新型紫外线吸收剂1,4-二芳基-1,3-丁二炔类化合物的合成及其性能研究

本文以含有端基炔的芳硫醚为原料，碘苯二乙酯为氧化剂，氯化亚铜为催化剂，室温下反应30 min，合成了1，4-二（2-芳硫基苯基）-1，3-丁二炔化合物。通过¹HNMR、¹³CNMR等对其进行了结构表征，并研究了其光学性质，以及作为紫外线吸收剂在紫外光固化涂料中的应用。结果表明：该类化合物能够有效吸收270~360 nm的紫外光，且光降解程度小，并具有与树脂、单体相容性好、无气味等特点。同时，合成的目标化合物在光固化过程中不参与自由基体系的固化，且增强了涂料及固化涂层的光稳定性，有益于紫外光固化涂料的存储，是一类具有发展前景的紫外光吸收剂。     

紫外光固化聚氨酯丙烯酸树脂的研究进展

综述了紫外光固化聚氨酯丙烯酸酯树脂的研究,讨论了其合成方法、固化机理以及性能。     

电子束辐射固化环氧树脂的动态力学分析——树脂化学结构、分子量及其分布的影响

应用不同化学结构、分子量及其分布的环氧树脂进行了电子束辐射固化实验 ,对固化物进行了动态力学分析 ,研究了不同样品凝胶含量、内耗tanδ及动态模量的变化规律 .分析结果表明环氧树脂辐射反应活性与其化学结构有很大关系 ,酚醛型环氧树脂的辐射反应活性高 ,固化后高温模量及玻璃化温度较高 ,而脂环族环氧树脂反应活性小 .在低辐射剂量下 ,环氧树脂的固化度随分子量增大略有下降 ,但固化物的玻璃化温度随分子量增加而升高 .增大辐射剂量 ,树脂固化度的提高受分子量大小的影响很小 ,分子量较大样品的网络均匀程度有所提高 ,在较高反应程度下 ,玻璃化温度主要受固化度影响 .树脂固化程度也是决定其模量高低的主要因素 ,而在固化程度相近的情况下 ,分子量的影响作用很大 .在同样辐射剂量下 ,分子量分布宽的树脂固化反应程度高 ,但交联网络均匀性低 .     

乙二醇二缩水甘油醚的合成及作为阳离子型紫外光固化稀释剂性能研究

以三氟化硼乙醚络合物为催化剂,以氢氧化钠为成环反应的闭环剂,利用乙二醇和环氧氯丙烷为原料合成了乙二醇二缩水甘油醚.研究了催化剂三氟化硼乙醚络合物用量、环氧氯丙烷和乙二醇摩尔比、氢氧化钠和乙二醇摩尔比,以及成环反应温度这些因素对合成反应的影响.结果表明较好的合成反应条件是:三氟化硼乙醚络合物质量分数为0.40%,环氧氯丙烷和乙二醇较佳摩尔比为2.4:1,氢氧化钠和乙二醇较佳摩尔比为2.2:1,较佳的成环反应温度为30℃.同时,把乙二醇二缩水甘油醚作为稀释剂加入到环氧树脂E-51中,利用三芳基锍鎓六氟锑酸盐作为引发剂,制备了阳离子型紫外光固化涂料,其紫外光固化膜的拉伸强度为46.25MPa,杨氏模量为1487.26MPa,断裂伸长率为6.27%.     

紫外光固化脂环族环氧丙烯酸酯涂料的制备及性能

通过丙烯酸（AA）与脂环族环氧树脂的开环反应合成了可紫外光（UV）固化的脂环族环氧丙烯酸酯树脂（CEA）。采用红外光谱（FT-IR）对树脂结构进行了表征,研究了反应温度、反应时间对产率的影响。用活性稀释剂与CEA制备了涂料预聚物,用转板黏度计测定了预聚物的黏度,采用差示扫描量热（DSC）仪、综合热分析仪和铅笔硬度计对树脂固化膜进行了分析。结果表明：当丙烯酸与环氧基团摩尔比为1.03,120°C下反应25.8 h时,反应转化率可达96.58%。CEA固化膜的玻璃化转变温度为64°C,初始分解温度为314°C,活性稀释剂的加入增强了固化膜的耐热性,固化膜铅笔硬度可达6H。     

端噁唑啉聚醚对环氧树脂的固化与增韧作用的研究

用IR、DSC等分析方法研究了端2-噁唑啉聚环氧丙烷(活性聚醚)与环氧树脂的固化反应,对固化机理作了讨论。并考察了不同分子量活性聚醚对环氧树脂的增韧作用。结果表明,此活性聚醚对环氧树脂增韧效果明显,固化树脂综合性能较好。     

一种低分子量带有羧基的聚丙烯酸酯丙烯酸树脂的制备和性质

制备了一种紫外光固化预聚物——带有羧基的低分子量聚丙烯酸酯丙烯酸树脂(Polyacrylate acrylic resin, PAAR).其主链由丙烯酸烷基酯和丙烯酸进行共聚而得,当采用丙烯酸甲酯、丙烯酸乙酯和丙烯酸(摩尔比1:1:1)作为共聚单体,引发剂AIBN为1.5%,链转移剂十二硫醇为2.5%时,聚合得到的聚丙烯酸酯(Polyacrylate, PA)分子量在1100-1400之间,多分散性小于2,反应速率快,转化率高;由这种PA和甲基丙烯酸缩水甘油酯(GMA)进行酯化反应,制备得到最终产物聚丙烯酸酯丙烯酸树脂,酯化率可以达到80%以上,其光固化膜具有较好的涂膜硬度和柔韧性,光泽度饱满.     

水性紫外光固化树脂的研究进展

综述了近年来水性紫外光固化树脂及其涂料制备的最新研究进展.详细介绍了各类水性紫外光固化树脂的结构特点、制备方法及其在涂料中的应用情况,尤其对水性紫外光固化环氧树脂、聚氨酯树脂和超支化聚合物树脂等作了重点介绍,并展望了本领域的未来发展趋势.     

环氧树脂固化过程的红外光谱研究

通过对环氧树脂和顺丁烯二酸酐在加热固化过程中红外光谱演变情况的观察,阐明了树脂在不同固化阶段和不同固化温度所进行的各类反应和相应的结构变化。在固化过程中使树脂的分子量增大和形成交联结构的主要反应是酯化反应。Fisch等提出的醚化反应在红外光谱中没有得到证实。树脂在酯化反应中生成的顺丁烯二酸酯的结构受热的影响会产生顺、反异构化反应。反应的进程取决于固化温度。在180℃加热已固化的树脂将导致部分碳-碳双键和剩余环氧基的减少,同时产生新的羟基和羰基。     

聚正己基三苯乙炔基硅烷树脂的合成及其热稳定性能

以正己基三氯硅烷、镁条、溴乙烷和苯乙炔为原料,通过Grignard反应合成单体正己基三苯乙炔基硅烷（NTPES）,其结构经¹H NMR,¹³C NMR, ²⁹Si NMR和FT-IR表征,采用非等温差热扫描量热法（DSC）研究了其热固化行为。通过热聚合合成了聚正己基三苯乙炔基硅烷树脂（PNTPES）,运用热重分析（TG）技术研究了固化树脂的热稳定性。结果表明：树脂在氮气气氛中质量损失5%的温度高于445 ℃, 800 ℃残存率大于60%,具有较好的热稳定性。     

阴极电泳涂料用颜料分散树脂及颜料浆的研制

采用多异氰酸酯制备一种季铵化剂,该季铵化剂和环氧树脂反应制备含有季铵盐基团的阳离子颜料分散树脂及颜料浆。本文研究了TDI单体类型、环氧树脂分子量、IO封闭TDI摩尔比例对颜料分散树脂水溶性、分散性及颜料浆稳定性的影响,并对颜料分散树脂和颜料浆的性能进行测试,结果表明:该颜料分散树脂对颜料具有优异的分散效果;该颜料分散树脂和常见颜料分散研磨而成的颜料浆贮存稳定性、施工稳定性性能优异,该产品具有良好的市场应用前景。     

Rubber Seed Oil-Based UV-Curable Polyurethane Acrylate Resins for Digital Light Processing (DLP) 3D Printing

Novel UV-curable polyurethane acrylate (PUA) resins were developed from rubber seed oil (RSO). Firstly, hydroxylated rubber seed oil (HRSO) was prepared via an alcoholysis reaction of RSO with glycerol, and then HRSO was reacted with isophorone diisocyanate (IPDI) and hydroxyethyl acrylate (HEA) to produce the RSO-based PUA (RSO-PUA) oligomer. FT-IR and ¹H NMR spectra collectively revealed that the obtained RSO-PUA was successfully synthesized, and the calculated C=C functionality of oligomer was 2.27 per fatty acid. Subsequently, a series of UV-curable resins were prepared and their ultimate properties, as well as UV-curing kinetics, were investigated. Notably, the UV-cured materials with 40% trimethylolpropane triacrylate (TMPTA) displayed a tensile strength of 11.7 MPa, an adhesion of 2 grade, a pencil hardness of 3H, a flexibility of 2 mm, and a glass transition temperature up to 109.4 °C. Finally, the optimal resin was used for digital light processing (DLP) 3D printing. The critical exposure energy of RSO-PUA (15.20 mJ/cm²) was lower than a commercial resin. In general, this work offered a simple method to prepare woody plant oil-based high-performance PUA resins that could be applied in the 3D printing industry.     

High‐performance aromatic thermosetting resins with hydroxyl and ethynyl groups

A novel hydroxyl‐ethynyl‐arene (HEA) resin was synthesized via Aldol condensation and Sonogashira reaction. The structure of the obtained resin was confirmed by the techniques of mass spectroscopy (MS), gel permeation chromatography (GPC), proton nuclear magnetic resonance spectroscopy (¹H‐NMR), Fourier transform infrared spectroscopy, (FT‐IR) and elemental analysis (EA). Differential scanning calorimetry (DSC) results showed an exotherm at the temperature range of 187°C–245°C, attributable to crosslinking reaction of the acetylene groups. After thermal cure, the obtained cured resin possessed excellent thermal stability. Thermal gravimetric analysis (TGA) in nitrogen showed the Td₅ (temperature of 5% weight loss) was about 400°C, and the char yield in nitrogen was about 78% at 900°C. The laminate composite of HEA resin was prepared and its mechanical and thermal properties were determined. The usefulness of the HEA resin as matrix for ablative composite was evaluated. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and properties of UV-curable polysiloxane methacrylate obtained by one-step method

In this study, a UV-curable polysiloxane methacrylate (PSMA) was synthesized by a one-step method. The reaction was catalyzed by chloroplatinic acid between polymethylhydrosiloxane (PMHS) and hydroxyethyl methacrylate (HEMA), as proved by FTIR and ¹H-NMR. The preliminary results indicate that the obtained UV-cured PSMA film has very good thermal stability, excellent transparency and satisfactory tensile strength. Our work provides a simple but efficient way to prepare UV-curable PSMA, which may find potential applications in UV-curing optical fiber, metal and glass coating and other fields.     

Synthesis and characterization of UV-curable polydimethylsiloxane epoxy acrylate

UV-curable polydimethylsiloxane epoxy acrylate (PSEA) was synthesized by hydrosilylation of allyl glycidyl ether with hydrogen-containing polydimethylsiloxane to give polydimethylsiloxane-type epoxy resin which modified with acrylic acid. The curing speed and the double bond conversion in the UV cured film were influenced by the purity of PSEA with Fourier transform infrared spectroscopy (FT-IR) measurements. The influences of the synthetic process, such as, the reaction temperature, the concentration of reactants and the catalyst which determined the purity and activity of resins were discussed in detail. The structures of this resin were characterized by ¹H-NMR and FT-IR spectra. The molecular weight was checked by gel permeation chromatography, and M_n is 45,000. The properties of the cured film were also investigated by thermogravimetric analyzer, dynamical thermal mechanical analysis, and etc. For example, tensile strength (6.9 Mpa), elongation (20%), hardness (A; 18), water absorption (24 h; 2%), weight loss (40 min, 300 °C; 5%) and etc.     

超支化聚氨酯阻尼涂层的制备及性能

以甲苯-2,4-二异氰酸酯(TDI)和二乙醇胺(DEOA)为原料, 采用一步法合成了超支化聚氨酯, 并对其改性制备了光固化超支化聚氨酯(UV-HPU)和超支化杂化聚氨酯(HHPU)两种树脂. 用傅里叶红外光谱(FTIR)和核磁共振氢谱(1H NMR)表征了预期产物. 以其为预聚物制备阻尼涂层, 动态力学分析(DMA)研究表明, 这两种涂层都具有高阻尼因子(tanδ≥1.0)、宽阻尼温度范围(tanδ≥0.5, 大于50 ℃)和宽阻尼频率范围(20～160 Hz); 通过基本性能测试和热重分析(TGA)发现杂化涂层聚氨酯较光固化聚氨酯具有更好的机械性能和热稳定性能; 杂化涂层聚氨酯的FTIR分析可知杂化涂层中硅氧烷水解缩合, 提高了交联密度; 杂化材料的断面扫描电镜(SEM)分析表明, 硅氧烷的水解缩合并未形成大颗粒纳米粒子而是形成均相体系.     

含三氟甲基聚酰亚胺的合成与性能研究

通过在4,4′-二氨基二苯醚(4,4-′ODA)单体中引入三氟甲基合成了一种新型二胺单体2-三氟甲基-4,4′-二氨基二苯醚(3FODA),该单体具有良好的溶解性和高的反应活性,使用3FODA替代4,4′-二氨基二苯甲烷(MDA)制备了PMR热固性聚酰亚胺树脂.树脂溶液高浓度低粘度,具有室温下良好的储存稳定性;树脂具有很好的加工性能,成型后的模压件显示了优异的热性能和耐热氧化稳定性,玻璃化转变温度在336~379℃之间;此外树脂具有较好的电性能和较低的吸水率.     

稳定剂对COM燃料流动性的影响

ＣＯＭ(油煤混合燃料 )燃料是将煤粉分散在燃油中 ,加入稳定剂制得的一种流体燃料。由于使用方便、热值高、价格便宜。因此 ,作为廉价的石油替代品具有广阔的用途。ＣＯＭ燃料的质量指标主要有 :稳定性、流动性、碳含量的高低。前文已讨论了稳定剂结构对ＣＯＭ稳定性的影响[1] ,至于影响ＣＯＭ流动性的主要因素 ,至今文献报道的很少。中昭广、杉山浩等较详细地讨论了多支链高分子量非离子型表面活性剂对水煤浆 (ＣＷＳ)流动性的影响[2 ] 。他们的研究结果表明 :稳定剂的支链越多、分子量又较大时 ,ＣＷＳ的流动性就越好。本文以多元醇 -ＰＯ…     

Viscosity Properties for Aqueous Solution of Urethane Acrylate Cationomer

Abstract

Water-soluble and UV-curable urethane acrylate cationomer was synthesized incorporating N-methyldiethanol amine (MDEA) on the molecular backbone and its viscosity properties were examined with respect to shear rate, temperature, and weight fraction of resin. All shear rates showed shear rate independence within given fraction regions. The viscosity trends of urethane acrylate cationomer solutions followed the Arrhenius equation well. The logarithmic infinite viscosity and activation energy showed linear relationship with the fraction below the weight fraction of 0. 325. However, above the fraction of 0. 325, the deviation from linear relationship was observed. This was believed to be attributed to the intermolecular interactions among molecular chains. From the obtained linear correlation of the logarithmic infinite viscosity and activation energy with the fraction, rheological equation of state was proposed. The viscosities obtained from the equation of state successfully corresponded to the results of experiments.