聚氨酯/对乙烯基苯甲酸铕光致发光材料的制备及性能

以对乙烯基苯甲酸为配体,稀土铕离子为中心离子,制备出带有活性官能团(C=C)的对乙烯基苯甲酸铕配合物。将该配合物引入到聚氨酯(PUR)体系中,合成了PUR/对乙烯基苯甲酸铕(PUR-Eu)光致发光材料。PUREu材料为无定形态,随着对乙烯基苯甲酸铕含量的增加,PUR-Eu材料的透光率逐渐降低,当对乙烯基苯甲酸铕质量分数为3%时,PUR-Eu材料的透光率(46.0%)与纯PUR的透光率(90.1%)相比降低了44.1%。对乙烯基苯甲酸铕的含量对PUR-Eu材料的热稳定性几乎没有影响,PUR-Eu材料的热分解温度在230℃以上,具有较好的热稳定性。PUR-Eu的荧光强度随着对乙烯基苯甲酸铕含量的增加而逐渐增大,在对乙烯基苯甲酸铕质量分数为5%以内,PUR-Eu材料没有出现荧光淬灭现象。     

光致发光性透明高分子材料的制备

在合成聚氨酯丙烯酸酯大分子单体的基础上,通过原位聚合法制备出一类稀土配合物掺杂的透明性高分子材料,表征了稀土配合物在基体中分散情况以及材料的动态力学性能和荧光性能。结果表明：当稀土配合物质量分数为1．4％时,材料具有优异的综合性能,其拉伸强度达15．85MPa,透光率达91．2％;且该材料在波长为246nm的激发光下,在363nm出现最大荧光发射峰,荧光强度为454,有望应用在光致发光性透明高分子材料领域。     

光致发光PVC膜的制备及研究

将稀土铕的氯化物与邻菲罗啉(Phen)、乙酰水杨酸(aspirin)合成的光致发光稀土铕的配合物,掺杂到PVC的四氢呋喃(THF)溶液中,利用流延法制得一系列表观无色透明的光致发光PVC膜。用红外光谱、透射电镜、紫外光谱、荧光光谱及热分析对一系列光致发光PVC膜进行了表征和性能测试。实验结果表明:当稀土铕配合物在PVC膜中的含量超过25%时,该配合物在PVC膜中会产生局部聚集,从而引起光致发光PVC膜的表观透明性下降;光致发光PVC膜的紫外吸收和荧光强度随着稀土铕配合物含量的增加而增强;稀土铕配合物对PVC膜的热性能有很好的改善作用。用本实验方法制备的荧光PVC膜,稀土配合物在PVC中分散均匀,粒径均一,膜的透明性好。     

钆掺杂铕聚氨酯荧光剂的制备与发光性能研究

以噻吩甲酰三氟丙酮（HTTA）为第一配体,邻菲啰啉（phen）为协同配体,二羟甲基丙酸（DMPA）为功能性配体,合成了含羟基的钆掺杂铕荧光配合物功能性单体,在此基础上,通过与二异氰酸酯、低聚物二元醇等的加聚反应,制备了钆掺杂铕聚氨酯荧光剂。通过红外、元素分析、EDTA滴定分析、紫外、荧光光谱分析,对功能性单体和聚氨酯荧光剂的结构及性能进行了表征及测试。结果表明：钆掺杂铕荧光配合物功能性单体及由此合成的聚氨酯稀土铕高分子荧光剂都表现出了较好的共发荧光效应,荧光剂与聚氨酯具有良好的相容性,有望作为油墨连结料应用在荧光防伪油墨领域。     

稀土高分子配合物发光材料的合成

发光稀土高分子配合物是一类很有价值的功能材料,本文就其3种合成方法进行评述。以稀土离子与含配位基团的聚合物进行反应,难以获得发光强度高的高分子配合物;使稀土离子与高分子配体和小分子配体同时作用,可以得到荧光强度比较理想的产物,但反应难以定量控制;以小分子稀土配合物单体进行聚合反应,也可获得荧光强度较高的高分子配合物,但聚合反应的空间位阻较大。并针对方法3提出了改进的思路。     

稀土配合物及其共聚物的合成与性能研究

以丙烯酸(HAA)、甲基丙烯酸(HMA)及1,10-邻菲罗啉(Phen)为配体与氧化铕(Eu2O3)反应得到二元配合物Eu(AA)3、Eu(MA)3和三元配合物Eu(AA)3Phen、Eu(MA)3Phen。将生成的配合物与HMA和甲基丙烯酸甲酯(MMA)共聚,得到一系列三元共聚物。通过元素分析、红外光谱、荧光光谱和热分析对配合物进行了分析与表征,发现配合物具有良好的荧光强度和热稳定性。三元配合物的荧光强度相对于二元配合物有显著提高。共聚物可发射Eu3+的特征荧光,荧光强度随配合物含量的增加而增加,且未发生浓度猝灭现象。三元配合物在反应单体MMA和HMA中的溶解度低于二元配合物,从而使在最大溶解度下二元配合物与反应单体生成共聚物的荧光强度高于相应的三元配合物与反应单体生成的共聚物。     

苯丙烯酸邻菲罗啉铕钇配合物的合成及荧光特性

在乙醇介质中，合成了标题化合物，测定了其组成，红外光谱及荧光光谱，结果表明，羧酸的羟基氧及邻菲罗啉中的氮原子均与稀土离子配位，铕钇配合物的荧光强度值高于铕配合物。     

键合型铕聚氨酯荧光涂料的合成和发光性能的研究

以铕离子为发光中心,噻吩甲酰三氟丙酮、二羟甲基丙酸、邻菲罗啉为配体合成了分子中含羟基官能团的稀土铕配合物,并将其以键合的方式引入到水性聚氨酯高分子链中,制备出一系列铕含量不同的聚氨酯高分子.通过红外光谱、热重分析、荧光光谱等对样品进行了表征.结果表明:不同铕含量的聚氨酯高分子的吸收特征由于Eu3+含量低的缘故而表现为聚...     

四元羧酸稀土配合物的合成与表征

在水溶液中合成了铕和铽的四元羧酸稀土配合物。通过红外光谱,元素分析,热分析及荧光光谱,对其组成及其荧光性能进行了表征。结果表明两种稀土配合物具有较好的荧光性质。     

2,3,5-吡啶三酸与稀土铕配合物的合成及发光性质

采用水作溶剂,用2,3,5-吡啶三酸与稀土铕的氯化物反应合成了一种配合物,通过EDTA络合滴定分析,确定了配合物中铕离子的含量;并对配合物进行了熔点、红外光谱测定,测试了固态铕配合物的荧光激发和发射光谱。结果表明,该配合物具有良好的光致发光性质。     

Photoluminescence emission of a stable and well‐dispersed unsaturated polyester‐co‐rare‐earth complex

A series of unsaturated polyester (UPR)‐co‐rare‐earth complex (REX) photoluminescence materials with red and green luminescence were fabricated. REXs with double bonds, including complex of europium (Eu³⁺) (methacrylic acid)₃ and 1,10‐phenanthroline (Phen) [Eu(MAA)₃Phen], and complex of terbium (Tb³⁺)(methacrylic acid)₃ and Phen [Tb(MAA)₃Phen], and UPR acted as functional monomers and the polymer matrix, respectively. Fourier transform infrared and UV absorption spectroscopy confirmed the chemical structure of the resulting UPR‐co‐REX according to the free‐radical polymerization mechanism. The study of fluorescence distribution by means of laser scanning confocal microscopy indicated that the REX materials were uniformly dispersed in the UPR matrix. The effects of the type and dosage of REX on the fluorescence intensity and stability were examined via fluorescence spectrometry. We found that the optical/physical properties of the REX were improved by UPR molecular skeleton structures. The fluorescence intensity increased with increasing use of the REX and reached a maximum value when the REX content was 12 wt %. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45253.     

具有荧光响应的多元可聚合稀土配合物的研制

以氧化铕、邻菲啰啉、苯甲酸、丙烯腈为原料,合成了一种具有聚合反应活性的四元铕配合物。研究了氯化铕、邻菲啰啉、丙烯腈物质的量比对产品结构、发光性能、热稳定性以及产率的影响。采用红外光谱、荧光光谱、热失重对产物结构、发光性能、热稳定性进行了表征。结果表明:该铕配合物具有可聚合的能力以及良好的热稳定性。在波长为342nm紫外光激发下,能发射出强烈的,来自于Eu3+离子的特征红光,强度最大的发射峰在615nm。     

New poly (urethane-methacrylate)s obtained by adjusting the structure of the polyols moieties: synthesis, transparent, thermal and mechanical properties

A series of novel cross-linked poly (urethane-methacrylate)s (PUAs) were synthesized in a three-step process: Four kinds of low number average molecular weight aromatic polyesters (PEs) with terminal hydroxyl groups were obtained by phthalic anhydride (PA) reacted with 1,2-propanediol (PDO), 1,4-butanediol (BDO), 1,6-hexanediol (HDO), and diethylene glycol (DEG), respectively. Then, a series of urethane-methacrylate macromonomers(UMAs), which have double bonds at the end of the chain, were prepared from isophorone diisocyanate (IPDI), the PEs obtained in first step, poly(ethylene glycol) 600 (PEG600) and ß-hydroxyethyl methacrylate(HEMA). Dibutytin dilaurate (DBTL) was used as catalyst. Finally, a series of thermosetting PUAs were synthesized by the polymerization of novel functional UMAs using 2,2'-azobis(isobutyronitrile) (AIBN) as catalyst. The compositions of the PEs and UMAs were determined by ¹H-NMR and fourier transform infrared (FT-IR). The properties of PUAs were measured by dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), wide-angle X-ray diffraction (WAXD), water uptake and optical properties testing, and mechanical performance measurements. The results revealed that the mechanical and degradation properties of PUAs were influenced by the kinds of PE or polyether polyols in the PUAs remarkably. The obtained PUAs present the good thermal and mechanical properties, low water uptake (below 1%) and high transparence (above 90%). The diversity of properties suggests that these PUAs can be used in a wide range of excellent optical polymer applications.     

UV固化生物基改性柔性环氧丙烯酸酯的合成及性能

以甲基丙烯酸羟乙酯、衣康酸为原料，所合成的衣康酸甲基丙烯酸羟乙酯（HEMAIA）与环氧大豆油进行开环反应，合成含有侧甲基和多个碳碳双键的ESO-HEMAIA。研究不同反应条件对ESO-HEMAIA合成的影响，用红外光谱（FTIR）和核磁共振氢谱（1H NMR）对所合成的产物进行表征分析，结果表明，ESO-HEMAIA的碳碳双键含量最高可达5.2。同时，对纯ESO-HEMAIA与AESO的涂膜性能进行研究，结果表明：固化后的纯ESO-HEMAIA与AESO有着相似的性能，而纯ESO-HEMAIA比AESO涂膜有着更好的硬度、热稳定性，吸水率降至1.01%。     

Semi-IPNs based on Polyacrylamide and Poly(itaconic acid)

Summary Semi-IPNs based on polyacrylamide (PAAm) and poly(itaconic acid) (PIA) were prepared by two different techniques, polymerizing itaconic acid in the presence of polyacrylamide gel (Samples I) and by makiug the polyacrylamide gel in the presence of poly(itaconic acid) (Samples 11), with different PAAm/PIA ratios. The swelling behavior of the semi-IPNs reveals that gels with low PIA content swell more, while those with high PIA content swell less than a pure PAAm gel, probably due to the formation of intermacromolecular gel-polymer complexes on the basis of hydrogen bonds.The results of thermal analysis indicate an improved therinal stability of the hydrogels and complexes compared with PIA and PAAm.     

聚(丁二酸丁二酯-co-衣康酸丁二酯)的合成

用含不饱和双键基团的衣康酸作共聚单体,采用直接熔融酯化聚合法制备可生物降解的聚(丁二酸丁二酯-co-衣康酸丁二酯)。共聚物的相对分子质量及其分布、溶解性能、热性能及结晶性能均受分子链中衣康酸含量的影响,当衣康酸摩尔分数达50%时,共聚物成为不溶/熔的交联弹性体。     

铕高分子配合物荧光强度与铕离子浓度的关系

稀土离子发光材料性能优良,既可电致发光又可光致发光,广泛应用于生物分析化学,激光材料,防伪商标等领域。本文以邻菲哕啉为小分子配体,聚丙烯酸-甲基丙烯酸甲酯为高分子配体,制备铕的高分子荧光配合物,研究了配合物中荧光强度与铕离子浓度的关系,发现Eu^3＋的浓度在1．25×10^-5mol／L和2．0×10^-4mol／L之间配合物的荧光强度与Eu^3＋的浓度呈线性关系,其加标回收率为98．6—101．3％,在该浓度范围内可对配合物中Eu^3＋浓度进行定量测定。     

ATRP法合成大分子单体及其在微球制备中的应用

以α-溴代丙酸乙酯(EPN-Br)为引发剂,氯化亚铜(CuCl)与N,N,N′,N″,N″-五甲基二亚乙基三胺(PMDETA)组成的混合体系为催化剂,使甲基丙烯酸叔丁酯(tBMA)进行原子转移自由基聚合(ATRP),得到了端基为溴原子的聚甲基丙烯酸叔丁酯大分子中间体PtBMA-Br。使其末端的Br与甲基丙烯酸发生亲核取代反应,得到甲基丙烯酸封端的大分子单体。FTIR和1H-NMR的分析表明大分子单体结构明确,双键导入率高;再用该大分子单体与苯乙烯分散共聚制得形态规整的高分子微球。     

Preparation and characterization of a series of novel EuIII-complex-polyurethane acrylate materials based on mixed 6-hydroxy-1-naphthoate and 1,10-phenanthroline ligands

Hydroxyl groups in the coordination complex {[Eu( L )₃(phen)]·H₂O}₂ ( L = 6-hydroxy-1-naphthoate and phen = 1,10-phenanthroline) were used to react with  NCO functional groups of isophorone diisocyanate in the presence of dibutyltin dilaurate. A series of new luminescent Eu^III-complex-polyurethane acrylate materials, poly(Eu^III-complex-polyurethane methacrylate (PUA complex)), were prepared through in situ polymerization of polyurethane acrylate macromonomers and the resulting material was characterized by X-ray diffraction, IR spectra, thermogravimetry analysis, dynamic mechanical analysis, and fluorescence spectroscopy. The result indicates that both Eu^III complex and PUA complex can emit characteristic fluorescence of Eu^III ion. Moreover, the emission intensity was enhanced under the same experiment condition when the content of Eu^III complex in the PUA complex was increased. In addition, we have not found the fluorescence quenching in this work even the content of Eu^III complex was increased to 5 wt %. Such rare-earth complex-polyurethane acrylate hybrid materials are suitable for the photoluminescent applications. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Design of functional macromonomer derivatives of poly(isobutylene‐co‐isoprene)

The development of new peroxide‐curable poly(isobutylene‐co‐isoprene) (IIR) elastomers is described, wherein pendant oligomerizable C=C groups are introduced in combination with a range of serviceable functional groups. Ring‐opening of itaconic anhydride with functional alcohols or amines, followed by esterification of the resulting acids with brominated IIR, yield macromonomers that crosslink efficiently under the action of dicumyl peroxide alone. More importantly, the additional graft functionality improves the physical and chemical properties of the resulting thermosets. The introduction of fluorocarbon functionality is shown to lower surface energy and improve the material's extrusion characteristics, and trialkoxysilane functionality is used to improve filler dispersion within silica‐reinforced composites. This strategy is extended to prepare thermosets bearing polymer‐bound phenolic antioxidant. Details of macromonomer production are followed by demonstrations of their utility as engineering materials.