chosen as test system. Aligned fibers of DR1/PMMA are deposited by means of the rotating collector electrospinning technique. The processing parameters are optimized to obtain an oriented texture of fibers and the NLO activity is characterized by means of second harmonic generation measurements. Comparison with spin coating and corona poling samples of the same material is discussed. The results point toward a low efficiency of chromophore orientation for the electrospun samples in comparison to the poled ones. An improvement in the electrospinning apparatus is proposed to enhance the chromophore orientation in the polymeric fibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40913.     

Novel, side-on, PVK-based nonlinear optical polymers: Synthesis and NLO properties

A novel, poly(vinylcarbazole)-based nonlinear optical polymer (side-on type), in which the chromophore was attached to the polymer backbone at the centre of the D-π-A bridge, was synthesized conveniently via the post-Knoevenagel condensation reaction. The structure of chromophore was further modified by the introduction of an isolation spacer (carbazole group) to improve poling efficiency. The ensuing polymer displayed good solubility and high thermal stability and its poled film exhibited a relatively large d₃₃ value of ≤56.0 pm/V.     

Synthesis of novel polyurethanes containing dioxybenzylidenecyanoacetate,as non‐linear optical chromophores and their properties

Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate (3) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate (2). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4, 5 and 6 containing the non‐linear optical (NLO) chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4–6 were soluble in common organic solvents such as acetone and DMF. T_g values of the polymers obtained from DSC thermograms were in the range 80–102 °C. Polymers 4–6 showed thermal stability up to 300 °C in TGA thermograms, and electro‐optic coefficients (r₃₃) of the poled polymer films were in the range 10–12 pm V^?1 at 633 nm, which are acceptable for NLO device applications. © 2002 Society of Chemical Industry     

New second-order nonlinear optical polymers containing the same isolation groups: Optimized syntheses and nonlinear optical properties

Based on control experiments, a new series of second-order nonlinear optical polymers with fluorene moieties as isolation spacers were successfully prepared. In the polymers, the chromophore moieties were embedded into the polymer backbone with one position at the donor side, and another point in the π bridge. Different acceptors were used to construct the push-pull structure of chromophore moieties, including nitro groups, sulfonyl groups, 3-phenyl-5-isoxazolone, 1,3-diethylthiobarbituric acid and TCF groups. The tested NLO properties of the polymers demonstrated that the isolation groups with big size do not always benefit the resultant NLO effect. Also, for different acceptors, there should be different suitable isolation groups to balance the good and bad effects caused by the introduced isolation spacers.     

Preparation and electro‐optic properties of novel Y‐type polyimides with highly enhanced thermal stability of second harmonic generation

BACKGROUND: In the development of nonlinear optical (NLO) polymers for electro‐optic device applications, stabilization of electrically induced dipole alignment is one of the important criteria. Polyimides for NLO applications have attracted attention because of their high T_g values and high thermal stability. In this work we designed and synthesized a new type of NLO polyimide, in which the pendant NLO chromophores are parts of the polymer backbone. These mid‐type NLO polymers are expected to have the merits of both main‐chain and side‐chain NLO polymers: stabilization of dipole alignment and good solubility. RESULTS: 3,4‐Bis‐(3,4‐dicarboxyphenylcarboxyethoxy)‐4′‐nitrostilbene dianhydride was prepared and reacted with the corresponding aromatic diamine to yield unprecedented Y‐type polyimides containing 3,4‐dioxynitrostilbenyl groups as NLO chromophores, which constituted parts of the polymer backbones. The resulting polyimides are soluble in polar solvents such as dimethylformamide and dimethylsulfoxide. These polymers showed a thermal stability up to 320 °C in thermogravimetric thermograms with T_g values obtained from differential scanning calorimetry thermograms in the range 143–164 °C. The second harmonic generation (SHG) coefficients (d₃₃) of poled polymer films at the 1064 nm^?1 fundamental wavelength were around 9.45 × 10^?18 C. CONCLUSION: The dipole alignment exhibited exceptionally high thermal stability even at 30 °C higher than T_g. There was no SHG decay below 180–190 °C because of the partial main‐chain character of the polymer structure, which is acceptable for NLO device applications. Copyright © 2007 Society of Chemical Industry